CA2174756A1 - Addition polymers derived from norbornene-functional monomers and process therefor - Google Patents

Abstract

Addition polymers derived from norbornene-functional monomers are terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes and at least one of said carbon atoms has two hydrogen atoms attached thereto. The addition polymers of this invention are prepared from a single or multicomponent catalyst system including a Group VIII metal ion source. The catalyst systems are unique in that they catalyze the insertion of the chain transfer agent exclusively at a terminal end of the polymer chain.

Description

~ WO 95114048 2 1 7 4 7 5 6 PCrllJSg4113166 ADDITION POLYMERS DERIVED FROM NORBORNENE FUNCTIONAL
MONOMERS AND PROCESS THEREFOR
BACKGROUND OF THE INVENTION
The well-known advantages of a polymer having chains containing directly linked polycyclic repeating units free of have driven those skilled in the art to search for a 1~ ' ' "addition polymer" of one or more multi-ringed I ~ lly, ' cycloolefm monomers such as nUllJUll~.C, bicyclo[2.2.1]hept-2-ene or "NB" for brevity, and substituted tl~bu~' thereof, such as ~LIlylhl~,~l~lull)u~ , or d.,~,yh.ulbul~ " and Luly those monomers of NB having at least one substituent in the 5-(and/or 6-) positions. The foregoing monomers are collectively referred to ' herein as "Iwlllùll..,..~,-type" or "llulbul..~.c functional" o} "NB-type" or "NB-functional" monomers, for w.... , lI;iW~,..i~;llg that, just as in NB, or 15 substituted NB, each NB-type polymer is l l., h-,'` ';' 'I by containing a repeating unit resulting from an addition pul~ ' derivative of bicyclo[2.2. I]hept-2-ene. A first NB-type or NB-functional monomer may be pul.~..._.;~ by WUI~' pOl~ .;~liu.. to form (i) an addition I , l~ , or, (ii) with a second NB-type or NB-functional monomer, either one (first or second) of 20 which is present in a major molar proportion relative to the other, to form an addition NB-type copolymer; or, (iii) with a second monomer which is not an NB-type monomer, present in a minor molar proportion relative to the first, to form an addition copolymer with plural repeating units of at least one NB-type or NB-f~mctional monomer.
rdlJ .. , l.. ~. .. .- or "poly(bicyclo[2.2. 1]hept-2-ene)" or polyNB for brevity, was originally produced a long time ago (U.S. Patent No. 2,721,1~9).
However this original material was found to contain two types of polymers, one brittle, the other ~ .r.. ~ !~ and 'drawable'. The brittle polymer was laterfound to be a low molecular weight ('mol wt') saturated polymer which was 30 termed an rddition type polymer; and, the l: , .r....- - ~ Ir polymer was shown Wo 95114048 PCI/US94/13166 ~
21 7~756 2 to be formed by ring opening metathesis polymerization ('ROhlP'). A ROMP
polymer has a different structure compared with that of the addition polymer in that (i) the ROMP polymer of one or more NB-type monomers, contains a repeat unit with one less cyclic unit than did the starting monomer, and, (ii) these are S linked together in an unsaturated backbone ~ of a RO~ polymer and is shown below.
~ ROMP ~n It will now be evident that, despite being formed from the same monomer, an addition-polymerized polyNB is clearly ' ~ over a ROM3' polymer. Because of the different (addition) mr~r ~ -irm, the repeating 0 unit of the former has no backbone C=C as shown below:
~3 ADDITIO ' ~ ~ ]
The difference in structures of ROMP and addition polymers of NB-functional monomers is evidenced in their properties, e.g., thermal properties.
The addition type polymer of NB has a high Tg of about 370DC. The ' ROMP polymer of NB exhibits a T~ of about 35DC, and exhibits 15 poor thermal stability at high t~ LUl ~ above 200DC because of its high degree of C=C ullar Lulr~iull.
Some time later, reaction conditions were optimized so as to enable one to choose, and selectively make, either the low mol wt addition polymer, or the ~ WO 9~/14048 2 1 7 4 7 5 6 PCT/US94113166 ROMP polymer. In U.S. Patent No. 3,330,815, the disclosure taught that only the addition polymer was ~ ' ' with TiCI~/Bt2AlCI or Pd(C6H5CN)2CI2, under particular conditions, except tbat the polymers produced were only those in the mol wt range from 500 to 750 in which range they were too brittle for any S practjcal arFlir .tir,n Addition polymers of norbornene have been shown to be produced with ~LilUUllV~.CII~, type" catalysts such as those taught by Kaminsky et al, and others, all well known to those skilled in the art. These polymers have been found to bea highly crystalline form of a "llulbo~ll.,l,c-~ddition polymer", that is, an addition 10 polymer of a NB-functional monomer, which is totally insoluble, amd reportedly does not melt until it J~ ...,1,..~-~ at ~600C (under vacuum to avoid oxidation).
Itisthereforeulll~iu~,c.~lc(W.Kaminskyetal,J.Mol.Cat.74,(1992), 109;
W. Kaminsky et. al. ~' ' . ' Chem, Macromol. Symp., ~_, (1991) 83; and W. Kaminsky, Shokubai, 33, (1991) 536.). An added ., ~v 15 cll~ ci~,l;aL;C of the L;l ~UIIOC~I~G catalyst system is that it catalyzes the Copolyl.._liL,Il;ull of ethylene and norbornene. In such copolymers, the amount of NB i~,ul~JU~ ~,d into the ethylene/NB copolymer can be varied from high to low (W. Kaminsky et. al. Polym. Bull., 1993, 31, 175).
The polymer formed with a LilUUll~Ccllc catalyst can incorporate 20 ethylene (or compounds containing ethylenic l at a terminal end thereof) in its backbone, randomly, whether in runs of a lllul~ lh,iLy of repeating units, or even a single unit. It should also be noted that tbe ionic n. ~ . r catalysts, such as L;l CUIIVI~GII~ and ~n~c~ , use metals from Group IVB as the cation with a compatible weakly l,UUI~ v anion. These catalysts are 25 entirely distinct from the catalysts used in this invention.
Research has continued toward the production of a melt-lJluc addition polymer of a NB-type monomer, and is the subject of an on-going effort By "melt-~,lu, ' l~" it is meant that the polymer is adequately flowable to be ~h` . ....1`~..1.. `~l in a i r ' G window above its T8 but below its ~ l t~ Ul C, To date, there has been no disclosure of how to WO 95/14048 PCI`/US94/13166

2 ~ 7~75~

olve the many problems inherent in the production of a heat-resistant, yet and p-~ ' '- polymer of a NB-functional monomer which polymer can be extruded, injection molded, blow molded, and the like, using .,u..~. ' equipment.
To date, we know of no practical or reliable method for commercially producing an amorphous NB addition polymer with controlled mol wt.
Polymers formed with too low a mol wt are of limited utility in i~.. ,....r.., . ^~
articles. Polymers with too high a mol wt can only be cast from solution and in some cases are completely insoluble and difficult to j r The goal has been to produce an addition polymer having a mol wt Mw in the range of 50,000 to 500,000, using only one or more NB-functional monomers, in a reliably controlled manner. The only method available to produce such a polymer has been through premature dLc~,~;va~iù~ of the catalyst systems which produce amorphous polymers of NB, the I~U~I~UIJOIYII~ having mol wts in the millions.
Predictably, this method ûf mol wt control leads to low catalyst ~ )du~ivi~y andrequires the use of high catalyst levels when the mol wt Mw is to be in the range from about 150,000 - 3 50,000. Since the problem of forming a ~,.u.,~ l,lc NB-type polymer was never solved, the second, equally serious problem of obtaining a useful or practical level of conversion wafi never addressed.
A few years ago the reactivity of cationic, weakly ligated, transition metal compounds was studied in the pol~ iL~ILiu~. of olefins and strained ring , (A Sen, T. Lai and R. Thomas, J. of O~ i, ' Chemistly 358 (1988) 567-568, C. Mehler and W. Risse, r~ Chem., Rapid Commun.12,255-259(1991)). Pdcomplexes ~ theweakly ligating CH3CN (acetonitrile) ligand in, ' with a weakly WUldi~
could only be used with aggressive solvents such as acetonitrile or ..il.~ ' - When Sen et al used the complexes to polymerize NB, a high yield of a homopolymer which was insoluble in CHCI3, CH2CI2 and C6H6, was obtained.

WO 95114048 PCr/US94/13166 21 7~756 The iden~ical .~A~J.,I ' I procedure, with the same catalyst and reactants, when practiced by Risse et al used one-half the molar amount of each Risse et al reported the synthesis of a polyNB llu....~vl.~l.~ which had a mol wt Ml, of 24,000. In other runs, using different ratios of NB to Pd2+-S compound, polyNBs having mol wts Mn of 38,000 and 70,000 ~ ,Li~.ly with narrow dispersities MW/Mn in the range from 1.36 to 1.45, and viscosities in therange from 0.22 to û.45 dl_/g were made. A I r ~/ which had a viscosity of I . I waS synthesized, which upon eALIlliJola~iul~ from the mol wt data given for the prior runs, indicates the Mw was over lo6. See Mehler and Risse r~ Chem., Rapid Commun. 12, 255-9 (1991), CA~ section at the bottom of page 258 and the GPC data in Table I on pg 256. The polymers were soluble in 1,2-dichlulul,~l~.,..c in which Risse et. al. measured mol wts by GPC (gel permeation ~ UII~LU~;I~II.Y) and viscometry, as did Maezawa et al in EP 445,755A, discussed below.
Maezawa et al disclosed the production of high mol wt NB polymers with a two-component catalyst system. The disclosure states that the polymer is preferably formed in the molecular weight range from 105 to 107. The manner of obtaining the desired mol wt is sho vn to be by i ,, the pol~ ,.i~Liùll reaction after a ~JIr~ . . ".;,..~1 period. Such i is 20 effected by ~F ~ J~; "g the catalyst with an external terminating agent such as acidified methanol, which is added to the reaction to stop the polyl..~i~iun.
There is no internal control of the mol wt within a ~ ' range by an agent that does not deactivate the catalyst.
Specifically, three known methods of controlling the mol wt are 25 suggested: (i) varying the amount of the transition metal compound used; (ii) varying the poly,..~ Liul~ h~ , and (iii) using hydrogen as a chain transfer agent "CTA" (see page 9, lines 20-23 of the '755A disclosure) as suggested by Schnecko, Caspary and Degler in "Copolymers of Ethylene with Bicyclic Dienes" Die Ar.~.. Mah~ )! ' ' c Chemie, 20 (1971) 141-152 (Nr.283). Despite the foregoing Cl~g~ctir~nc, there is no indication in '755A

WO 95/14048 PCI/US94/13166 ~

that any of them was effective, as is readily concluded from the illustrativeexamples in the .1,. .; 1;. .- l ;. .., As stated in their illustrative Example I in which the catalyst included a ~,ulllb;~lai;u~l of nickel l,;~ac,e~: Ni(acac)2 and ' ' ~ ("MAO"), a polyNB having Mw = 2.22 x 106 (by GPC) was formed. As shown in Table I of the '755A reference, only Exs. 5, 6 and 7, in which the (L-;~Jh~ , ' , ' )Ni-containing catalysts were used, made homopolymers with M~". = 234,000; 646,000, and 577,000 ~ .Li~.,ly. These nickel catalysts with a L~ ' ~ ligand, are shown to hâve relatively lower ~JIudu~LiviLy than the ~;._y~,h)u~.hdi~,..yl~ l (Ex 3) and û bis-,y~ ylllh,L~I (Ex 4) which were also used.
One is therefore led to conclude that only those Ni-based catalysts which have substantially lower productivity than Ni(acac)2 with a MAO catalyst system would effectively decrease the mol wt of the IIUIIIUIJOIYI.~-I produced.
There is no suggestion that any of the polymers disclosed in the '755A reference15 are likely to be melt~ A conclusion that they are not melt-~luc~i~>aLle is supported by the evidence that all the polymers made by Maezawa et al were cast from solution.
A key aspect of the '755A disclosure was that the catalyst system disclosed was a ' nn of at least two r ', namely, a transition 20 metal complex, and a m~tl~l ~ cocatalyst. Maezawa et al used this multi-component catalyst system to produce the high mol wt polymers in the range above 5 x 10~. It was critical that the transition metal component in the complex be from Groups VB, VIB, VIIB, and VIII, and that it be paired with the ' ' - cocatalyst in order to produce polymer in a reasonable yield.
2s The criticality of the cocatalyst was confirmed by illustrative examples of transition metal compounds which were generally catalytically effective only so long as m~tl.~,l - ~ was the cocatalyst (Comparative Examples 3, and 4).
The ~ lhl evidence indicated that attaining a high IJludu~L;v;Ly catalyst system was limited to specific nickel complexes in ' with MAO as 30 the activator. All the illustrative examples having been run in toluene, it is WO 95/14048 2 ~ 7 ~ 7 5 6 PCTIUS94/13166 evident that they were unaware that a polar solvent such as a I ' ' ~Jlu~b and the like1 might improve, ludu~,~;v;Ly.
It is evident that the results obtained with the '755A ~,aL~ ~u~,~LdlySt system are different from those with a Group VIII metal catalyst in which the S metal is weakly ligated to di~ ,e~lc ligands and a portion of a ligand ~enerates a ~-bond. Whether the ~-bond ~ hlg ligand has an allyl group or a canonical form thereof, the allyl metal linkage provides the initial metal-C ~-bond into which successive Nr,-type moieties are inserted to form a polymer chain. This insertion reaction is well known in the amalogous ,U.U~ iUll of 0 ethylene in Ziegler Natta catalysis described in detail in the text C~ , c' .
~ ' Chemistry edited by Geoffrey Wilkinson et al, in a chapter titled "Ziegler-Natta Catalysis" by Gavens et al, 1982, pg 484 et seq. Allyl-Ni cationic complexes have been synthesized for the pul~ of butadiene, but an allyl-Ni--iy.,lu I ("allyl-Ni COD") cation complex was reported 1s not to be ~ L.llyLh,l~lly active (see text, The Organic Cbemistry of Nickel P.W.
Jolly and G. Wilke, Vol I Academic Press New York, 1974 pg 352) On the other hand, it has long been recognized that cationic nickel compounds are active catalysts for the polymerization of butadiene (R. Taube, etal r~ Chem., r ~ ' Symp. 66, (1993) 245, L. Porri, G. Natta, M. C. Gallazzi, J. of Polymer Sci. Pt C. 16 (1967) 2525). Taube et al state "The chain growth proceeds by the insertion of butadiene into the allyl nickel bond always with formation of the new butenyl group in the 'amti' Wllrl~LllaLi (anti insertion)." The Luuld;ll.lL;un of an allyl type ligand to the nickel is maintained ~y throughout the butadiene l,ul~,...,.;~Liu... This 2s mechanism is clearly ~ from the insertion mechanism of a NB-fuhctional monomer in which insertion of only the very first monomer molecule occurs at an allyl type ligated metal center.
Allylnirl~lh~liA~c alone (no Lewis acid cocatalyst) have been used to produce polyNB, however the molecular weights of the NB polymer produced in these studies were actually low; eg 1û00 to 1500 mol wt (L. Porri, G. Natta, WO 95/14048 PCT/US94/13166 ~
2~ 74756 M.C. Gallazzi Chim. Ind. (Milan), 46 (1964),428). It had been thought that the low yields and the low mol wts of the polyNB were due to d~ a~iull of the catalysts.
Still more recently, in a lone example of the use of a nickel catalyst as a s transition meta~ equivalent to zirconium, Okamoto et al disclosed the production of high mol wt llu,l,o.,..,,.~ polymer with a three component catalyst system inexarnple 1 17 on page 46 of EP 504,41 8A. The three-component catalyst was made in situ by combining l~ ubu~yL.luminum; !'' ' y' ''' ' tetrakis(p ~ u~ .yl)borate; and, Ni(acac)2 in toluene. The polymer recovered had a Mw = 1.21 x I o6 and a mol wt distribution of 2.37. Though essentially the entire ~ ; r, ~ is directed to the ,u~.~ly of ~,y~,lOoh,r~ll, with Ir-olefins using zirconium-containing catalysts, Okamoto et al did not react norbomene and ~-olefin with a nickel catalyst. Nowhere in the '41 8A ~l .; r ~ is there a teaching that the use of an u-olefinic CTA will 1 s control molecular weight. There is no teaching of a polymer with a temlinalolefinic end-group. Nor is there any teaching that an ll-olefin would do anything but copolymerize.
The failure to recognize that an l~-olefin might function as a CTA, with or without the presence of an all.y' ' cocatalyst, was L ' ' ' ' 'C
since there existed a large body of work related to the ,upoly~ ;Lalivll of uy~lool~ll., with ll-olefins, and in none of such poly was there any disclosure that the ~-olefin might function as an effective CTA. Further, the great reactivity ûf ethylene or propylene buttressed an expectation that ~,uIJuly -i7~-~inn, not chain transfer, is the logical and expected result.
Since practical ' .~iUII relating to melt-processing cycloolefin addition polymers produced herein, dictate that their mol wt be controlled within one order of magnitude, e.g., in the range from 50,000 to 500,000, it is evidentthat the '755A invention was unable to provide either a solution to the problem,or even an enabling disclosure to solve it. They do not suggest they can reliably make a ~ Jludu.,;l,lc polymer in the defined mol wt range. They suggest the use ~ WO 95/14048 2 ~ 7 4 7 5 6 PCT/US9~/13166 of hydrogen as CTA, and provided no reasoD to explore using another, least of all a CTA with a terminal non-styrenic, non-vinyl ether double bond. Moreover, there is DO disclosure of a polymer with a terminal end-group derived from a compound having terminal l Neither is there any basis for estimating the effect of an l~-olefin as a CTA in an insertion reaction, particularly insofar as the a-olefin is effective to tailor the mol wt of the growing polyma chains in an addition pul~ --i7~tirm liv~ of whether a . ': . Group VIII catalytic system is used in a complex catalyst of the type taught by Maezawa.
An acyclic olefin, e.g., I-hexene, is known to be an effective CTA in the ROMP of cyclic olefins, to reduce mol wt via a cross ' merl~ ic n ROMP involves a metal carbene (or metal alkylidene) active center which i~teracts with the cyclic olefin monomer to afford a metallo."y, ' "
jl~t~ '' ' A repeating unit contains a C=C double bond for every C=C
1 s double bond in the monomer. How effectively the acyclic olefin reduces the mol wt of the copolymer formed depends on the structure of the olefin and on the cata~yst system (K.J. Ivin, Olefin M. ' , Academic Press, 1983). In contrast, addition (or vinyl type) poly~ Llo~l of olefins and diolefins involves the insertion of the monomer into a metal-carbon o-bond, as in Ni-C, or Pd-C. Despite the many disclosures relating to the formation of copolymers of NB-type monomers, and the well-known fact that an olefin is an effective chain transfer agent in a ROMP pOI yll.~,l ;~livn, it will now be evident why the difference in the ' of chain termination failed to suggest the use of an olefin as a chain transfer agent in the .~u,~vly~ taught herein.
Chain transfer via ~-hydride elimination has been previously described.
See, for example, r~ , r and other Polyolefins r~,ly ;~lh,.~ and Char~ ". by Ser van der Ven, Stl~ oC ;n Po1vm~ S~ nf~ 7, Elsevier Amsterdam, etc. 1990, Chapter I POLYPROPYLENE; CATALYSTS AND
POLYMERIZATION ASPECTS by Brian L. Goodall, and Section 1.6 thereof titled "The Effect of Catalyst and Process Variables on the Molecular Weight WO 95/14048 2 1 7 ~ 7 ~) o PCTIUS94113166 ~

and its Distribution ("Chain Transfer"), and particularly Section 1.6.3 On The ~.~rl.~nicnn of ('h:lin Tr~nCfer~ pg 82-83. In typical l-olefin pUIyll.. .iL ~;01~
hydrogen is introduced to control molecular weight. There is no teaching that the uJu~L;I~:I of a second type of olefin will result in control of molecular S weight or will selectively terminate a polymer chain with a well-deflned olefinic end-group.
In typical ll-olefin poly" ;,~ , it is recognized that the known mechanism of "B-hydride elimination" can provide a double bond near the terminal end of the polymer chain. In this mechanism which modulates the mol 10 wt of olefinic polymers, a metal bonded to a IIY IIUC bYI radical with hydrogens on the carbon B to the metal, can undergo a rcaction where the B-hydrogen is abstracted to the metal, leaving an olefinic group. This results in an unsaturated polymer chain and the metal hydride. In general, the rate of B-hydride elimination vs. the pOIyll.~.. iL l~iVII rate, controls the molecular weight of the 15 polymer. I~or most pOIylll~ . ;L l~iOIl catalyst systems, the proclivity of the catalyst system toward B-hydride elimination must be extensively researched and is not predictable. The polymer mol wt depends upon a host of process variables: the choice of monomer or monomers, the presence of or absence of hydrogen, the ligand CII~/;IVIIIII~ I.; around the transition metal, the presence of additional donor 20 ligands, type of catalyst (1.. ,.".~,.. ,.. ~ or }.~,tl,lV~,_.. ,VU~), presence or absence of a cocatalyst (and choice thereof), and JUI~ liL ~ l medium (bulk, solution, slurry, gas phase), i~ler alia. It will be clear from the above and is well J in the literature that the resulting poly(a-olefin) contains a mixture of end-groups both saturated and l The factors that influence ~-hydrogen elimination in the ease of Group Vlll metal catalysts are also u~ cdi~ , for example, nickel catalysts have been used in the poly,l.~,. i~;Ol~ of ethylene. Depending upon the Ni eatalyst ehosen, it is possible to generate exelusively the dimer (I-butene), higher olefins ;~
(oligomers), or high mol wt pol~ ,. Tl"--- ~ . v~ Ni eatalysts for the poly,.,.,, ;L~l;Ol~ of ethylene to high mol wt pvl~.,tll~h,llc have been dcscribed by ~ WO 95/14048 PCI'IUS~4/13166 ?~7~756 Il Klabunde et al. (U. Klabunde et al., J. Polym. Sci., Polym, Chem., 25 p 1989 (1987)) and Ostoja Starzewski (P.W. Jolly and G. Wilke, Vol 2, slJpra) where the polymer mol wt is controlled by the ligand .~ ill around the nickel and tbe choice of reaction medium. The polymerization of ethylene has been 5 reported to occur in the presence of a variety of different nickel containing Ziegler catalysts and single-component nickel catalysts, while otha nickel catalysts give only dimers (see P.W. Jolly and G. Wilke, Vol 2, supra). Shell Oil Co. uses a nickel-catalyzed ,- ' " of ethylene to Ill~lur~ ul e linear Ic-olefins on a large scale (see G.W. Parshall and S.D. Ittel, 0 1'- O - Catalysis: The ~ aDd Chemistry of Catalysis by Soluble Transition Metal C~ , , John Wiley and Sons, 1992).
The mechanism by which an l-olefin affects both initiation and pl up~;~Liull rate in a different pùl ~ system, namely the cobalt-catalyzed polymerization of butadiene (to butadiene rubber) was known, as 15 stated by Goodall supra, on pg 83, but the rate at which the reaction occurs, and the amount of butadiene which is ;II~,UI ~JUI _~"J in the rubber chains is not predictable,, jr ~ the presence in the reactor, of a major molar amount of Ic-olefin relative to the butadiene. From the foregoing ~ ' there is no basis in the art to predict the effect of an Q-olefin on the pDI,~ " of a 2D NB-functiona~ monomer.
It is noted that nickel catalysts have been used in the pulyl..~ iull of butadiene where the solvent is neither a ~,lllulvll~Jlu~ bOli nor an aromatic solvent such as toluene or xylene. With some catalysts, the l~lh,lu~LIuuLul~ of the polymer is a function of its mol wt. With others, unsaturated llrJlu~bull~ such 2~ as acetylenes and allenes retard initiation and ,ulup~ liuli and enhance chain transfer, but do not affect III;I~IU:~UUI..~UI~: (see ~ - Of Polymer Science and F- o ~ Second Edition, Vol 2, pg 537; John Wiley and Sons, 1985).
However "..... ol~ r;,.~ were reported to have no effect on the 3D pOIylll~ iun of butadiene, at least when the amount added is relatively small 21 7475~

(see R. Sakata, J. Hosono~ A. Onishi and K. Ueda, 1~ Chem., 139 (1970) 73). Still other nickel catalysts (with different ligand CllV;lUll~ .lt~) give only (cyclic) dimers and trimers, such as "COD" and Gy' ("CDT").
S It should be noted that the structure of the Ni-~,y~ complex has been illv~L;~P~,~ in the interest of exploring numerous transition metal complexes with weakly ligated compounds in ~ ;..., with a w, Such a study was published by R. Kempe amd J. Sieler in Zeitschrift fur Kr ' " O , ' 201, 287-289 (1992) who did not suggest it would have 10 catalytic activity. Also known are compounds related to (7~-C3H~NiCI)2-TiCI4,which compounds are formed by reacting 71-allylnickel halides with strong - Lewis acids (e.g., TiCI4, AlBr3), and these are used for the pol~ Liull of butadiene and the .l;.. ;,-l;.. " of olefins. There was no logical reason from known facts about nickel catalysts which would suggest the use of the known 1~ metal complex as a particularly effective catalyst for NB-functional monomers.
There is a need to control the TE f NB-addibon polymers. The effect of an alkyl substituent on the TE f a copolymer was disclosed in an article titled"Synthesis and ~ " of poly(5-alkyl-2-llulbu.ll~)s by cationic ~ol~ ;~l;o.~. Effect of alkyl substituent length on monomer reactivity, 20 polymer structure and thermal properties" by T. Sagane et al, r~
Chem. 4, 37-52 ( 1993). The longer the sidechain, the lower the TE of the polymer. However, the copolymers were made with a AlEtCI2/ferJ-butyl chloride catalyst system, and the mol wt Mw of the longest chain made was less than 2500. There was no suggesùon that any other complex metal system, or 25 any other catalyst system might yield higha mol wts.
In view of the foregoing discussion, the prior art has not described or - - . ' ' NB-type addition polymers having a single olefinic group located at a terminal end thereof Nor has the prior art described or, , ' ' a method of controlling the molecular weight of an addition pol~ l NB-type 30 polymer in the presence of a chain transfer agent having a terminal double bond.

~ WO951140~8 ~17475~ PCTJUS94J13166 Moreover, ti~iere is no teaching that the ;~Liu~iul~Lio~ of a selected ~-olefln CTA
into the reaction medium will selectively terminate a NB-type addition polymer chain with a well-deflned olefinic end-group. Additionally, the prior ai-t does not address the effect of alkyl substituent leng~i for the conuol of Tg of N~-type s polymers over 2,5ûû Mw.
SUMMARY OF THE INVENTION
Accordingly, it is a general object of this invention to make a NB-type addition homo- or copolymer having chains with a terminal end-group derived from a chain uansfer agent ("CTA") containing a terminal olefinic non-styrenic, 10 non-vinyl ether double bond, without the chain uansfer agent being introduced into the polymer chain except near an end thereof.
It is anouher object of this invention to produce a N~-type polymer with a controllable Mw.
It is still another object of this invention to make a CTA terminated 1 s addition polymer having a repeating unit derived from (i) an ' ' NB
or NB-functional monomer including l~u~L~ , (ii) NB substituted with a (Cl-C20)alkyl, (Cl-C20)haloalkyl, (C~-CI2)cycloa'ikyl which, in turn, may be substituted; or, (iii) (Cl-C6)alkylidene group; or, (iv) an aryl or haloaryl group, e.g., phenylNB, p-chlorostyrylNB; or, a (C7-CI5)aralkyl or haloari~ikyl group, 20 e.g., 5-benzylNB; or (v) v;~ylliulLlulll~.c (vinylNB); or (vi) (C3-C20)aikylenylNB provided it does not terminate with a vinyl group, that is, the double bond in the substituent is an internal olefinic bond.
In another object of the invention 1- r ~ CI > or copolymers derived from NB-functionai monomers are formed in a desired mol wt range by using a 25 i~ amount of a CTA having an olefinic terminal double bond. The amount of CTA used is a function of the mol wt chosen for the polymer, iUlC~ iV~ of which addition polyl...,l;~iiu.l cata'iyst is used. Preferably the catalyst yields only an addition polymer terminated with the chain transfer agent as a chain end in which the oleFmic double bond is preserved.

2 1-~ 755 It is a furtiler object of the present invention to control the mol wt ramge of polymer by the use of a terminal olefinic CTA in the presence of a NB-functional monomer, a transition metdl complex, and a sufficient amount of an ~ I' yl~ . cocatdlyst.
S It is another specific object of this invention to provide a homopoiymer or copolymer derived from a norbornene-functional monomer having a controlled mol wt in a ~l rd~ range wherein the monomer preferably has a single (C6-CI6)alkyl or (C6-CI2)haloalkyl, or etilylidene substituent at the 5and/or 6 positions, and the length of the substituent on at least one of the monomers is chosen to provide a polymer of desired Tg.
It is still another specific object of this invention to provide a copolymer derived from NB-functional monomers, at least one of which is a NB-functional monomer having a single aikylene substituent having from 2 to 20 carbon atoms, in which copolymer the length of the substituent on at least one of the monomers15 and the ratio of the ,.",.~ is so chosen as to provide a copolymer of desired T8.
It is yet another object of this invention to provide a copolymer of a first monomer selected from the group consisting of NB amd substituted NB present in a major amount relative to a second monomer chosen from a mono(C4-20 C8)cycloolefin; l~u.bo,dd;.,l.~; dimers of ~Y~r ' 1' , trimers of l,Y~lLr ' -, and a multi-ringed ~;y, ' ' ~ structure d.,li~.~,J r~ulll at least one NB unit, the structure including up to five fused rings; and, preferably, the CTA is present in an amount less than lO mole %, preferably less tilan S
mole %, relative to the first monomer.
2s It is a further specific object to enhance the yield of the addition polymer formed in the presence of a single or '~ `- r component catdlyst system il l t~ iV~ of whether the polymeri2ation is carried out in the absence or presence of a lower (Cl-C3) alky' ' - cocatdlyst, by the simple expedient of using a l~dlull~JluCcuiJull solvent rather than a non-polar solvent, without regard to the transition metal used to form the . .. ~ 'I complex. In .

particular, when the trar sition complex in ~ with an aLky' ' - cocatalyst in an amount effective to convert at least one NB-functional monomer with another NB-functional or .I.u..o.,y.,l;c monomer ~,ul~ dl,le with NB, into an addition polymer, and the metal is selected from s the group consisting of chromium, molybdenum, tungsten, cobalt, manganese, nickel, palladium and platirlum, it is found that with the I ' ' yJI~,~bol~
solvent the conversion of mûnomer(s) to polymer is at least 100% higher than when said reactants are poly ' in an essentially non-polar solvent. The amount of ~1,..,,;"". .."r used is preferably from 50 to 500 equivalent of Al for 0 each equivalent of transition metal in the catalyst.
It is an object of the present invention to produce a melt-p.u~,~ ,~l~ NB-type polymer having a CTA terminal end and a Mw in the range of 50,000 to SOû,OOû.
It is another object of this invention to provide a method for appending a 1s terminal olefinic end-group on a NB-type polymer.
These and other objects of the present invention are . ' ' ' by pol~.,l.,.;~;l.g a 11UIbU~ functional monomer in the presence of a single or '''~'11;~ ""'I"J ~l catalyst system containing a Group Vlll transition metal ionsource. The ~ulylll.,~ i;GIl reaction can be carried out with or without a chain20 transfer agent having a terminal olefinic double bond between adjacent carbonatoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least oneof said adjacent carbon atoms has two hydrogen atoms attached thereto.
The present invention is directed to addition polymers derived from NB-functional monomers wherein the chains of said polymer are terminated with an 2s olefinic moiety derived from a chain transfer agent selected from a compound having a non-vinyl, non-vinyl ether terminal olefinic double bond between adjacent carbon atoms and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto, wherein the moiety derived from said chain transfa agent is exclusively located at the terminal end of said polymer chain.
30 The chain transfer agents of this invention are exclusive of conjugated dienes.

21 7~756 The NB-type addition polymers of this invention are prepared from a single or mlllti~ - catalyst system comprising a Group VIII metal ion source. These catalyst systems are unique in that they catalyze the insertion ofthe chain transfer agents of this invention exclusively at a terminal end of theS polymer chain. By exclusively located at a terminal end of the polymer chain does not exclude minimal amounts (less than I mole %, based on the total repeating units present in the polymer chain in addition to the terminal end-groups derived from the CTA) of the chain transfer agent being;- - . .,1,. " Alrd into the polymer chain.
The catalyst systems of our invention do not incorporate ethylene or any ~-olefin having a non-styrenic or non-vinyl ether double bond into the polymer formed, except at the terminal ends thereof. As will presently be evident, the term "catalyst'' is used because the function of said catalyst is that of both an initiator of a chain as well as that of its termination by inciting B-hydride ~limir~ir~n In ~,ulllb~ Liu~ with the catalyst systems used in this invention, a ; 1 Ir d amount of an olefin with a terminal double bond, functions as an efficient chain transfer agent (CTA), and reliably produces higher mol wt polym ers of p. tU~,tUI ~ weight average molecular weight Mw in the range from about 500 to about 2,000,000 or more. By "olefin with a terminal double bond'' we refer to an olefin which has a CH2r-C(R')2 structure, wherein R' r I ~5/ represents hydrogen, a l~ydlu~,~l)yl group, or a group as defined Il." ~;llb~,lu n/. The terminal double bond is a non-styrenic, non-vinyl ether double bond. In other words, R' cannot represent an aromatic moiety such as 2s phenyl or an -OR moiety wherein R is l~yd~u~ lJyl. The CTA of this invention also excludes conjugated diene ~,u...~ ' The M~,. range given above is determined relative to pul~Ly~ ., by GPC
(gel permeation ul....,. ~ y) A NB-type polymer with a Mw which is ~,u..L ull~lc within a desired 30 relatively narrow range, is produced by using a l~ydlu~,~ubull with a terminal .

double bond, most preferably an ~-olefin, as a CTA preferably in a minor amount relative to the cy~,luch,r~ being polymerized, and ~l U~UI ~iùll.,d to provide the desired mol wt; the more olefin used, the lower the mol wt of the copolymer. The resulting cycloolefin (co)polymer has a ~ ;r terminal double bond which results from a ~-hydride elimination reaction terminating a i lg chain.
When the olefin is ethylene in the pOI~ ;Ul~ of a NB-functional monomer, the ethylene ends up as vinyl end group. If the chain of addition-polymerized cycloolefin repeating units is not too long, the vinyl end group 10 affords a polymerizable Ina.,lull,ul,u,..~ or oligomer having from about 4 to 5û, preferably from 4 to 30 and most preferably from 4 to 20 NB-type repeating units.
Thus, to make a polyNB l~la~l~ having a Mw in the range from 500 to 3,ûO0 (corresponding to from 4 to about 30 linked repeating units), one 1 s simply uses the calculated molar amount of olefin, based on the desired chain length, for the CTA. In an analogous manner, a polymer in the range from about 3,000 to 2,000,000, preferably from 3,000 to 1,000,000, more preferably 20,000 to 500,000, and most preferably from 50,000 to S00,000, is made by using a proportioned amount of olefin, and if desired, even higher mol wts. The 20 ease with which either a .~a~", , or a melt-lJIucG~aabl~ (co)polymer is made, is a function of the ~ la~ Lil,~ of the particular cycloolefin species being (co)polymerized.
This invention provides such polymers. For obvious reasons, crystalline NB polymers which do not melt and are insoluble in ~ull~.,.. iullally used 25 solvents are unsuitable for such "forming" or "drawing" operations.
Most preferably, a polymer in the M~" range from about 50,000 to 500,000 is produced which is readily IJIUCG~ with ~U~ ;Ul~
E. techniques, though tailored polymers with even higher Mw are Iulu.,G"al,lc if a monomer is substituted with an alkyl, alkylene or alkylidene 30 substituent. Which substituent is chosen, along with the number of carbon 2~ 7~75~
l O
atoms (number of aliphatic carbon atoms) in the chosen substituent, determines the processability and toughness of the polymer.
The polymer produced can be i' ~( 1, extruded, injection molded, vacuum formed, ~a;vll molded, blow molded, press molded, cast 5 from solution, solvent processed, fiber formed, and sintered, into various shapes and forms. End-use All~u~ include automotive and Ll~a,uul L ll;ull such as lighting, glazing, under hood , , body panels, bumpers, dash boards, and the like; medical Al,l.l;. -l;.."~ such as fluid handling equipment, and the like; electrical and electronic Alll~li. -l;...- such as computer 10 housings, insulators, and the like; building and uu~ tluc~ion A~ . such as glazing, coatings, and the like; appliance panels and trim; consumer products such as IIUUacw_lca, microwave equipment; packaging; industrial parts and , and optical ~ r ' Sheets, tubes and other forms of arbitrary length and cross-section may also be formed by extruding the polymer Because 1 s of the controllable mol wt of the polymer, such forms may be adapted for use as membrane means for the separation of gas from liquid, as in p~ \~ ul al;ull l..1. , or, in the separation of liquids having different molecular weights as in nanofiltration or reverse osmosis The lower Mw polymers (oligomers or I ) of this 20 invention can be used in waxes, additives, coatings, adhesives, sealants, and the like.
The common source of a processability problem with known addition cycloolefin (co)polymers having a repeating unit with a NB-type structure is that they are not melt- ~.lu~,c,.,AI.I~. The problem stems from an inability to control 2s the growth of the polymer chains. This inability is endemic to all known pOl~ l;~Liu.. systems for the addition pul~ Liull of norbornene-functional monomers. Therefore, when the problem of forming a melt-,uluuca~ polymer of a NB-functional cycloolefin monomer was addressed, neither the essential .. ~I.u~ of an appropriate catalyst nor its structure could 30 be deduced from known catalysts used for the purpose at hand. This purpose is ~ WO 95~14048 2 1 7 ~ 7 5 6 PCI`/IJS94113~66 to produce holuv,uvly,..crs of a multi-ringed cycloolefin, or, a copolymer of first and second multi-ringed ~y.,lvol.,l,...,, or, a copolymer of a multi-ringed cycloolefin and another ~.,lool.,l,.,. We have provided several catalyst systems bu.,~,;rc~lly adapted for use in the addition .,uv.- pOI~ auu 5 of huu~v~ul,~ --.c and copolymers of ,yulOOh,lula, effected in solution or in slurry.
In "solution", we refer not only to a polylll.,.;~llull in the classical sense where initiator, catalyst, reactants and reaction products are in solution, in asingle phase, but aiso to ~JDIy ' ' in which a phase of III;~IU,U-II L;cles 10 smailer than I ~m are present, which particles are so smail, typicaily less than 0.1 Ilm, as to behave as a single phase. Such a two-phase reaction mass is referred to as a colloidai solution. In "slurry", we refer to pol.~ in which (i) the presence of poiymer is evidenced by a distinct separate phase which typicaily ~le , out of solution; or (ii) catalyst is anchored to an 15 "active" support, ;1l riaAu~,~L;ve of the phase in which the polymer is present. An "active'l support is one which exhibits a distinct ;buL;vll with respect to the polymer formed, compared with an "inert" or "inactive" support such as silica which fails to exhibit such .,U..LI;I,uL;ull.
Bi~EF DESCRIPTION OF Ti~lE DRAWINGS
The foregoing and additionai objects and advantages of the invention will best be understood by reference to the following detailed description, with schematic ill~lerrAtinnc of preferred ' ' ofthe invention, in which jll~ctrArinnc llke referencè numerais refer to like elements, and in which:
Figure I is a schematic illustration depicting the manner in which a cataiyst of this invention (Ni is illustrated) is believed to produce the copolymer.
Figure 2 is a graph depicting the effect of the ..,. _..1,,.1;..., Of 5 d~ luu~i~u~ , on the T~ of a copolymer of norbornene and 5-de~,yl"o,vu,n~,llc.

WO 95/14048 2 l 7 ~ 7 5 6 PCI/US94/13166 ~

Figure 3 is a graph depicting the effect of l-decene U~ J d~iOII on the weight average molecular weight of poly(norbornene) formed.
Figure 4 is a ~3C-NMR spectrum at 50 MHz of a nickel catalyzed polymer of the present invention.
s Figure S is a 13C-NMR spectrum at 50 MHz of a palladium catalyzed polymer of the present invention.
Figure 6 is a l3C-NMR spectrum at 50 MHz of a nickel catalyzed polymer of the present invention.
Figure 7 is a 13C-NMR spectrum at 50 MHz of a palladium catalyzed polymer of the present invention.
Figure 8 is a IH-13C 2D NMR correlation spectrum at 500 MHz of a nickel catalyzed polymer of the present invention.
Figure 9 is an expansion of the aliphatic region of the 2D NMR spectrum shown in Figure 8.
1s DETAILED DESCRIPTION OF THE INVENTION
In one ~ ,ho.l;,.-- l of this invention, a novel, essentially anhydrous, reaction mixture of a NB-functional monomer and any pre-formed single component complex metal catalyst has been found to propagate polymer chains of controllable mol wt, provided the catalyst initiates a polymer chain by an 20 insertion reaction of the monomer, and this occurs in the presence of a-p,cd.,; ' amount of a terminal olefinic chain transfer agent ("CTA"). This reaction mixture is remarkable because it does not require purified monomers, nor is the reaction mixture sensitive to the presence of organic impurities which are not highly reactive with the catalyst. This property is unlike that of catalysts 25 containing an effective transition metal from "the other side" of the Periodic Table, specifically, such as ,i.~ , hafnocene and titanocene catalysts.
Under typical operating conditions, these ''other side" catalysts are well knownto be totally ineffective in the presence of even trace amounts of water as low as 10 ppm, and sensitive to a wide variety of reactive functions requiring ~ WO 95114048 2 1 7 4 7 5 6 PCT/US94/~3166 ;r pl~rifjro~irn of monomers. By ''essentially anhydrous" is meant that tbereisnomoretban 1%byweightofmoisturepresentinthepol~....,,i~,~Liu., reaction mixture, and preferably less than 0.1%.
~ ore specifically, the reaction mixture is most preferably a solution of a s pre-formed, single-component ionic catalyst of nickel or palladium with a NB-functional monomer, in ~,ullllJ;lld;ull with a ~ . I--; F-1 minor molar amount of an olefinic CTA relative to the moles of monomer in the mixture, in the absence of a cocatalyst such as an: ' - (e.g., MAO), or an aluminum alkyl (e.g., L i~LllyL~lu~llinum, dl~,Llly' ' , chloride, ethylaluminum 10 dichloride, clllyLIlulllillu,.l s~lui~lL~rid~, and the like), though other specific Group VIII transition metals ("M") produce some copolymers, but less effectively. The CTA is either ethylene or a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least ûne of said adjacent carbon atoms has 15 two hydrogen atoms attached thereto.
The pre-for~ned single component u", ~ complex catalyst is 1 by Ll [ \M - L3]1 CA
L~ Structure I
wherein, M represents a Group VIIT metal, preferably a metal selected from the group consisting of Ni and Pd;
Ll, L2, and L3 represent ligands, which separately, or, two, or all three together, 25 provide up to three (3) ~-bonds and a single metal-C a-bond to M; and Ll, L2,and L3 may each be the same, or different, and when different, provide three individual ligands; or, two of the three ligands may be portions of an individual ligand; or, all three ligands may be portions of the same ligand; and, CA-represents a weakly l_UUld;l-~liillg counter anion chosen to solubilize the cation in WO95/14048 2 1 ' 4 7 5 6 PCTNS94/13166 an inert, that is, non-reactive, cosolvent for all reactants.
The phrase "compatible weakly wuld;ll~lL;I~g anion" refers to an anion which is only weakly ~,uu-~ to the cation, thereby remaining sufficiently labile to be displaced by a neutral Lewis base. More specifically the phrase 5 refers to am anion which when functioning as a stabilizing anion in the catalyst system of this invention does not transfer an anionic substituent or fragment thereof to the cation, thereby forming a neutral product. Compatible anions are anions which are not degraded to neutrality when the initially formed complex The reaction mixture most preferably consists of a single phase which may include a colloidal solution. Alternatively, the reaction may be effected ina hct..u~ vu~ system with a L,~ u~ .,vu~ catalyst, illustrated in particular by one anchored to an "active" support such as aluminum fluoride to control the morphology of the polymer formed.
The single component catalyst consists essentially of (i) a cation of said organo"M" complex which most preferably consists of a single "M", preferably Ni or Pd atom, and (ii) a weakly ~,uo.~ "., the cation hæ a llydlu~ lJyl group directly bound to "M" by a single metal-C a bond, and also by at least one, but no more than three 71-bonds. By l~ydlu~,~byl is meant a 20 group that is capable of stabilizing a Group Vlll metal complex by providing a carbon-metal a bond and at least one or more olefinic 7~ bonds that may be conjugated or non-conjugated, or aromatic rings. RL~ l; ve llydl u~,~ I,yl groups are (C3-C20) alkenyl groups which may be, non-cyclic y~,l;., or polycyclic and can be substituted with branched and (Cl-C20) 25 alkoxy, (C6-C,s) aryloxy or halo groups. Optionally, the cation is bound to aweakly wul d;~ .,g neutral donating ligand by not more than two x-bonds or an aromatic ring. This complex cation most preferably consists essentially of (i) asingle allyl ligand, or, a canonical form thereof, which provides a a-bond and a~-bond; or, (ii) a compound providing at least one olefinic ~-bond to the metal,30 and a a-bond to the metal from a distal C-atom, spaced apart from either olefinic PCT/US9.t/13166 C-atom by at least two carbon-carbon single bonds. The weakly CUUI U;IIG~
neutral ligand is preferably a chelating bidentate cyclo(C6-Cl2)diolefin, for example ~,y Ino ~ t: ~ ("COD") or diben20COD, or an aromatic compûund such as ben2 ene, tûluene~ xylene, or mesitylene.
s Embûdiment (i) of the complex cation is illustrated by: .
Rl ~ Rl +
R~ -¢M ~ CA R~ ~M ~ CA-R3 _ R3 Structure IIA Structure IIB
+
, 3 CA
Structure III
where Rl, R2, R3 are each ;~ IJ' ..~1. ..;ly a hydrogen atom, or an alkyl, aralkyl, or cycloalkyl group containing ~rom I to 8 carbon atoms. Optionally, any two 10 of Rl, R2, R3 may be linked together to form a cyclic ring structure.
~mh~-lim~nt (ii) of the complex cation is illustrated by:

WO 9!i/14048 2 1 7 4 7 5 6 PCT/US94/13166 -- - -- + :: , ~ ~3 CA `
Structure IV
OMe +
~:~M ~1 CA
Structure V
It is a specif c object of this invention to provide the above-described complex cation of "M" with a weakly cuu.~" ,, or non-uuu~ ' 3~, S ~UUI~t~ ;U~ which is a relativeiy inert and poot ",., ~ h l~, which provides the cation with essential solubility in ll~dlU~4lbUI- and I ' ' YdIU~ JOII solvents such as toluene, xylene, and 1,2-d;(,l~lul~ ' The anion is prefetably selected from the group consisting of a tetrafiuoride of Ga, Al, and B, or a hexafiuoride of P, Sb and As, and a phenyl borate in which the phenyl ring has F10 or CF3 ~,,1.~1;1 ,. .1>

-WO 95114048 2 1 7 4 7 5 ~ PCl~/US94/13166 ~J5 Such a preformed single-component complex may be formed in solution, in situ, and added to one or more monomers; or, the preformed single-component complex may be recovered from solution as a solid, then added to the monomer(s). In either form, whether as solution or as solid, the preformed 5 single-component complex necessarily has a Group Vlll metal in . ~"1, -- -l;.~., with a labile bidentate ligand.
In another ~ of this invention, a reaction mixture of a NB-functional monomer and a .- ': r ' catalyst system compnsing a Group VIII transition metal ion source, an Ol~, ' compound, and an optional third component has been found to propagate polymer chains of controllable mol wt. also in the presence of a ~,- tl I ' ' ' amount of the non-styrenic, non-vinyl ether chain transfer agent as described above. This is ~ by the same insertion mechanism as described above for the single component catalyst systems.
The transition metal ion source is a Group Vlll transition metal compound that is preferably soluble or made to be soluble in the reaction medium The Group Vlll transition metal is bonded to ionic and/or neutral ligands.
As used herein the term "or~pn~ n~rn compound" is non-inclusive 20 of ~1"".;.,~ ~,, however, an Pl o, e.g., MAO, can be employed when the reaction medium contains the CTA of the present invention or in the absence of a CTA so long as a IIGIUh,yl.llU~.O,I I)UII diluent is employed In the description below, reference to the "~-allyl complex" refers equally to a canonical form thereof The bidentate ligand in the complex M
cation is labile and easily displaced from the ~I-allyl complex. Upon Aisr'~ by a NB-functional moiety providing a ligand, an insertion reaction occurs which results in an, , 'Iy facile addition polyll..,.i~Liul~.
This i~ and subsequent addition reaction occurs only when a NB-functional monomer is in the liquid phase, and tbe monomer is used in a much 30 larger molar amount than the diolefin in the Ni-complex, typically in a molar WO95/14048 2i 7475~ : PCl`fUS94/13166 ~

cxcess of at least 1000:1. Despite the 'xnown stability of a bidentate ligand when bonded to "M", an insertion reaction of the monomer in the 7~-allyl complex results in the formation of a unique cationic transition metal ~JIOp~ species.
In addition to the well-defined single component catalyst system defined above~
s we also have found it possible to generate these cationic transition metal propagating species using a l.lulL;, r ' catalyst system including a Group ~)111 transition ion source, an or~nr.~ min~m compound and, optionally, a third component.
In the absence of the CTA of the present invention in an appropriate 10 amount chosen to provide polymer chains of desired average length, the dL;llg species results in a cycloolefin addition polymer having essentially no measurable Ull~iUIdl;OI~ but an undesirably hiBh mol wt. Besides the unique structure of the p. ~ L;~g species consisting of the "M-complex" in which a i"g monomer moiety is inserted~ the species forms a polymer in which J both its mol wt. and its glass transition LCIIIIJ..d~UlC (T~) are tailored to provide a weight average mol ~t 1~ > SO~ûO0 but preferably not greater than about 500,000. Lower mol wt polymers with M~" in the range from about 20~000 to 50~000~ and oligomers with M~ in the range from about 500 to 20,000. may also be formed by carrying out the pol~ dLiull in the presence of a tJIu~ ,'y 20 larger amount of olefin CTA
Referring to Fig 1~ there is crh~om.tir~lly illustrated the manner in which an olefin is believed to function as an efficient CTA in the ~OU~d;lldL;ol~
polymerization~ in a manner analogous to that in which chain transfer occurs viaB-hydride elimination in a transition-metal-catalyzed vinyl-type pol~ ;~L;v 2s (e.g., of ethylene or propylene). This mechanism proceeds via a growing poly(NB) chain which contains two B-hydrides, neither of which can be eliminated since one is located at a bridgehead and the other is situated "an~i" or "~rQ~/s" to the metal. The result is that, in the absence of a CTA, the molecular weight of the poly(NB) formed typically runs into the millions.

~ wo 951140~8 2 1 7 4 7 5 6 pCT~ITS94/13166 However, as soon as an ll-olefin (in Fig 1, l-decene is illustrated. for which R = C6HI3) inserts, the resulting metal alkyl can undergo ~-hydride p~ tinn generating an olefin-terminated poly(NB) chain, and, a Group Vlll metal hydride, i.e., a nickel hydride specieS in which a NB molecule inserts to - s initiate the next poly(NB) chain. The overall effect is a highly effective chain transfer process. In the absence of the chain transfer agents of this invention, the metal hydride cannot be formed for the purposes stated h~,..,;l.l.vu~
Irrefutable evidence for the ;~ . " 1l - .y of a Group VIII metal hydride species in the catalytic cycle for polymerizing norbornene in the presence of a 0 CTA (ethylene, '50 psig) was found upon isolation and characterization of low molecular weight norbornene oligomers from a polyl...,.;L~l;u.~ using [(crotyl)Ni(COD)]PF~ as the calalyst. The methanol solubie fraction of the resulting polymer was subjected to GC-MS (gas ~lllu~ tu~ yhy-mass a~ LIu~ ly). Two si~nificant peaks were found in the GC trace which had a s mass of 716 and 2~4, respectively Using preparatory GC methods. the peaks were separated and isolated Using one~ mpncinn~l and two- ' ' NMR
techniques the compounds ~ ere determined to be dimers of norbornene with a ~ in-~l and a hydrogen substituent (mass = 716) and a vinyl and an ethyl substituent (mass = ~44) as shov~n below (the structures as drawn are not meant 20 to favor one ~ UCl~ n~e.~o or racemic, over another since this has yet to be determined).

WO 95/14048 2 1 7 ~L 7 5 6 PCT/US94/13166 :2g The isolation arld ~ t~,.i~Liull of these dimers can be taken as concrete evidence for the following R
Ni~
K I
!~i~
Rl = H or ethyl In this Ir erh~-icrn the nickel hydride catalytic ;~ tr inserts S norbornene to gi~ e a nic~;el-norbornene moiety which cannot ~-hydride eliminate for reasons mentioned previously. This moiety can insert an additional norbomene followed b~ ethylene at which time ~i-hydrogens are a~ailable for elimination and production of the dimer with mass = 216 (the inyl, hydrogen substituted norbornene dimer).
0 Under the conditions employed, insenion of ethylene into the nickel h~dride catalytic intermediate is competitive with the first insenion of norbornene. Insenion of two subsequent norbornene units followed by ethylene and ~-hydride elimination produces the dimer of mass = Z44 (the vinyl, ethyl substituted norbomene dimer).

Thus, the presence of arl olefinic end-group in the rlorbornene polymer chairl can bc taken as proof of the ;,. ~ . ",~ y of a Group ViII metal hydride catalytic species.
Referring to Fig 7, it is evident that the TB of the copolymer formed is a s function of the ~.U~ llLl ~lL;ull of the 5-decylNB in the mixture of monomers. the ' greater the ..1,"- - ,1. ,-1;, ,,l of S-decylNB, the lower the T~ of the copolymer.
Referrins now to Fig 3, the efficacy of the ~I-olefin as a CTA is evidenced by the relatively low ' < 10 mole%, typically from 0.25 -S mole %, of l~-olefin necessary to provide the desired molecular weight.
0 Relying on the mechanism illustrated, a calculated amount of olefin affords a polymer of desired molecular weight which is ~c~u~iuc;i~ly tailored for a particular purpose. Without the knowledge that the ~-olefin would function as described, such an accurately tailored ~,ùol~i;ll~L;ull addition polymer of cycloolefins could not have been I~ u~iuc;iJly produced by modifying any 15 known prior art process.
In the single component catalytic system ~. . ,h~ ; " . F of this invention where the Group ~111 metal M represents Ni, the ulL; ",.~:~llic Ni cation has a formal CUO~i;llGLjOI~ number of 4 but an oxidation state of 2. The surprising effect of the anion which is both relatively inert, and a relatively poor 20 nucleophile, not only accounts for the solubility of the Ni-complex in halol.yJ.u~,G.i,u..s (e.g., 1.7-dichloroethane) and aromatic solvents (e.g.j toiuene and xylene), but also appears to favor the rapid d ~ '~ ~ of the bidentate ligand and formation of an addition polymer in a chosen, desirable relatively narrow mol wt range, e.~., from 2~0,000 to 300,000 in the presence of the CTA
25 of the present invention.
The key to proper anion design requires that it be labile and stable toward reactions with the cationic metal complex in the final catalyst species and that it renders the sin~le component catalyst soluble in the l-~ i-u~,a.l,o.. orhalul.y~ilu"Gubull solvents of this invention. The anions which are stable toward 30 reactions with waler or Br0nsted acids, and which do not have acidic protons 6 ~
WO 95114048 2 1 7 4 7 5 ~ ~ PCTIUS94/1316 located on the exterior of the anion (i.e., anionic complexes which do not reactwith strong acids or bases) possess the stability necessary to qualify as a stable anion for the catalyst system The properties of the anion which are important for maximum lability include overail size, and shzpe (i.e., large radius of s curvature)~ and n~clPoFhili~i-y In general, a suitable anion may be any stable anion which allows the catalyst to be dissolved in a solvent of choice, and has the following attributes:
( I ) the anion should form stable salts with the drul : ' Lewis acid, Brnnsted acids, reducible Lewis Acids, protonated Leu~is bases, thallium and 0 Sjlver cations; (2) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; (3) theanion should be a relativel~ poor nl~ nFhil~; and (~) the anion should not be a powerful reducing or oxidizing agent Examples of anions meeting the foregoing cnteria are the following:
s BFJ ,PF6-: AIF303SCF3', SbF6-, B[C6H3(CF3)~]~'; SbFsS3F; and B[C6Fs]~
A preferred pre-formed, single catalytic cpmponent is formed by protonating a knov n tris- or tetr~ nl~finnirL-~I compound (see P.W. Jolly and G. ~'ilke. Vol I .~llpra, pgs 75-' and 338) and this protonated cPmpound does not ha- e to be separated from solution before being added to NB-functional monomer(s) to be pol~merized .~ convenient proton source to convert the tris-or l~:L.dL.~ ",cLel is N.l~.'-dimeth~lanilinium tetrakis(bis-3,5-trifluoromethyl)phenvlborate The precursor is most preferably chosen from (i) ~,t,~-1,5~9-~yl,lododc~ )nickel or bis(~y~ lno~ ~- 1; )nickel; and, (ii) the reaction product of one of the foregoing with butadiene, which reaction productsare represented by structure belou WO 95/14048 2 1 7 ~ 7 5 6 Pcrlus94Jl3l66 A preferred active species containing Ni is a pre-formed, single catalytic component consisting of the . ~ ;. ., . of the 71-allyl-Ni-diolefin cation, for example, the 71-allyl-Ni-cyclo-l,~-octadiene cation, referred to as a "lallyl-Ni-COD] ' complex", with a compatible weakly 1,UUlU;lI.:liiU~ for the complex. There is no cûcatalyst required and none is used. However, the use of an alkylaluminum compound as a cocatalyst can be dUV_ ' _ in C;l I,UUU Lu~.c~ where the reagents are unusually high in protic impurities. Forexample, water prent in the monomer can be scavenged by the alkylaluminum compound.
0 The catalyst may be prepared by any known synthesis which results in combining a [~-(C6-CI2)cycloalkadienyl]M complex containing two ligands each of which react with an acidic hydrogen atom (i.e., proton); and, a salt which will provide both solubility in a commercially easily available and ilUll~ lLdlly acceptable solvent, as well as a compatible weakly uuul~ illg 5 counteranion for the complex which provides the cation.
In this Culllb;ll~lliùll. it is preferred to use an anion of a Group IIIA
telrafluoride, e.g., BE~4-, ûr a Group VA }IGAdnUUI id." e.g., PF6- anion; or a phenylborate having plural fluoro or Lfilluulull..,llyl ring ~ , or an arylborate having plural fluv~ul~l~illyl ~..l.,l;:... : Such anions provide desired 20 solubilily and are compatible with and ùull~,uuldil~ toward the Ni-complex cation for~ned. Yet such anions effectively stabilize the cation without adversely affecting its ability to polymerize NB-functional monomers.
The specific catalyst: allyl-Ni-COD/weakly ~ùuld;lldlillg anion is pre-formed by first forming a neutral NirCOD]2 complex, reacting the complex with 25 an allylbromide to generate a bis(allylNi bromide) complex which is then subjected to scission with a halide abstracting agent and an anion-providing salt such as thallium hexafluùlu~,ho~yL.. or silver l`~ dnllù~ ~ The sequence is written as follows:

WO95114048 2 1 7475,~ PCrlUS94/13166

3~
Ni ~ ~, Br 3~ ~ Br -- -- + Tl PF h Ni ;~ PF h When partitioned, onl~ one COD ligand remains, and it is bonded through t~vo ~ bonds to the nickel.
The m~ irompnn~nT catal~st system ,~mhorlinn~nt of the present in~ ention comprises a Group ~'111 transition metal source, an ul v. . 'i .., .; ,......
s compound~ and an optional third component.
The Group Vlll transition metal source is selected from a compound containing at least one transition metal selected from Group VIII of the Periodic Table. There are no restrictions on the transilion metal compound so long as it provides a source of catal-tically active Group VIII transition metal ions.
0 Preferably, the Group Vlll transition metal compound is soluble or can be made to be soluble in the reaction medium. The Group VIII transition metal preferably is selected from iron, cobalt, nickel, rhodium, ruthenium, palladium and platinum. Of these~ nickel, palladium and cobalt are particularly preferred.The Group ~111 transition metal compound comprises ionic and/or 5 neutral ligand(s) bonded ~o the Group ~'III transition metal. The ionic and neutral ligands can be selected from a variety of ,..~ J~ - - -, bidentate, or mlllti~ nt~t~ moieties and combinations thereof wo 95/14048 2 1 7 4 7 ~ 6 PCT/USs4/1316C
Rc~lc~llL~Live ofthe ionic ligands that can be bonded to the Group ~'iII
transition metal to form tbe transition metdl compound are anionic ligands selected from the halidcs such ~is cbioride, bromide, iodide or fluoride ions;
r~ such as cyanide, cy~inate, thiocyarlate, hydride; carbanions such as S branched and u~b ' ' (Cl-C40) aikylanions, phenyl anion;
~ Y~ ..yl;de anions; r~-allyl groupings; enolates of ~-dicarbonyl compounds such as dCcLy~ r, 2~4~r ~; and hAI ~d ace~y' such as I,I,1,5,5,5 h_~lluu~u-2,S-~ - ' , 1,1,1-trifluoro-2,4,r ~ - , anions of acidic ûxides of carbon such as 10 UAIiJw~y~ and hAIr~ nAtPd ~dfl~u~.yl~Lc~ (e.g., acetates, 2-ethylhexanoate, n~od~r~- , trifiuoroacetate, etc.) and oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aiuminates, etc.), of silicon (e.g., silicate, etc.), of ~ v~llu~uu~ (e.g., I ' , ' , phosphites, rhr,crhin~c, etc.) of sulfur (e.g, sulfates such as triflate, p-toluene sulfonate, s sulfites, etc.); ylides; amides; imides; oxidcs; ~ r ~iPC sulfides; (C6-C24) aryloxides, (Ci-C20) alkoxides, hvdroxide, hydroxy (Cl-C20) aikyl; catechols;
oxylate; chelating alkoxides and aryloxides; complex anions such as PF 6.
AIF303SCF-3, SbF-6 and compounds represented by the formulae:
Al(R7)-4, B(X)-4 20 wherein R7 and X in.l. 1....~i~ ..lly represent a halogen atom selected from Cl, F, 1, and Br, or a substituted or llncl~hc~in~ i l-yJIu~.~byl group. R~ ive of ~y~ilu_olbyl are (Cl-C25) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, 2s docosyl, tricosyl, tetracosyl, pentacosyl, and isomeric forms thereof; (C2-C25) alkenyl such as vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, LcLldd~,~,cl~yl ~ J~,c~lyl, h~Ad~,cllyl, heptadecenyl, o~ .deccllyl, llc,ll.lJ~,.,cllyl, ii~,.lL~.u~ yl, and isomeric forms thereof (C6-C25) aryl such as phenyl, tolyl, xylyl, naphthyl, andtile like; (C7-C25) aralkyl such as benzyl, phenethyl, phenpropyl, phenbutyl, phenhexyl, rlapthoctyl, and the like; (C3-C8) cycloaikyl such as cyciopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbomyl~ 2-norbonenyl, and the like. ln addition to the above definitions X represents the radical:

The temm substituted l~yLiluu~byi means the l~y~lu~.~uiJyl ~roup as pre~ iously defined wherein one or more hydrogen atoms have been replaced uith a halogen atom such as Cl, ~, Br, and I (e.g, as in the ~,.riULJIUph 10 rr~dical); hydroxyl; amino; alkyl; nitro; mercapto, and the like The ionic ligand also can be chosen from cations such as, for example, Ul`'.:IllOCl~llllUlllUII~, Ul~ IIU~ Ull;UIII, Ul~ and pyridinium compounds represented by the for~ ~ae:
~i A+(R8) 1~ (Rlo) iR~

WO 951140~8 2 1 7 4 ;7 5 6 PCr/VS94/13166 wherein A represents rlitrogen, arsenic, and I ' , ' uua and the Rx radicals canbe j~f~ fl ~lly selected from hydrogen, branched or, ~ (Cl-C20) alkyl, branched or unbranched (C2-C20) alkenyl. and (Cs-C~6) cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. R9 and Rl are S i"~ y selected from hydrogen, branched and u~ I.,h~,J (Cl-C50) alkyl, branched and ~ (C2-C50) alkenyl and (C5-CI6) cycloalkyl groups as defined above; and n is I to 5, preferably n is 3, most preferably n = I . The Rl radicals preferably are attached to positions 3, 4, and 5 on the pyridine ring.
It should be noted that increasing the sum of the carbon atoms contained 10 in the R8 radicals confers better solubility of the transition metal compound in organic media such as organic solvents and NB-functional monomer.
Preferably, the Rg radicals are selected from (Cl-Cl8) alkyl groups wherein the sum of carbon atoms for all R8 radicals is 15 to 72, preferably 25 to 48, more preferably 21 to 42. The R9 radical is preferably selected from br4nched and s ul..b~ul~h~,d (C~-C50) alkyl, more preferably (C1o-C40) alkyl. Rl is preferably selected from branched and unbranched (Cl-C40) alkyl, more preferably (C2-C30) alkyl.
Specific examples of u.g, "~ - ,....; 1 cations include LliJùd~.,y' I~ ylLI;~,4~Jly' tris(tridecyl` and 20 trio~,~y~ Specific examples of, , and U1~ cations include Ll;Jud~ ' and I ' , ' ~n.,LllylLlh,~.~)lyl~u~u~ l and I ' , ' , L-ia(L~;J~ l)arsonium and j ' , ' . and trio~,Lyl41au,l;ull1 and 1 ~ ~1,1"...: , Specific pyridinium cations include eicosyl-4-(1-butylpentyl)~.~l ' . docosyl-4-(13-2s pentacosyl)pyridinium, and eicosyl-4-(1-butylpentyl)~.yl ' Suitable neutral ligands which can be bonded to the Group VIII
transition metal are the olefins; the acetylenes; carbon monoxide; nitric oxide,nitrogen compounds such as ammonia, isocyanide, isocyanate, ;avLIl;ul~y , pyridines and pyridine derivatives (e.g., 1,10~ ' , 2,2'-dipyridyl), 1,4-dialkyl-1,3-~ , amines such as represented by the formulae:

WO 95/14048 2 1 7 4 7 5 6 PCT/US94/13166 ~

N(RI 1)3 , N(RI 1)2 . N(RI 1)2 (CH2)n (CH2)n N(R )2 NRI I
(CH2)n N(RI 1)2 10 whereinRIlisin-iPrpn~lpntlyllyJ~u~ lbylorsubstitutedllyJluualbylas previously defined and n is 2 to lû. Urea3; nitriles such as - ', bPn7nnitrilP and h~ln~P"qtPd derivatives thereof; organic ethers such as dimethyl ethe} of diethylene glycol, dioxane, hllallyJ urulall~ furan diallyl ether, diethyl ether, cyclic ethers such as diethylene glycol cyclic oligomers; organic sulfides 15 such as diethyl sulfide; thioethers; arsines; stibines; phosphines such as Llialy'l ' , ' (e.g., Ll;~ (e.g., trimethyl, triethyl, tripropyl, ~ ,.ILal,ùSyl, and ~qlnæ~9~9tP~ derivatives thereof), bis(J;,ul.~,.ly~ )ethane, bis(u;t,h~ .llu~ull;llo)propane, bis(J;I~ lly~i ' , ' )propane, bis(J;~ lpllua~,ll;llu)butane, (S)-(-)2,2'-20 bis(J;~l,.,llyl~,hJ",ll;llo)-l,l'-binaphthyl,(R)-(+)-2,2'-bis('il' ~j' .' )-I,l'-binaphthyl, and bis(2- ' . ' ~II.I,n~ ;..f.~ :I.yl)j ' ~11 ' , ' ~; phosphine oxides, phosphorus halides; phosphites represented by the formula:
P(ORI 1)3 wherein RI I i~ Iy represents a llyJ~u~,albyl or substituted ll~u~,albyl 25 as previously defined; phosphorus oxyhalides; I ' 1 l ,1 ' , ' I,l,,l~l,l,;..;t~ ~ ketones; sulfoxides such as (Cl-C20) ~ " ~laulruAides; (C6-C20) arylsulfoxides, (C~-C40)alk~yl~ulruAides, and the like. It should be recogni2ed that the foregoing neutral ligands can be utilized as optional third ~ r ' as will be described h~,lu;llb~,lu~..

wo ss/l404s 2 1 7 4 7 5 6 PCr/US9V13166 More ~ ,.,;r~odlly, the Group VIII transition metal source of the present invention can be lq!",.,~ .,J by the following formula:
C~C[MmmXXxYyyLl]
wherein C represents a cation as previously described;
s M represents a Group VIII transition metal selected from the group of iron, cobalt, nickel, ruthenium, palladium, and platinum. Preferably M is nickel, cobalt or palladium;
X and Y ;~ ly represent anionic ligands as previously described;
L represents neutral ligands as previously described;
x, y, and 1 are 0 to 1~ with the proviso th2t x, y, and I cannot all be ze~o at the same time;
cisO, 1,2,or3;
c' is the charge of C
m is I to 4 m' is the oxidation state of the Group VIII transition metal M which is determined by the equation = (xx' + yy')-cc';
m x' is the absolute value of the charge of X;
y' is the absolute value of the charge of Y;
Examples of Group VIII transition metal compounds suitable as the transition metal ion source include:
nickel a-,e~yl4~,0tu"
nickel C4~bUAY~
nickel dimO~ ly, nickel ~LIlyll,.,A4llu cobalt n~o~
- iron napthenate palladium oLlly"

NiCI2(PPh3)2 NiCI2(PPh2CH2)2 nickel (II) ~ dlluuluac~yll '.( i ' y~' nickel (Il) Ll;llUu~ua.. eL~'l dihydrate S nickel (n) ,I.. eLy~ JIa Pd cl2(PPh3)2 palladium (Il) bis(L"lluull ) palladium (Il) bis(a~.e y' palladium (Il) 2-~LI,~"
1 J Pd(acetate)2(PPh3)2 palladium (Il) bromide palladium (Il) chloride palladium (Il) iodide palladium (Il) oxide ~ ;yletris(~lipll~.yll~l.v~, .lf;) palladium (Il) UUl IJl~UI dLI~
tetrakis(acetonitrile) palladium (Il) ~,Lldnuulubula r' " u~ acetonitrile)palladium (Il) 'I;` llIOIUl';J(l' l ' Y'l ' , ' ) palladium (Il) .' ' ' ul,;~(t.,~.~u.~;Ll;l~,) palladium (Il) iron (Il) chloride iron (III) chloride iron (Il) bromide iron (m) bromide 2s iron (II) acetate iron (III) a.,eLy'a ~.
ferrocene ";. 1~ If~.,e nickel (II) acetate 3J nickel bromide ~ WO 95/14048 2 l 7 4 7 5 6 PCTNS94/13166 nickel chloride d;~l.loll ' yl nickel acetate nickel lactate nickel oxide s nickel I~Ll~luulubu cobalt (Il) acetate cobalt (Il) ace~y~i cobalt (III) acety';
cobalt (II) benzoate cobalt chloride cobalt bromide dichlorohexyl cobalt acetates cobalt (II) stearate cobalt (II) t~LldIluvlul)~ L~
bis(allyl)nickel bis(~y~ yl)nickel palladium a.,ety' ( palladium bis(acetonitrile) dichloride palladium bis(.l;.l._Lllyl~ulrv~ide) dichloride platinum bis(LI;.,llly~ ) llyllu~
ruthenium tris(LI, ' y~, ' , ' ~) dichloride ruthenium u;~ Jh_.ly~l ' . ' ~) hydrido chloride ruthenium trichloride ruthenium tetrakis(acetonitrile) dichloride 2s ruthenium tetrakis(!' ' ylaulru~;~e) dichloride rhodium chloride rhodium tris(u;~ yll~llu~Jh;..c) trichloride The or~nru~llln inllm component of the catalyst system of tne present invention is It~ ' by the formula:

AlRI23.xQx wherein Rl2 ;~ y represents branched and, ' ' ' (C~-C20) alkyl, (C6-C24) aryl, (C7-C20) aralkyl, (C3-Clo) cycloalkyl; Q is a halide or selected from chlorine, fluorine, bromine, iodine, branched and s unbranched (Cl-C20) alkoxy, (C6-C24) aryloxy; and x is 0 to 2.~, preferably 0 to 2.
RC;~ GLjV~ or~:~nr.~l compounds include trialkyl~
suchasLl;..l.,lly' ' Llh,~l~y' ' tripropylaluminum, L-;;su~.lv~,y~_luminum, L~ vl,u~ylGluminum, tri-2-m~Ll.yll,uLylGLIlll;llulll~ tri-3-10 lu~.Lllylbu~yldlulll;l~ul~, tri-2-meLl,yl,u~,.,Ly' ' tri-3-yl~ LylGluminum, tri-4-",.,.hyl~ ..yl~lu...i"u"" tri-2-y" y~ ~Ulll;IIU.. , tri-3-mr,LI~yll.~ Ayll ~ ' , Lliu~,Ly' ~ , tris-2-norbomylaluminum, and the like.
Dialkylaluminum halides such as d;.~-LIIYIGIUIII;IIIJIII chloride, diethylaluminum chloride, d;;~v~ul~ylGluminum chloride, d;i tubuLy' ' chloride, Gnd the like.
Monoalhy' ' in~lm dihalides such as ",.,."y' ' dichloride, ~:LIly' ' dichloride,~ll,y' ' diiodide,l.,ul.yl_h",l;..u",dichloride, ;~ul"u~.y' ' dichloride, butylaluminum dichloride, ;.,vl,uLy' ' 20 dichloride, and the like.
Alhy' ' I ' ' ' such as ~ Lhy' ' , ' ' ', r,LllylGlulllillulll 5P~]llir.hltuj/1P, ~lulJy , I ~, isobutylaluminum cP~r~ hlrlri-lP, and the like.
In the practice of the present invention, the catdlytic system obtdined 25 from the Group VIII transition metal source and the ulL, component can be effectively used, however, if desired, the catalyst system employed can optionally contdirl a third component or third ~ r ' ~
Examples of such third ~ ~ ""l"'" ' - are Lewis acids such as the BF3 et~erate, TiCI4, SbF5, tris(p~,lnuu.v~ n.yl)boron, BCl3, B(OCH2CH3)3;

2f 74756 strong Br0nsted acids such as l~ uulucl~Lul~onic acid (HSbF6), HPF6 hydrate, Lli~luuluc..~Lic acid (CF3CO2H), and FSO3H-SbF5, H2C~SO2CF3)2 CF3SO3H, and ~ ..lr~...;r acid; h~''6f ' compounds such as In.~.,Llvlucc~..v..c, h~".a[luulua.,etv~l~, 3-butenûic acid-2,2,3,4,4-S ~ " ubulylester, ~ dlluulu~;h~Lsulc acid, h~UII1UUIU;~U~ U~JCIIOI~ andchloranil, i.e., Cl~CI
CI~CI
electron donors such as phosphines and phosphiles and olefinic electron donors selected from (C4-CI2) aliphatic and (C6-CI2) cyrlr,~lirh~ic diolefins, such as butadiene, cyclno~t~ n~, and llu~bvlllcl;.,l~c.
AcidityofstrongBronstedacidscanbegaugedbyderr~mininrtheir Hammet acidity function Ho. A definition of the Hammet acidity function is found in Ad~anced Inorganic Chemistry by F. A. Cotton and G. Wilkinson, Wiley-llll~,c-,l~ , 1988, p. 107.
As set above the neutral ligands can be employed as optional third 15 ~ as electron donating rnmrol~n~lc In one ~ ho~ the ~ catalyst system can be prepared by a process which comprises mixing the catalyst ..~,...1-.,,.. - ~, i.e., the Group VIII transition metal compound, the o~ n~ compound, and third component (if employed), together in a llydlu~.cll/oll or hal~ dlu..~ vll solvent 20 and then mixing the premixed catalyst system in the reaction medium comprising at least one l~ulbvl~ e functional monomer. Alternatively, (assuming the optional third component is utilized), any two of the catalyst system ~ ~ . can be premixed in a ll.yJIul,a~bull or halully.llu..cll,un solvent and then introduced into the reaction medium. The remaining catalyst 2s component can be added to the reaction medium before or after the addition of the premixed .. ~.1,.,~ .llc WO 95/14048 PCI'/US94/13166 In anotber c ~,l ,,,.l;..,~ .,l, the catalyst system can be prepared in situ by mixing together all of the catalyst l,u---r in the reaction medium. The order of addition is not important.
The reactions of the present invention are carried out in an organic 5 solvent which does not adversely interfere with the catalyst system and is a solvent for the monomer. Examples of organic solvents are aliphatic (non-polar) llyJlu~ L~ull, such as pentane, hexane, heptane, octane and decane; alicyclic ILlyJlu~ ulls such as ~;Y~ r and ey~ ~ L ~; aromatic l~yJ~u~ LIull~
such as benzene, toluene, and xylene; I - ' ,, ' (polar) llyJluL~ubu~ such as 10 methylene chloride, ethyl chloride, I,l-J~ lul~ ' 1,2-d;~ hJIu~ill~.~, 1~2-dL,IIlulu~.Lllyl~ c, I-chlulu,u~ r , 2-~llUIU~ r , l-chlorobutane, 2-~ uL ~, I-chloro-2~ llyll~luLclc, l-chlo~r , ~' ~ uL~ Ic, O-J;cl~lulub~ e, m-dichluluL,.,.,~.,.Ie, and p-JL,llluluL~
The choice of reaction solvent is made on the basis of a number of 15 factors including the choice of catalyst and whether it is desired to run the pOIylll".;L~ as a slurry or solution process. For most of the catalysts described in this invention, the preferred solvents are chlorinated l~yJlu~,~lbusuch as methylene chloride and 1,2-J;~ lul~ ' with simple llyJlu~uL~O,~s being less preferred due to the resulting lower conversion of the norbornene 20 monomer(s). Surprisingly the inventors have discovered that certain of the catalyst systems, most notably catalysts based on Group Vlll metal compounds and&l'~y' ' halides, specifically, " y' ' dihalides, (e.g., c~llyl.dulll;llulll dichloride), also give excellent results (and high monomer conversion) when run in simple liyJlu~bu.. ~ such as heptane and cyc'~L
25 The solubility of the pOIyllùl IJOII~ ,... described in this application is highly dependent on the catalyst employed; for example, nickel-based catalysts afford polymers soluble in simple llyJlu~bù.l~ while palladium-based catalysts typically afford essentially insoluble polymers (soluble only in hot o-J;eL~u U~ ,). All of the ~IulL,ull..",~-based polymers are insoluble in 1~2-30 dichloroethanq or Jh,lllulull~ alle at ambient i , c~ making these ideal diluents for slurry ~vl.~ aliul, processes (i.e., poly --i7:~ti~n~ in which the polymer is formed as a precipitate) regardless of the choice of catalyst type Using o-,li,,l.L,.ul,~ ,c or ll.~JIu~,albu~ such as ~. ' ' , heptane or toluene in ,UllliJ IdLiUII with suitable nickel-based catalysts results in the solution 5 I,ol.~,ll.,l;~iuu of IlUlbulll.,llC~ (i.e., pùl.~ ;. ,.... in which the polymer is formed as a solution).
The molar ratio of total monomer to Group VIII transition metal for the single and ' . catalysts can run from l,OOO:I to 100,000:1, preferably 1,000:1 to 20,000:I, and most preferably 3,000:1 to IO,OOO:I.
In the ' , catalyst systems, aluminum metal to Group VIII
transition metal molar ratio ranges from less than or equal to 100:1, preferablyless than or equal to 30:1, and most preferably less than or equal to 20:1.
The optional third component is employed in a molar ratio to Group VIII
transition metal ranging from 0.25:1 to 20:1. When acids are employed as third - -~r - . the acid to Group VIII transition metal range is less than or equal to 4:1, preferably less than or equal to 2:1.
The t~,l..,U~,.d~UI~ at which the pOIyll.~ aL;ull reactions of the present invention are carried out typically ranges from - I OOoC to 120nC, preferably -40OC to 90C.
The optimum t~,~.lp~,ldLu.~ for the present invcntion is dependent on a number of variables, primarily the choice of catalyst and the choice of reactiondiluent. Thus, for any given IJulyll~ .aL;ull the optimum; . ~ will be c,~.. "y determined taking these variables into account. To exemplify such an ~ I process, we have discovered that (when using a 25 m~ ..J .~1 catalyst made by reacting nickel ~;Lhy~ with h~"~dnuul, ~ acid, followed by boron trifluoride etherate and triethylaluminum) even though catalyst activity is extremely high over a wide rarlge of t~ ,.aLul ~ in both dichloromethane and 1,2-l' ' ' u~,;hall~, there exists an optimum in tl,~lp~.ldLUI~ if a freely stirring slurry is desired. In the case 30 of dichlu~ ,L~.. ~.c the optimum ~ is 1 0C to 20C while in the case WO 95/14048 ~ 1 7 4 7 5 6 PCIIUS94/13166 of 1,2-d;~hlul~ ' the optimum i . c is 30DC to 40DC. Operating below this optimum tends to result in a slush or cake which, while still resulting in very high monomer conversion with control of molecular weight, is less desirable to process in most commercial hardware. Operating above the S optimum ~...p. c, while still giving a very high polymer yield with controlled molecular weight, results in particle ~g' dL;ull or even a fused mass. When running a continuous process it is desirable to operate within this t~ ItUI C window; when operating a batch process it is preferred to initiate the pOIyll..,l; ~.aLiull below these t~lllp~ Lul C~ and allow the exotherm to raise tbe 0 process t~ p~.aLulc to within the optimum range.
Other solvents and other catalysts each have their own preferred ~ UI C ranges depending on the criteria against which the ~Ulyl~ aL;ull rulll-a 11~ (e.g., conversion, rate, etc.) and parameters (e.g., ease of stirring a slurry, solution viscosity, heat removal, etc.) are being measured.
1s -rO control the explosive speed of the l~uly reactions carried out with the single or ~ catalyst systems of this invention, a suitable monomer to catalyst molar ratio is selected, the reactor can be cooled to slow down the reaction, and the reaction can be carried out in a high boiling solvent. By high boiling solvent is meant that the solvent has a boiling point 23 above the pOlylll~ aLiull ~CIIl~J~,la~Ule. If a pressure reaction vessel is employed to contain the l~uly~.. . iLaLiull reaction, the foregoing . ' do not have to be taken into account In one ~mho~ nt of the . ' r ' catalyst system of the present invention, a typical catalyst system comprises a Group Vlll transition metal salt, 25 e.g., nickel eLIly'~ , an or~n. ~ nnin~ compound, e.g., u ;.,LIlyl~lulllillulll~ and a mixture of optional third , e.g., BF3-etherate and II~AaIIUUI~ ~ acid (HSbF6), in a preferred molar ratio of Al/BF3 etherate/Ni/acid of 10/9/1/0.5-2. The reaction sequence is written as follows:

WO 95114~48 2 ~ 7 4 7 5 6 PCTrUSg4113166 Nickel ethylhexanoate + HSbF6 + 9BF3-etherale + 10 triethylaluminum ~ active catalyst Inanotherr"lv,l;, ~ :ofthe. ~ ;.. ,p.. , :catalystsystemofthe invention the optional third component is a I ' ~, ' compound se~ected from s various ~ ' ,, ' activators A typical catalyst system comprises a Group VIII transition metal sadt, an u.v ' and the third component g~- ' compound shown in the reaction sequence written below Nickel ,~u~v~Y' + tri~Ll.yldLJ~ ul~ + chlorardl >
active catalyst In still another ~mho~lim~nt of the m~ l l - catalyst system of this invention no third component is present The catalyst system comprises a Group Vlll metal salt and a monoalkylaluminum dihalide component run in a llydluu ubùll or l~dlvlly~lv~ubvll solvent as shown in the reaction sequence below Nickel ethylhexanoate + ethylaluminum dichloride +
llyd~u~, ul,on solvent (heptane, ~:y, ' ' ) ~ active catalyst By llu~v~ ..c-functional or NB-functional is meant that the monomer isual,L~ by containing at least one norbornene-functional group in its 20 swcture including IlVdJVIII~ as identified by the formulae below which can be substituted or 1 . ~
-WO 9S/14048 21 7 4 7 5 ~ PCTNS94/13166 wherein "a" represents a single or double bond R~ cacllLa~ e monomers are identified by formulae VII and VIII as follows ~- R4' ~' VII VIII
s wherein R4, R4 R5, and Rs ;"~ ly represent hydrogen, halogen, branched and ullblrllch~ (Cl-C20) alkyl, branched and ulll,.~ul.,l.~d (Cl-C20) haloalkyl, substituted and ~ (C5-CI2) cycloalkyl, (Cl-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl, (C7-CIs) aralkyl, (C7-C~5) haloaralkyl, (C3-C20) alkynyl, branched and unbranched (C3-C20) alkenyl, o provided the alkenyl radical does not contain a terminal double bond, that is the double bond in the radical is an internal olefinic bond, or vinyl; R4 and R5 when taken with the two ring carbon atoms to which they are attached can represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms; "a" represents a single ~r doublebond, and Z is I to 5. It should be noted that when R4, R4 R5, and R5 represent an alkylidene radical the carbon atom to which the alkylidene radical is connected does not have another substituent, and when "a" is a double bond R4, R4' R5, and R5' cannot be alkylidenyl.
Examples of norbornene-functional monomers include nu.~ . --r, 2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidenyl-2-norbornene, ~lylllolbulll~lle~ di-:y~ yllu~ ,yl l-r ,yl Ir~.ll~.l.~. ~IIF~ llyll~Ll~ hdFC~PnF~ t~ rlr. _rl ..F
~ 11 lly; ~ ,y. 1.~ yl~ y~ Ih.l.. -lF~---, ethylidenyl WO 95114~148 2 1 4 7 5 6 PCT/lTS94113166

4'7 t~.LIc~,y .Ir~ F, pl~...y' y~,lOd~.~,c~, trimers of cyrln~ t~ nr (e.g., s~ ' and ~laylll~ll~..l;~.rl trimers) and I ' O ' nulbu~ d;~.., and norbomene-functional monomers wherein R4, R4' Rs, and R5' :- ' . ' '~
represent hydrogen, halogen (e.g., Cl, F, I, Br) arLd fully 1~ , ' alkyl S groups of the formula C"F2~ wherein n represents the number of carbon atoms from I to 20. R~ Liv~ l ' are Ll;n~oll ~1, -C4Fg. -CloF2l-and -C20F4,.
The ~ 3 ' l~u~bu~ ..c-functional monomers can be synthesized via the Diels-Alder reaction of ~,y~ ; -r with the appropriate ' ' ,, ~o ,1 -~phih~ as shown in the following reaction schemes:

+ F3C-C--C-CF3 CnF2n+~
+ R62C = CRS~CnF2n+l ~ ~RR66 wherein R6 j~ , represents hydrogen or F and n is I to 20.
The chain transfer agent or CTA is selected from a compound having a non-styrenic, non-vinyl ether terminal carbon-carbon double bond wherein at least one of said carbon atoms in said carbon-carbon double bond has two - 15 hydrogen atoms attached thereto, said chain transfer agent excludes conjugated dienes. By non-styrenic, non-vinyl ether is meant that compounds having the following structures are excluded from the chain transfer agents of this invention:

WO 95/14048 2 1 7 ~ 7 5 6 PCIIUS94/13166 CH2 = C(R or H), CH2 = CH
A OR
wherein A is an aromatic substituent and R is l~ydlu~ b~
The preferred CTA compounds of this invention are represented by the following formula:
R' CH2 = C
R"
wherein R' and R" ' l ' lS~ represent hydrogen, branched or I
(Cl to C40) alkyl, branched or U.lb ' ' (C2 to C40) alkenyl, halogen, or the group 1 !; -CH2(CH2)n-OR- -CO2-R--Si (OR-)3 r7 -(CH2 )~-Si(OR-)3 -(CH2)-(CH2)"-B ~'(7 -(CH2)n-OSi(R-)3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2) ~(CH2)n~X
2!j O

$~

wo 95/14048 2 1 7 ~ 7 5 ~ PCTIUS94113166 wherein R'~ is branched or u,~b.ol~,h.,l (Cl to C~0) alkyl, preferably methyl orethyl, branched or l ' ~ ' (C3-C90) alkenyl, substituted or ., .~
(C6-Cl5) aryl wherein said b. - if present are selected from branched or ' ~..,h~d (C~-C10) alky or haloalkyl, and halogen, X is chlorine, fluorine, S bromine or iodine, and n is 0 to 20, preferably I to 5.
Of the above chain transfer agents the ~-olefins having 2 to 10 carbon atoms are preferred, e.g., ethylene, propylene, 4-methyl-l-pentene, I-decene, 1,'7-octadiene, and 1,6-octadiene, or isobutylene.
The choice of the optimum olefinic chain transfer agent is dependent on 10 a number of factors such as the choice of catalyst type, the process conditions (le~ ul~, solvent, etc.), the presence or absence of alkylaluminum cocatalyst and the nature of the olefinic end group desired in the resulting polymer, oligomer or l.lac,lul.lol..~,.. The level of the olefinic chain transfer agent required for a given molecular weight is dependent on all of the above variables as well 15 as the type of olefinic chain transfer agent selected.
While the optimum conditions for any given result should be CA~ IIY determined by a skilled artisan taking into the account all of the above factors there are a number of general guidelines which can be ~,u~ / utilized where ~pl~u, One observation that we have made is 20 that the efficacy of any given chain transfer agent is highly dependent on the selection of Group VIII transition metal used in the catalyst. Notably nickel catalysts are more sensitive than other metals (i.e., a given level of olefin causes a bigger decrease in molecular weight when applied to a nickel catalyst than when applied to, for eAample, a palladium catalyst). r.. ~.. 0.l;, we have 2s learned that, in general, Il-olefins (e.g., ethylene, propylene, I-decene, 4-methyl-I-pentene) are the most effective chain transfer agents with 1,1- 1 ~ ~
olefins (e.g., ;~ubul~ c) being less efficient. In other words, all other thingsbeing equal, the l,UlI-~ iUII of isobutylene required to achieve a given molecular weight will be much higher than if ethylene were chosen. Styrenic WO 95/14048 2 1 7 ~ 7 5 6 PCrrUss4/l3l66 olef s, conjugated dienes, and vinyl ethers are not effective as chain transfer agents due to their propensity to polymerize with the catalysts described herein.
The CTA can be employed in an amount ramging from about 0.10 mole % to over 50 mole % relative to the moles of total NB functional monomer.

5 Preferably, the CTA is employed in the range of 0.10 to 10 mole %, and more preferably from 0.1 to 5.0 mole %. As discussed above, depending on catalyst type and sclla;LiviLi~ CTA efficiencies amd desired end group, the dLiU~
of CTA can be in excess of 50 mole % (based on total NB-functional monomer present), e.g., 60 to 80 mole %. Higher of CTA (e.g., greater than 10 100 mole %) may be necessary to achieve the low molecular weight I,o,li~ of this invention such as in oligomer amd Illr~ r It is important and surprising to note that even such high of CTA do not copolymerize into the polymer backbone but rather insert as a terminal end-groups on each polymer chain. Besides chain 5 transfer, the process of the present invention affords a way by which a terminal ~-olefinic end group can be placed at the end of a polymer chain.
The pOlyl-ull,vl-..,.l., materials of both the single and catalyst systems can be classified by their solubility . .~ ;rr In general, the nickel-catalyzed materials are readily soluble in lly~u~ Jlls such as 20 Cyl l( ~ at room t~ .,.dLUlC even at molecular weights greater than 500,000. The palladium-catalyzed materials are markedly less soluble- In general, these materials must be heated in chlorinated aromatic solvents such aso-dichlolul,~,.-L~,I.c or trichlulul,...lL~ , before any significant solubility is noted.
The differences in solubility are due in all probability to differences in 25 llli~l u:,LI U1LUI ~ between the two types of polymers.
Carbon-13 NMR a~ ,Llusl,u~Jy allows one to investigate the polymer u:~LIu~.Lulcoftheadditionpolymersofthisinvention. Thel3C-NMRspectra in Figures 4 through 7 were measured in a mixture of deuterated trichlulub~.L.,llcA:/.,.lL.,lle at 363DK. In Figure 4 is presented a spectrum of a 30 sample of rlulbu~ e addition polymer synthesized using a single-component ~ wo 95~14048 2 ~ 7 ~ 7 ~ 6 PCr~US94/13166 catalyst system, [(crotyl)Ni(COD)]PF6. In Figure 5 is presented a spectrum of an addition polynu,l,ull.~"~e made using the palladium analog, - [(crotyl)Pd(COD)]PF6. Note that the two spectra are entirely different indicating that the polymer mi-,.u,L U~tUI~ depends, in this case, on the nature of s the transition metal used in the pUIy....,.;~lUùll. This trend also is apparent for the ' . catalyst systems. For examp]e, in Figure 6 is presented a ,ul ~ciuLai; ~ ~ spectrum of an addition pol~ bulll~ c made using a Ni(II) 2-~lhy" , triethylaluminum, l~ lu~ u~c~,tu..~ catalyst system. In Figure 7 a spectrum of an addition pùlyllull)ull~ made using a Pd(ll) 2-Lr" ~ h.~ll~l~lLIlll;llllu, hexa~lllul, - catalyst system is presented. Again, the nickel-catalyzed polymer is entirely different from the palladium-based material. We have found that ligands also affect the polymer 1l,;." u~ u~ le. For example, the polymer isolated from a PdCI2(PPh3)2, triethylaluminum, I.~ ,.,lllu., - catalyst system exhibited a ~3C-NMR
15 spectrum different from both the Ni and Pd 2-~ y" systems mentioned above.
By comparing the '3C-NMR spectra of nickel catalyzed ~ul~llu~vl~..,.~e to the 13C-NMR spectra of palladium catalyzed polyllulbu~ .e, we found that the nickel catalysts give ~Julyl.ul~ull.~l.~ with a distinctive resonance in the CH
region between 45 to 55 ppm, with a major intensity peak at about 47.5-48 ppm as shown in Figures 4 and 6. In contrast, the '3C-NMR spectra of palladium catalyzed poly~u~bul~,~,..e (Figures 5 and 7) are devoid of a major intensity resonance peak at 48 ppm.
IQ Figure 8 there is shown lH-I3C (proton-carbon) N~ correlation 25 spectrum (measured in deuterated l~tl ' ' , ' at 323 K) of a poly~lù~bu~ ,..c prepared by a nickel catalyst in the presence of a CTA (i.e., ethylene). The region between 45-55 ppm w. . ~ ulld~ to the resonance of a norbornene non-bridgehead CH group. This region shows a narrow multiplet at 45-50 ppm (centered at about 47.5 ppm) amd a broad multiplet at 50-55 ppm.
30 These multiplets exhibit l,Ullt~pUllU .lg proton-N~ resonance at 1.6-2 ppm amd WO 95/14048 PClllJS94113166 21 7475~ --1.2-1.6 ppm It~ y. The bridgehead CH group exhibits 13C-NI~
resonance at 3 8-42 ppm ,UI I e~,uulld;llg to a proton-NMR resonance at 1.75- 5ppm. In addition, two different types of vinyl end-groups are noticed in the IH-13C-NMR correlation spectrum, one having a CH resonance at 142.4 ppm in the 5 13c N~ spectrum and a proton resonance at 5.90 ppm, the other having a CH
resonance at 141.8 ppm in 13c and a proton resonance at 5.73 ppm. When propylene is employed as the CTA, the end groups observed by 13C and IH-NMR correspond to the following structures:
poly(NB~ and poly(NTB~cH3 cis and trans For longer CTA's the end-groups observed by 13C and IH-NMR
10 correspond to these strucnlres:
pol,~ (NB~ R and poly(NB~R
cis and frarzs cis and trans -The ethylene and isobutylene CTA's are unique in that only a single well-deflned end-group is observed.
pol~(NB~ and poly(NB~Z

~ wo 95114048 2 ~ 7 4 7 5 6 PCT/U594/13166 .
The foregoing structures exhibit resonances that are ..~ ;C of olefinic end groups These end-groups are easily identified and interpreted by those skilled in the art.
While not wishing to be bound by a specific theory of invention~ we 5 believe that the difference in IOh,luaLlu~,~ul~ as confirmed by the spectra isattributable to dif~ering tacticity (e.g., diisotactic vs d;l~ ,uL~:~Lic vs d;:,~lliiuL~Lic) andlor differing repeating unit ~ in the polymer backbone (e.g., 7t3~ . II VS 2~7~ ;11lll -- ). We believe that the nickel catalyzed polymers of this invention contain 2.7-repeating unit rll~ IIA;II.. ~I in addition to the typical '2,3-repeating unit c ~. sel forth in the prior art.
~ vs -- n -- -- n 2,7 el.c' ~ 2,3 ~
-The foregoing 13C-NI\~ spectra are It~ a~ L_~iv~: of L _~ ~
pol) l.ù.~u...~l.e homopolymer. As one of ordinary skill in the art will recognize the multiplet peaks can shift upon adding ~ ' - and/or -r units 21 74756 ::

into the backbone. According~y, it will be evident that the 13c and IH-NMR
spectrum of polyl.ull~vl~ c llull~v~vl~ can be utilized as a . l "~ " ;, ~
tool for the presence (including the type of) or absence of an olefinic end-group as well as differeQces in IlliClu~Llu~lulc s In the following illustrative examples, various complex catalysts are p}epared and used as illustrative examples in the preparation of l~u~v~oly of NB and substituted NB monomers, and of copolymers thereof.
FY~n~lPC of Pre-formP~I SblplP Con~?onPn~ C~ts~ly~tc Catalyst A: [(T~3-crotyl)(cycloocta-l,S-diene)nickel]
II~AdI1UUI ulJllv~illaLe To a flask containing bis(cycloocta-1,5--liPnP)~irkPI (2.75g, 10 mmol), was added a solution of crotyl bromide (1.35g, 10 mmol) and butadiene (2.5g) in toluene (24 ml). A deep-red solution of (crotyl)~ hull"u..l;de dimer resulted.
After 2 hours at ambient t~ UlC the solvent was removed under reduced 15 pressure. To the resulting powder was added a solution of 1,5- Cyl '~c (3.6 ml) in t~bàllydlurul- (THF) (32 ml). After cooling to O~C thallium h~[luo~, ' , ' (3.5g, 10 mmol) was added and the resulting mixture allowed to warrn to ambient t~ dLule (21~C) and be stirred for one hour.
The solvent was stripped away under reduced pressure and 20 dh,l~lul~ (24 ml) was added. Insoluble thallium bromide was removed by filtration (under nitrogen) to afford the complex catalyst product as â solution in dh,lllulu~. ' - This solution was reduced in volume and d;.,;l.jh,~.~ was added. The catalyst was washed thoroughly with d;.lh~h,~l~,., then dried under reduced pressure, to afford the catalyst as ~ .3 g of orange crystals. This catalyst, 25 identified hereafter as "catalyst A" is referred to as [(~3-crotyl)(cycloocta-1,5-diene)nickel] II~ d[luu~u~
Catalyst B: Tetrakis(acetonitrile)palladium (II) t~h~uulubul~l~e Purchased from Aldrich Chemical Company, used a~c received.

~ WO 95/14048 2 1 7 ~ 7 5 6 PCTNS94J13~66 ~i5 Catalyst C: [(~3-crotyl)(cycloocta-l,S-diene)nickel] tetrakis(3,5-~;,,(L illuù~ull..,Lllyl)-phenyl) borate.
3,5-b;..~l;lluu~ul~ llyl)bl.. .1,. .., - (50g, 170 mmol) in (lieLl~yh,;~
(150 ml) was added slowly (over about 2 hours) to magnesium powder (5.1 g, 5 210 mrnol) followed by ref~uxing for about 3 hours to give a dark grey solution.
Sodium t~,ualluulul)ul (3.4g, 3û mmol) was added and the resulting slurry was refluxed for 24 hours. The refluxed slurry was added to an aqueous solution of sodium carbonate (75g in I liter), stirred 20 minutes, then filtered.
The aqueous layer was separated and extracted 4 times with d h..hjl.,L~I~,. (200 ml so aliquots). The ether layers were combined and dried over sodium sulfate and treated with dc~,ulul i~illg charcoal. The solYent was removed under high vacuum to afford an amber slush. Methylene chloride was added until the solid was thoroughly wetted, then chloroform was added and the resulting solid was filtered and dried. An essentially ~lu.ulli~ulive yield of recovered sodium 15 tetrakisr3,5- bis(lJ inuul ~ yl)phenyl]borate ( 18 g), was in the forrn of a light tan, crystalline solid.
COD (1.3 ml) in THF (16 ml) was added to u~ul~ ,L,l~lul~ e dimer (0.5 g, 1.75 mmol). The mixture was cooled to 0'C and the above described sodium tetrakis[bis(l.inuulu,l.~,llyl)phenyl]borate (3.1 g, 3.5 mmol) was added.20 The mixture was warmed to room t~,..,l,~,...~l ~ and stirred for 1 hour to give a clear, dark brown solution. The solvent was removed under vacuum and methylene chloride added to give a slightly hazy solution. The solution was filtered to give a clear, amber solution. The solvent was removed under vacuum, washed three times with hexane, filtered and dried under high vacuum 25 to afford the product, [(l~3-crotyl)-(cycloocta-l,S-diene)nickel] tetrakis(3,5-bis(LIinuulu.G.,Lllyl)phenyl)borate (3.42 g) as a pale yellow powder.
Cataiyst D: [6-methu~yl.ull,olll~.. 2-yl-5-palladium(~,y. I~U~ 1 )]
h~ Uulr WO 95/14048 ` PCT/US94113166 217~756 To a flask containing (llu~bu~ llc)palladium dichloride (I.û g. 3.7 mmol) and methanol (20 ml) waS added a solution of potassium methoxide (0.256g, 3.65 mmol) in methanoi (20 ml), the addition being made at -78C.
After an hour at that t~ ul e the mixture was allowed to warm to ambient S tClll~ Lul ci and was filtered and dried to afford a light green-brown solid uAy~lùlvvlll~ n~hlori~ dimer). A portion of this material (0.5g, 1.65 mmol) was placed in a stirred flask with T~ (50 ml) and COD (2 ml). Then a solution of thallium h~,Adl'iuul~r' , ' (0.57g, 1.65 mmol) in Ir LI ' ~y~ilurul~ul ( 17 ml) was added ûC. After warming to room U,.II~J.,.dlUI t: the 10 solvent was removed and then 1,2-dichloroethane (60 ml) was added to give a yellow solution and a pale colored precipitate (thaliium chloride). The solutionwas filtered and the solvent removed under high vacuum to afford tile product, identified hereafter as catalyst D, and referred to as mr,~ilu~llulbvll~
palladium(cynlnnrt~r;iPnr)] hexafluul~ I ' (structure below) as a greenish solid.
OMe +
.~Pd GJ PF 6 Catalyst E: [(7~3-crotyl)(cycloocra-1,5-diene)palladium] h~ iuul~, ' I ' To a 500 ml l~ .r.,. fiasl; was added sodium chloride (2.95 g, 50.4 mmol), palladium dichloride (4.44 g, 25.3 mmol), methanol (150 ml) and water ('.''5 g, 125 mmol). The resulting suspension was stirred at a!nbient 20 ~ Ul ~ for an hou~ affording a dark-brown solution. To this solution was added crotyl brûmide (7.6 ml, 74 mmol).

~ WO95/14048 2 ~ /~ 7~ PCT/USY4/13166 The vessel was then pur~ed with carbon monoxide for 30 minutes (at a rate of 40 ml per minute). After several minutes the solution became lighter in color with a noticeable amount of a precipitate. The mixture was then poured into water (I liter) affording an amber-brown colored solid. The miYture was S extracted with 3 aliquots of chloroform (total volume 500 ml). Removal of the ' .
chloroform from the resulting solution afforded a yellow green solid which was by proton NMR methods as (Tl3-crotyl)palladium halide dimer.
The yield was essentially quantitative. This yellow-green solid was dissolved in.ucll,ydlu~ul~ll (1OO ml) and 1,5-cy~ l~.o l~ i;. -- (8.7 ml) was added. Thereafter 0 thallium h.. ~ UOlU~ ' (8.8 g, 25.3 mmol) was dissolved in THF and both solutions were cooled to 0C. The thallium ll~dllUUI~ ' solution was added slowly to the solution of the palladium compound. An immediate off-white precipitate was observed, the amount of which increased as mûre of the thailium solution was added.
1s After the addition was completed the ice-bath WilS removed and the suspension was allowed to warm to ambient t...~ , with stirring. The THF was removed under vacuum and d;~!ik)lull~ihr~ ( 100 ml) was added.
The mixture was filtered and the solution was ~ ' to a volume of about 40 ml. To this solution was added d;~LIIYh~ (100 ml) which resulted in the 20 formation of light yellow-white crystals in high yield. The crystals are identified hereafter as catalyst E, and referred to as [(~3-crotyl)(cycloocta-1,5-diene)-palladium] h~riuu~ ' The material was .,11~.,.,.~ ,1 by NMR ~ lUi~U~JiC methods.
EY:~n~l- of a two-~nnu~n~nt ~t~iySt With ~O nnn ~t~ly,c~t 25 Catalyst IF: nickelethylhexanoate: f~rst component, and MAO second Nickel(lI)~,ill~" , identified hereafter as Catalyst F, is obtained as a solution in mineral spirits and was used, as received (from OMG Inc.) in ..~..1.l,;. -l;.,,l with MAO as cocataiyst.

WO 95/14048 PCI'NS94113166 21747~ --A~-iitinn~l FY~ 'C Pre-fo~rn~i ,Si~ Cnn~on~nf (`~ lYSts Catalyst G: r~3, Tl2, TI2-dOdeCa-2(E)~6(E)~IO(Z)-tr;ene-I-YIn;CkeI
L~AdnU~JI Ur The synthesis of this catalyst, the structure of which is represented 5 below, is described by R. Taube et al., Makromol. Chem., Macromol. Symp., 66, (1993) 245-26û and in references cited in Taube et al.
_~_ +
Catalyst ~i: Tetrakis(octanonitrile)palladium (Il) hu.lnuu.ui"
Heptylcyanide (octanonitrile) (40 ml) was added to tetrakis(acetonitrile)pal~adium (Il) I~LldnUUlUbU~d~ (1.5 g) and the resulting 10 slurry was allowed to stir for 4 hours, after which time the solid had dissolved, affording a red solution. Hexane (60 ml) was added and then the hexane and excess nitriles were remûved under high vacuum, with the fiask being heated on a steam bath, to afford the catalyst product (which was washed 3 times with hexane and redried), as a red, viscous oil identified as [tetrakis(octanonitrile)-15 palladium (Il) tetrafluoroborate].
Ca:alyst 1: [(l13-cyclooctenyl)(cycloocta-l,S-diene)nickel] tetrakis(3,~-bis(trifluulu.,.~ yl)phenyl) borate in toluene To a mixture of bis(~;yuluu~ladh~ )nickel (0.011 g, 0.04 mmol) and N,N-dimethylanilinium- 3,~-bis(L-inuu.~,..,~, ilyl)-phenyl)borate (0.046 g, 0.047 20 mmol), was added toluene (2 ml). This resuited in an orange solution of the catalyst which was used as such.

2174~ ~
WO 95114048 5 ~) PCT/US94113166 Catalyst J: {CH3Ni(C2H4)23- I,i{(CH3)2NCH2CH2N(CH3)2}2~, an anionic catalyst.
This compound was made according to a method taught by Klaus Jonas et al Augew. Chem. Int. Ed. Engl., 15. 621-2 (1976).
S Catalyst K: Bis(.,3-allyl nickel l~inuu~ua~el.~t~,) This compound was made according to a method taught by F. Dawans et al J. O.~, ~~ ' Chem., 21, ^~59-61(1970).
Catalyst L: .~3,r~2,~î2-dodeca-2(E),6(E),lO(Z)-triene-l-ylnickel on a support, forming an active support.
The synthesis of this catalyst is de3cribed by R. Taube et al., r ~
Chem., 194, (1993) 1273-88 and references therein. The active support, AIF3, was prepared by reacting BF3-etherate with triethylaluminum and isolating the product a3 a white solid. This support wa3 reacted with [Ni(CI2Hl9)]O3SCF3 at ambient t~ u. e in toluene for 24 hours. The ilu~ ulu~;ù~ of the nickel compound was originally yellow in color but became colorless as the reaction proceeded, affordin~ the supported catalyst as a yellow-brown solid which was filtered and dried. The catalyst (L) wa3 stored, under nitrogen as a yellow-brown powder.
Catalyst M: .,3-crotyl(cycloocta-1,5-diene)nickel on an active support Catalyst A (5mg) was dissolved in 1,2-dichloroethane (20 ml) and added to an active support (200mg) (obtained from Witco and used as received) consisting e3sentially of an alkyl All Im innY--^ (MAO) on a silica support. Theactive support contained 7.4 % by wt aluminum. The resulting mixture was stirred at ambient ~elllp~ UI ~ for 5 minutes and then used, without isolating, as 2s a supported catalyst.

Wo 95/14048 PCT/US94/13166 ~
2~ 74756 Catalyst N: Mangarlese Lin-AII
This material, manganese Lin-AII (a long chain mangamese v~bu~
sa~t), was obtained as a solution in mineral spirits (containing 6% wt Mn) From OMG Inc., amd was used as received in "",l,~ with MAO as cocatalyst.
5 Catalyst O: Molybdenum Hex-Cem This material, molybdenum Hex-Cem (a long chain IllUIyv~dvllvlll carboxylate salt), was obtained as a solution in mineral spirits (containing 15 %
by wt Mo) from OMG Inc., and was used as received in vGvlllb;ll.ll;u.l with MAO
as cocatalyst.
10 E~ample 1: Catalyst A with d.~' ; . . ~ and decene-l as Chain Transfer Agent "CTA"
To a 3-liter wide-mouth glass flask equipped with a mechanical stirrer were added the following materials in the given order: norbornene (163g, 1.73 mol), 1,2-dichloroethane (2,950g, 2,341 ml), S-dvvy' vv~ v,,v (71 .7g, û.3 1 mol), I-decene (3.57g, 4.8 ml, 0.0255 mol) and then catalyst A (û.187g, 0.51 mmol) dissolved in d ' ' ull.cthane (2 ml). I ' 'y after adding the catalyst to the stirred solution polymer started forming and the reaction ~AULI-. -1 to 44DC. The mixture was allowed to stir for a total of 6û minutes before methanol (I 0û ml) was added to destroy the catalyst. The polymer cake 20 was added to stirring methanol to afford the product as a white powder which was filtered off and washed with methanol and then ethanol. The polymer was then dried, dissolved in vyvlo~ (4 liter) and then ~ , ' by addition to acetone. The polymer obtained was filtered off, washed with acetone and dried under vacuum for 16 hours at 1 50C. The resulting polymer weighed 1 88g 2s (8û% isolated yield), showed a Tg of 2820C and molecular weight (relative to polystyrene standard) of 167,000 (Mw) as determined by GPC methods (Mn was 79,400). In addition to the reduction in molecular weight, the l-decene caused the polymer to be terminated with an olefinic group observed by proton NMR

~ WO 95/14048 2 1 7 4 7 5 6 PCT/ITS94113166 u,uy Resonances are observed at 5.35 ppm relative to t~ y' ' using a solution in perdeuterated o-dichlo-ul,~,.~.,AI~, at I IODC. The 5.35 ppmcorresponds to two overlapping protons of a 1,2~ double bond.
E~ample 2: Catalyst A with ~ ' ; . but no l-olefin s or otùe~ CTA
In this example no olefin was used to control molecular weight. To a 3-liter wide-mouth glass flask equipped with a mecharlical mechanical stirrer was added the following materials in the given order: norbomene (123g, 1.3 mol), 1,2-dichloroethane (Z,500g, 2,006 ml), 5-d~,ylllull)ùlll.,..c (53.1g, 0.23 mol),and then catalyst A (0.119g, 0.325 mmol) dissolved in dh,l~lulu.. A~,Ildll~ (2 ml).
T~ / after adding the catalyst to the stirred solution polymer started forming and the reaction . ~,l,.. . l--- rl The mixture was allowed to stir for a total of 60 minutes before methanol (100 ml) was added to destroy the catalyst. The polymer cake was added to stirring methanol to afford the product as a white 15 powder which was filtered off and washed with methanol and then dried unde}
vacuum for 16 hours at 60~C followed by several hours at 180C. The resulting polymer showed a molecular weight of 1,460,000 (Mw) as deter~nined by GPC
methods (Mn was 366,000). The polymer showed no resonances in the olefinic region in the NMR spectrum.
2û l~ample 3: Catalyst A with NB but no Mw control aDd no ~ ~
To a 3-liter wide-mouth glass flask equipped with a mechanical stirrer was added the following materials in the given order: norbornene (230g, 2.4 mol), 1,2-dichloroethane (2,950g, 2,341 ml) and then catalyst A (0.44g, 1.2 mmol) dissolved in dichlu., ' - (2 ml). I ' 'y after adding the 2s catalyst to the stirred solution polymer started fomming and ,ul~,;u;ldLillg from soluhon as a white powder to give a viscous white "cake" within about 5 seconds. The reactor f ~ to a maximum of 64~C. The mixture was allowed to stand for a total of 60 minutes before methanol (100 ml) was added WO95/14048 21 74756 PCI~/US94/13166 ~

to destroy the catalyst. The polymer cake was added to stirring acetone to afford the product as a white powder which was filtered offand washed with acetone and then methanol. The polymer was then dried overnight in a heated (60OC) vacuum oven. The resulting poly(norbornene) weighed 228.6g (99.4% isolated s yield), showed a T~ of 370OC and molecular weight of 1,640,000 (Mw) as determined by GPC methods (Mn was 436,000).
The addition hulllo~ . of NB exhibited a T~ at 370OC (nominally).
Though prone to oxidation in air at 370OC there is no melt flow. Specifically, ashear stress of 0.76 MPa was insufficient to induce any flow prior to 10 ' . An even higher ICIIIIJ~L~IIC, typically 50OC above the Ti~ iS
required to obtain melt flow necessary for fusion, that is, to progress from theelastic plateau into the terminal flow regime. r~ ;.,.. is ull~.vvhl~lc when such melt flow is obtained. The conclusion is that the homopolymer of NB is not ~J~u~ al: lc in the melt state.
15 Examples 4-13: Catalyst A with different levels of :' ,' I
) and decene-l (CTA) The following examples d~..,u..~u d~c the effects of an ~-olefin and a 5-alk~l.lu.l,u.l.~,..t comonomer on polymer glass transition ~ ,.dtUlC and molecular weight. All the POI~ ;L~ were run, in a 50 ml glass vial, at 20 ambient i . c in 1,2-dh,lllulu~,llallc (25 ml) using a magnetic stir bar for agitation. The ~ were added in the following order~
decene-l, 1,2-d;~ lu~u~ e, catalyst A (2.2 mg, 0.006 mmol dissolved in 0.5 ml 1,2-d;~l.lo.( ' -). In c~.~u~ 12 and 13, 4.4 mg (0.012 mmol) of catalyst A was used. In example 7 the NB was used as received without any 25 !Jul ir.~ ;u.. or drying The reactions were run for I hour (experiment 13, 30minutes) after which methanol was injected to terminate the reaction and the polymer was washed with excess methanol and dried. The results are set forth in the following Table I .

~ WO 95/14048 2 1 7 4 7 ~ 6 PCT/US94/~3~66 It is seen from the effect of increasing l-decylNB, , that by copolymerizing the NB with decylNEs`, the T6 of the copolymer formed can be ir~ f A copolymer with 20 mole% I-decylNB exhibits a TE of about 2500C. Flow is initiated for this copolymer with a shear stress of 0.76 MPa at 310eC. Theviscositycanbeadjustedbetweerl800,000and50,000poiseby changing Lc~ 4~ul~a between 3109C and 340'C, which is suitable for processing A negligible amount of oxidation and chain scission occurs during the short time required to process the polymer at these i . ~LIll~a 50 that the properties of the polymer, after melt flow, are retained. Thus COpOIy.ll.,ll~li 0 with a substituted-NB of choice one can lower the Tg sufficiently to allow melt processing at a desired L~lllp.,l~uit:.
TABLE I
EX. NOrbOmene DeCC~e.l, 5-DeCYI- POlYmer CCnV~n M M T, nO~OmCne, Yield, X W n 4 ,V, ~ (r ~ ~r.l ~) (e) (~) 10 10 C
15 4 2.32.24.6 0.035.025 0.03Ø125 2.~6 92 19S 80 353 5 2.31.Z4,5 0.053Ø38 0.03Ø125 2.18 93 124 44 351

6 2.25.23.9 0.053Ø38 O.laO.75 219 90 125 54 356

7 1.98.21.~ 0.018Ø125 0.88.3.75 2.49 87 310 129 285

8 2.2.233 0.07Ø5 0.29. 1.25 2.35 94 114 44 336 20 9 2.08.22 1 0.053.038 0.59,2.5 239 90 128 54 297 10 2.34.24.8 O.01g.QI25 O.01S.O.O63 2.26 96 331 117 375 II 1.95,20.8 0.07Ø5 0.88.3.75 26 92 110 50 265 12 1.7.18 0.84,6 0.0 1.7 100 11 6 274 13 ?1 24.5 0.0 0.0 2 87 17~n 335 370 Note that in each of the foregoing examples, the conversion obtained was baLIuliially ~ LiL~Live being generally above 90%. Further, when the molar ratio of l-dece-le to NB is 0.33, a - , . of NB is formed which h~ds a Mv~.ofonly lI,OOOwith 100/Oconversion.

WO 95/14048 , PCTNS94tl3166 0 2 1 74 7~6 E~amples 14-16: Catalysts A and C, solution t ~1~ ' " with different solvents In these three examples, catalysts A and C are used to polymeri4e NB
under solution conditions. Each example was run in 25 ml of ' ' ub.~.l4.,llc, o-S ~'~ ' I Ub~ ,.lC~ and toluene (as indicated in Table 2 below) in a 50 ml glassviai, at ambient (22~C) L~ll.l).,.dLul~ (example 14 was at 60~C) using a magnetic stir bar for agitation. The ~. ""l,. ." ~ were added in the following order:
norbomene (2.29g, 24.4 mmol, used as received with no further purification), chosen solvent, catalyst A (2.2 mg, 0.006 mniol dissolved in 0.5 ml of the 0 solvent), experiment 14 catalyst C (6.6 mg, 0.006 mmol). Each reaction was run for I hour to produce a viscous solution ('polymer cement') into which methanol was injected to temlinate the reaction. The polymer was then washed with excess methanol and dried.
TAi3LE 2 Expt Temp. Catalyst Solvent Polymer Conv'n, # C vield. ~ %
14 room A . " u1,~,.. 4~,.. , 2.05 89 15 room A o-di~ " ub~,.. 4~.. c 2.2 96 16 60 C toiuene 0.89 39 20 E~amples 17,18: Catalyst B using an l~-olefin for M,v control In one (#17) of these two examples, the p~l.r ;~.4L;OI~ carried out by Sen and Risse, using a palladium catalyst and no CTA, is substantially duplicated.
For comparison, the only difference in #18 is that iO mol% I-decene is added to a mixture analogous to the one which produced the l~u~llupulylll~,l in #17. Each25 polyl..~ L;ull was run in a 50 ml glass vial, at ambient i , ~ with II;Llull ' - (IO ml) as solvent, using a magnetic stir bar for agitation. The ~ WO 95/14048 2 1 7 ~ 7 5 ~ PCr/uss4/l3l66 .1~ in #18 were added in the following order: norbornene (Sg, 53.1 mmol), Iullu~ catalyst B (11 mg, 0.026 mmol which was first dissolved in 2 ml of II;LIUUI. '' ) then decene- I ( 1.0 ml, 5.2 mmol?. In # 17, the same procedure just described was followed, but no l-decene was used. Each reaction s waS allowed to proceed for I hr to allow a ~,UIl~r~l ~I,Ic margin for ~nn~rl~tinn Methamol was then injected into the solid reaction mass to terminate the reaction. The polymer was washed with excess methanol amd dried. The results are set forth in Table 3 below.

0Expt. I-Decene Polymer Conv'n Mw Mn # vield, %
17 no 2.7 54 141,000 70,200 18 ~les 3.4 68 92,400 39,100 In addition to the reduction in molecular weight the l-decene caused the polymer in experiment 18 to be terminated with an olefinic group observed by proton NMR methods (signals observed in the region of about 4.5 to about 6 ppm relative to TMS).
E:~ample 19: Catalyst D in the 'u r 1~ of NB
To a 50 ml glass vial was added norbornene (5g, 53.1 mmol) and 1,2-dichloroethane (10 ml). To this solution was added catalyst D (I Img, 0.026 mmol) dissolved in dichloroethane ( I ml). Upon addition (at ambient ~CIII~ UI C) the solution became cloudy and after I minute the solution became viscous, indicating polymer formation. The reaction was allowed to run for 24 hours after which the vessel was a solid plug of polymer. Methanol was injected to terminate the reaction and the polymer was washed with excess methanol and WO 95/14048 2 ~ 7 4 7 5 6 PCT/US94/13166 0 dried. The yield of poly(norbomene) was 4.6 g, 92% yield. The molecular weight was 13,200 (MD) and 44,500 (MW) E~ample 20: Catalyst E in the ~ " of NB
To a 100 ml glass vial was added norbomene (Sg, 53.1 mmol) and 1,2- .
r' ' ' J '' (40 ml). To this solution was added catalyst E (5.4 mg, 0.013 mmol) dissolved in d;l~h~-u~,.l'._.._ (3 ml). Upon addition (at ambient t~ ,ldLul~) the solution became cloudy and after about I mmute the solution became viscous, indicating polymer formation. The reaction was allowed to run for 24 hours after which the vessel was a solid plug of polymer. Acetone was 10 injected to terminate the reaction and the polymer was washed with excess acetone and dried. The yield of poly(norbomene) was 3.3 g, 66% yield.
E~ample 21: Catalyst F using propylene as CTA
To a S00 ml stirred, stainless steel pressure vessel was added a solution of norbomene (100 g, 1.06 mol) in toluene (40 ml) followed by propylene (126 g, 15 3.0 mol). Into this pressure vessel was injected catalyst F (.,;.,k~,h,LI.~
0.55 g, 1.~ mmol in mineral spirits) dissolved in toluene (20 ml) followed by MAO (20 ml, 44 mmol) in toluene ( 15 ml). After addition of the MAO there was an immediate exotherm (peaking at SO~C) which was controlled by cooling the reactor by circulating chilled water through the jacket. After 90 mins the 20 reaction was stopped by injecting methanol. After venting the excess propylene, the polymer was ~ .cu;~J;LdLcd by adding to a large volume of methanol and the polymer was washed with methanol and dried to afford 25.7 g of the product (25% conversion). The molecular weight was 3,680 (MD) and 6,520 (Mw). In addition to the reduction in molecular weight the propylene caused the polymer 25 to be terminated with an olefinic group observed by proton NMR methods (signals observed in the region of about 4.8 to about 6 ppm relative to TMS).

~ WO 9SI14048 2 1 7 4 7 5 6 Pcr/usg4/13l66 E~ample 22: Catalyst F from without CTA
Comparative Example To a 500 ml stirred serum bottle was added a solution of norbornene (50 g, 0.53 mol) in toluene. Into this solution was iniected catalyst F
S (Il;ukuh,Lllyll~ ulu~t~ 0.12 mmol in mineral spints) dissolved in ~
ml) followed by 1l ' ~ ' (5 ml of a 10%w solution in toluene). After 90 min the reaction was stopped by injecting ethanol. The polymer was u., , ' by adding to a large volume of methanol and the polymer was washed with methanol and dried to afford 31.6 g of the product (63%
conversion). The molecular weight was 1,030,000 (Mw) and 597,000 (Mn) E~ample 23: C~ ; of NB and ~
To a 50 ml glass vial was added norbornene (5 g, 53.1 mmol) and cyclopentene (S ml). To this solution was added a solution of catalyst H (100 mg, 0.128 mmol) in toluene (I ml). The reaction was allowed allowed to stir for 1 s 24 hours at ambient i . ~Lul .i after which methanol was injected to terminate the reaction and the polymer was washed with excess methanol and dried. The yield of polymer was 4.5 g. The resulting polymer was ~ t~ using NMR techniques as a I~UIIJUII.~ ,IU~ ~ copolymer and was shown terminated with an olefinic group.
20 E~arnple 24: Catalyst A with ethylene as M,v modifier To a 500 ml stirred, stainless steel pressure vessel was added a solution of nulbulll~lc (75 g, 0.8 mol) in 1,2-dichloroethane (200 ml) followed by ethylene (30û psi). Into this pressure vessel was injected catalyst A (73 mg, 0.2 mmol) dissolved in 1,2-dh,lllulu~ (4 ml). After one hour the reaction was stopped 25 by venting the ethylene and injecting ethanol (2 ml). The polymer slurry was worked up by adding to an excess of ethanol, filtering, washing the polymer with ethanol, air drying and then drying the product under vàcuum, at 80C for 20 hr. The polymer yield was 38.7 g (54%). The molecular weight was 2,120 WO 95/14048 ~ 1 7 4 7 5 6 PCT/US94/13166 0 (M~) and 2,840 (Mw). In addition to the reduction in molecular weight the ethylene caused the polymer to be terminated with an olefinic (vinyl) group observed by proton NMR ~ llu~wl,~. The Tg of the material was 170C.
Example 25: Catalyst A in r ~ ; " of methylNB and S ~ ' L using decene-l as M" modirler This poly~ ;~i;ul. was run in a 50 ml glass vial, at ambient i , d~UI~
in 1,2-dichloroethane (25 ml) using a magnetic stir bar for agitation. The were added in the following order: S ' ~IIIUII/U~ (2.03 g, 18.8 mmol), S-d~,~,ylllulbo~l..,..c (1.46 g, 6.25 mmol), decene-l (0.043 g, 0.31o mmol), 1,2-dichloroethane, catalyst A (4.4 mg, 0.012 mmol dissolved in 0.5 ml 1,2-dichloroethane). The reaction was run for I hour after which methanol was injected to terminate the reaction and the polymer was washed with excess methanol and dried. The yield of polymer was 2.02 g (58% conversion) amd the molecular weight was 20,000 (Mn) and 71,000 (Mw).
EYample 26: Catalyst I in solution ' ), '~. of NB
To a 100 ml glass vial was added norbornene (5 g, 53.1 mmol) and toluene (S ml). To this solution was added the solution of catalyst I in toluene (2 ml). Within I minute the reaction mixture became hot and stirring stopped due to the high viscosity caused by polymer formation. After 10 mins the reaction was stopped and the polymer was dissolved in toluene (400 ml) and 1/l ~ .
with methanol and filtered. The polymer was then redissolved in toluene, o"~,;p;LdLtd with methamol, washed with methanol and dried to afford the polymer (3.5 g, 70% wnversion)~ The polymer has a T~ of about 400C and molecular weight of M~. 520,000, M~ 128,000.
E~ample 27: Catalyst I in ~ of NB
To a 100 ml glass vial was added norbornene (5 g, 53.1 mmol) amd 1,2-diul~lulu.,LI~ (50 ml). To this solution was added the solution of catalyst I in WO 9S/14048 2 1 7 ~ 7 5 ~ ~ PCTIUS94113166 toluene (2 ml). The polymer started to form ' 'y and ~ , ' from solution. The contents of the reaction flask were added to excess methanol, washed with methanol and dried to afford the polymer (4.2 g, 84% conversion).
The polymer has a T~ of about 384C.
S Esamp~e 28: Catalyst F using ethylene as CTA
To a 500 ml stirred, stainless steel pressure vessel was added a solution of norbornene (30 g, 0.32 mol) in toluene (250 ml) followed by propylene (250 psi). Into this pressure vessel was injected catalyst F (~ ,Ll.L,d~yll~ lu~
0.046 g, 0.1 mmol in mineral spirits) dissolved in toluene (5 ml) followed by 0 m~th~ll-".;~ .. (14.8 mmol) in toluene (5 ml). After 40 minutes the reaction waS stopped by injecting methanol. After venting the excess etbylene, the polymer was IJlc~ J;LdLcd by adding to a large volume of methanol and the polymer was washed with methanol and dried to afford 15.1 g of the product.
The product was a IIUI~IO~JOIYII.~I of norbomene temminated with a vinyl group originating from the ethylene molecular weight modifier. The o~efinic (vinyl) end group observed by proton N~ methods (signals observed in the region of about 5.0 to about 6 ppm relative to TMS).
Examples 29-34: Catalyst A with different levels of either dodecyl or heYadecyl I L - and decene-l The following examples d~,~llull~LIdL~ the effects of an u-olefin and a 5-alkylllo.l,u,..~ on polymer glass transition t~ ,.dLu.c and molecular weight. All the pOlyl.. ;~Llu,~ were run, in lO0 ml glass vials, at ambient t~ dLUl c in I ,2-dichloroethane (40 ml) using a magnetic stir bar for agitation. The ' "~ were added in the following order: IIUIbUI~.
2s decene-l, 1,2-dichloroethane, catalyst A (4.6 mg dissolved in 3 ml 1,2-dichloroethame). The reactions were run for I hour after which methanol was injected to terminate the reaction and the polymer was washed with excess metbanol and dried. The results are set forth in Table 4 below.

WO95/14048 2 1 7475~ ~ ~ PCIIUS94/13166 ~

ExN~3 Decene-l 5~ ;yl-NB Polymer Mv~ M" T
#Ig) (ml) (type, ml) yield, x x C
(~) 10-3 10-3 294.16 0.1 dodecyl, 2.41 1.1 228 120 272 5304.4 0.05 dodecyl~ 1.61 4.95 322 142 n.d.
314.74 0.15 dodecyl. 0.5 4.8 137 63 n.d.
324.4 0.1 hexadecyl. 1.93 4 179 104 286 334.16 0.1 hex3decyl. 2.9 4.95 153 82 243 343.7 0.1 hex3dec~8.4.85 2.7 147 87 179 In a manner analogous to that which produces a hexadecyl substituent and the desired copolymer, a polymer with a C20 (eicosyl) substituent in a repeatingunit is made. Bven longer chains may be used as ' if desired, but there is no substantial difference in properties of a copolymer with > 20 C atoms over one which has 20, and therefore no economic incentive to make a 1s copolymer with a chain longer than 20 carbon atoms.
EYamples 35-38: Catalyst A with different levels of decene-l The following examples d~ u.. ~ the effects of various levels of an n-olefin (decene- I ) on l~u~u ~ molecular weight. All the poly."~ ..i;u....
were run, in a 50 ml glass vial, at ambient ~ in 1,2-d;~l,lu.. ' (25 ml) using a magnetic stir bar for agitation. The ~~ - . were added in the following order: norbornene, decene-l, 1,2-dichloroethane, catalyst A (2.2 mg dissolved in 3 ml 1,2-dichloroethane). The reactions were run for I hour after which methanol was injected to terminate the reaction and the polymer was washed with excess methanol and dried.
The results are set forth in Table 5 below.

Ex. ~ulbu~ c Decene-l, Conv' Mw Mn # (~mmol) (~. mmol) n (%) x 10-3 X 10-3 35 2.29, 24.3 0. 1, 0.7 93 80 33 5 36 2.32. 24.6 0.053,0.38 97 151 56 37 2.33, 24.8 0.035~0.25 94 205 78 38 2.34, 24.9 0.018,0.125 99.6 354 130 E~ample 39: Use of Catalyst A with ~ available NB.
This exarnple is presented as evidence of the excellent resistance to 0 dC~.,Li ~ CL;UII exhibited by the novel catalysts. Commercially available NB is used as received, without any ~.lc~lccLIll~, to remove impu}ities which might bepresent. The NB produced a I~UIIIUIJUIYI~ with excellent conversion. This d~ml the substantial immunity of the catalyst to impurities cull~.,;ulldlly present in commercial NB.
A procedure analogous to that in examples 35 to 38 was used here, except that the NB was used as received (from Aldrich Chemical Company). The high conversion ~ the high tolerance of these catalysts towards impurities.
The results are set forth in Table 6 below.
TABL~ 6 Ex. Nulbulll~lc Decene-l, Conv'n Mw M~
# (~. mmol) (~. mmol) (%) x 10-3 X 10-3 39 2.32, 24.6 0.1, 0.7 93 105 45 WO 95/14048 ` PCTNS94/13166 ~

l~amples 40-42 ((~ Li.., e~amples) The attempted ~oly" ;~ were run, in a 50 ml glass vial, at ambient Lc~ ,.aLul ~ in toluerle (25 ml) using a magnetic stir bar for agitation. The ...... ,1.. ,,,. - l~ were added in the following order: norbornene, diluent, catalyst.
S ~o molecular weight modifier was used. The reactions were run for 3 hours.
With these exceptions the procedure used was that of examples 35-38. At the end of 3 hours methamol was injected to kill the reaction, in every case no polymer was formed.
In experiment 40 catalyst J was used with toluene as the reaction solvent.
This illustrates that an anionic nickel complex is ineffective in the uoly~.~;~L;ull of norbornene In experiment 41 catalyst K was used and in experiment 42 bis(uy~ lr.o ~ t)nickel was used, in both cases di.,l.lul~ ' was applied as the reaction diluent. These two . All. .;1l.. .1l` illustrate that neutral nickel complexes and those with more-~,uul 1' ,, anions (Llinuu., ) are ineffective catalysts for the ~ol~ iUII of norbornene.
E~ample 43 This example d~,lllu~ the .,u~,ol~ i;VII of norbornene and cLIIyl; ;I.,~ vlbul ll.,..c (ENB). The polyll.~,. iLai;ull was run, in a 100 ml glass vial, at ambient Ltillll)~,.dLul~ in 1,2-d;~,lllul~ ' (50 ml) using a magnetic stir bar for agitation. The ~ were added in the following order:
norbornene (4 2 g, 45 mmol, used as received without furLher purification), ENB
(0.6 g, 5 mmol), decene-l (0.14 g, I mmol), 1,2- ' ' ' U~,illllll~, catalyst A (9.2 mg dissolved in S ml 1,2-dichloroethane). The reaction was run for I hour after which ethanol was injected to kill the reaction and the polymer was washed with excess acetone and dried. The polymer was ~ dCt~ J by proton N~
methods and found to contain 7% mole of ENB.

WO 95/14~48 2 1 7 ~ 7 5 6 PCTNS94113166 E~ample 44 This example d ~ I inr~ the homopolymeri_ation of - eLllyliJ~ bu~ c (ENB). The poly ~i7~tir~n was run, in a 50 ml glass vial, at ambient ~ ,l aLul c using a magnetic stir bar for agitation. The cu. ~ were added in the following order: ENB (12 g, 100 mmol), and catalystA(18mgdissolvedin I ml 1,2-d;chluJu. ' ). Thereactionwasrun for I hour after which ethanol was injected to l;ill the reaction amd the polymer was dissolved in toluene and p.l l ' with acetone, washed with acetone and dried i~l vacuum to afford the product, poly(cLllyl;d~ ,llull,ul-lene) (8.4 g, 70%
yield) as a white powder.
E~ample 45 To a 50 ml glass vial equipped with a magnetic stir bar was added Dorbomene (7.5 g, 80 mmo~ cLla~,y. l~ (3.2 g, 20 mmol) amd 1,2-~h,lllulu~ ' - (25 ml). To this stirred mixture (a colorless liquid) was added, at ambient t~ Id~ule~ catalyst A (9 mg in I ml methylene chloride). The polymer IJ~c~ J;LdLed from solution within 2 min and the reaction was terminatedafter 60 min. The resulting polymer was not furthe m,llal d~,tC: ;~.,d.
EYample 46 To a 50 ml glass vial equipped with a magnetic stir bar was added norbornene (8.5 8, 90 mmol), Il.. ,LIIylLcLlal,y 1.. 1.,.1. rr.,~ (1.7 g, 10 mmol) amd 1~2-J;L;IIUI~ ' (25 ml). To this stirred mixture (a colorless liquid) was added, at ambient t~ dLule, catalyst A (18 mg in I ml d;Ll~lul~ ' -). After 90 mins the viscous solution was added to excess acetone and the polymer plC, ' The polymer was washed with excess acetone and dried. It was cllGIàct~ ,d by proton NMR methods to be a copolymer of norbornene and ~ ,LllylLctlauy~ lo(~ r~ ~nl? and was found to have Mw 360,000 and Mn 150,000.

WO95114048 2 1 7 4 7 5 6 ~ Pcr/uss4/l3l66 0 E:xamples 47-~1 In these examples varying levels of an ll-olefin (decene-l) are used to control the molecular weight to assorted desired vaiues. In addition various levels of 5-dc~yl.luli,ùl..~,lle ~,ullluA.~ are applied to control the polymer glass transition t~ ly~ . In each experiment a third monomer was used as a minor 1l t, such that the resulting polymers are terpolymers. The third monomer applied in every case was tile trimer of ,y.,lvy ' ~ (in fact a mixture of various isomers including both symmetric and ~y ie, structures) which can be prepared by he4t- soaking of di~,y~ y. .~ . followed by distillation. All the pùlylll.,l;~;ull~ were run, in a 50 ml glass viai, at ambient Lul e in 1 ,2-dichloroethane (25 ml) using a magnetic stir bar for agitation.
The l.~ ,u : were added in the following order: l~u~bul~ ,., decene-l, 1,2-dichloroethane, catalyst A (2.2 mg, 0.006 mmol dissolved in 0.5 ml 1,2-dichloroethane). The reactions were run for I hour after which methanol was injected to kill the reaction and the polymer was washed with excess methanol and dried.
In the polymer chains formed in each of the foregoing examples, whether hu~l~uyO~ or copolymer, there is essentially no repeating unit which is linked in the chain by virtue of being ring-opened as in a metathesis pUlyll.~.l~Liùl~ By "essentially no repeating unit" is meant that there is no evidence in a NMR ~ u~,uyic analysis of a linked ring-opened unit. From this it is concluded that there is less than I mol % of a ring-opened repeating unit. Therefore all addition polymers made using the process of tilis invention are ~1 ~ A- .j. ' ;' ' ~ by having less than I mole % of a ring-opened, , preferably iess than 100 ppm.
Further, addition polymers of this invention are made in yields of at least 50 mol % preferably 80 mol % conversion of monomers to polymer, most preferably more than 90 mol %, and most preferably more than 95 mol %.

-WO 95114048 2 l 7 4 7 5 6 PCIIUS94/13166 .

r~. No~omene Decene-l, 5-Decyl- CPD P~ly. ConY bl., M" T~.
(g mmol) ~g,nunol~ norbomene, trimen:, yield, (%) ~ ~ ~C
10 ~ 10 472.2,23.3 0.07,0.5 0.276,1.19 0.012, 2.22 g9 106 50 337 0.06 548232,24.6 0.035, 0.03,0.125 0.001, 2.16 92 195 80 353 0.25 0.006 492.31,24.5 0.053, 0.03Ø125 0.001, 2.18 93 124 44 351 0.38 0.006 502.25,23.9 0.053, 0.17Ø71 0.008, 2.19 90 125 54 356 0.38 0.04 511.98,21.1 0.018. 0.832.3.56 0.037, 2.49 87 310 129 285 0.125 0.19 E~ample S2 To a 100 ml glass vial equipped with a magnetic stir bar was added IIUIbUII~ (4 g, 42.5 mmol), dichloroethane (40 ml) and 5-liu~luu~ubu~ylllollJol~ (3.3 g, 10.62 mmol). To this stirred solution was added, at ambient , ~LLUI~, catalyst A (13 mg, 0.035 mmol in 2 ml dichloroethane). Il.~ ,d;dl~ly upon addition of the catalyst polymer started to precipitate from solution. After 90 minutes the slurry was added to excess acetone and the polymer was collected by filtTation. The polymer was washed with excess acetone and dried. The yield of the copolymer was 5.4 g (74%).
The product was .,I.~ by IR and NMR methods (IH, 13C and l9F) as being a copolymer of norbornene and S-IIUII~1UUIUl)-~IIIOIIJUI~ C~ and exhibited a TE of 303~C.
E~ample 5~i - To a 50 ml glass vial equipped with a magnetic stir bar was added norbornene (7.5 g, 80 mmol), l-decene (0.072g, 0.5 mmol) and 1,2-ih,l.lvlu~,;La,.e (20 ml). To this stirred solution was added, at ambient um~ , catalyst L (15 mg in 5 ml 1,2-dichloroethane). After 1 hour the reaction was stopped by adding ethamol and the polymer was was isolated by adding to a large exce3s of acetone, filtered, washed and dried.
EYample 54 To a lû0 ml glass vial equipped with a magnetic stir bar was added norbornene (15 g, 160 mmol), I-decene (0.144g, I mmol) and 1,2-di~ lulu_Lilaue (20 ml). To this sirred solution was added, at ambient ~Lul~, catalyst M. After I hour the reaction was stopped by adding ethanol and the polymer was was isolated by adding to a large excess of acetone,filtered, wa3hed and dried.
EYamples 55-60 The following exampies illustrate the large ~U~ IIV..: ~ ,, effect of using a polar diluent (1,2-~ ,lllulu~ ~lc, DCE, wa3 used) rather than a non-polar ll,y~ilu~albull (toluene, TOL, was used in the example3) when (co)polymerizing ~ul i~ul l.~...,i using a catalyst comprising a group VIII metal salt in l ' .laL;un with a m~h~l....,;.".~ r In every example nickel ~LIly'' (catalyst F) was used in ~. 1,;., ~..,,. with ' (MAO7 10% solution in toluene). All examples were (co-)~,uly..l_liLa.kJ.~ of 20 norbornene (NB) and 5-du.,yllluliJull,.l., (NB-10).
The T8 f the polymer from example 58 was 1 70C.
Though conversion of monomer(s) to polymer in a non-polar hy~ilu~,ali~l solvent is generally about 80 mole %, the conversion of some monomers to n~ and of some ~ of monomers to copolymers may be in the range from 40 - 50 mole %. Such non-polar solvents are typically (C3-Cl2)aikane, or (C6-C20) arûmatic sûlvents~ In those in3tances where the conversion in a non-polar lly~ilu~,aliJ~I solvent are less than 50 mole %, at least a 50% illllJlU~. ' in conversion is realized in a polar I ' -' ~ilu~,alb~l solvent.

WO 95~14048 2 1 7 ~ 7 5 6 PCT/US94/1316C

Such polar solvents are typically halo(CI-C4)alkane, and (C6-C20) ' ' - U~ Li~
solvents. Effective polar llyJlu~ byl solvents are methylene chloride, 1,2-- dichloroethane, I, I, I -llh~lllulu~ ' , p~/ u~llulu~,Llly~Llle and lIaIU~UII~ iC
solvents such as ~ " ub_.l~ c, dichlulul,_ll~_.._ and trichlvlul,~,.~.,l..,. In some j~Stances the conversion can be doubled, that is a 100% ;.. IJIU~_III_III can berealized, by choice of the optimum polar solvent.

_ o ~ ` o~ X ~ ~C, X ~ V) I_ X X
o ~ `D o 1` o ~., E - ~ ~ ~ ~ ~ ~
x ' ~ ~ ~
o ~ ~ ~ ~ ~
f- -- E ~ ~ ~o ~
X rJ
-- X ~o ~. ~
E ` ` ` ~
Z r~ ~ O O
3 o ~ O ~ O ~
~ a ~
o _ .~
-- -- -- ~ ~ O
L. o o o o o o ~ E X K X X X X
C~ _ _ _ -- -- ~D
X ~ O

WO 9S/14048 2 l 7 4 7 5 6 PCTIUS94/~3166 E~ample 61 To a 50 ml glass vial equipped with a magnetic stir bar was added ~u~bulll~e (1.8 g, 18.8 mmol), I-decene (0.04g, 0.31 mmol), 5-d~,~,ylllulbull~ , (1.46 g, 6.2 mmol) and 1,2~ (25 ml). To this S stirred solution was added, at ambient i . c, catalyst C (13 2 mg, 0 û12 mmol in 2 ml 1,2-dichloroethane). After I hour the reaction was stopped by adding etbanol and the polymer was was isolated by adding to a large excess of acetone, filtered, washed and dried (yield 2 65 g, 81%) E~ample 62 The procedure used in Examples 49-51, in which the ~,uly, ;,~
were run in a 50 ml glass vial, at ambient t~,lllp~ Lulc in 1,2-d;~lllulO~,illall6 (25 ml) was repeated, ~ the same molar equivalents of IIUI hulll~J;~c for the trimer used in each example, and in each case, a terpolymer was obtained which had about the same T~ as the cu~lc~ol~J;Il~ terpolymer with trimer 15 E~ample 63 (Comparative example) To a ~ 00 ml glass vial was added norbornene (5 g, 53 I mmol) and hexane (45 ml) To this solution was added catalyst N (r~ ~ Lin-AII in mineral spi~its) (0.024g, 0 026 mmol) followed by MAO (1 0 ml of a 10%
solution in toluene). After 90 minutes the reaction was stopped by adding 20 ethamol. The mass of polymer was thoroughly washed with acetone amd methanol and then dried in a vacuum oven. The polymer yield was roughly 1.5 g (30%). The polymer was ul~ ;L~,d by proton NMR methods (o-dichiù-ul: .,.~.le solvent) to contain a high level of backbone olefinic ~;vll indicative of ROMP ~Jùl~ --j7~tinn Indeed the polymer 25 ~ ,u~lc~ull~cd to about 80% ring-opening (ROMP) and only 20%
addition WO95/14048 2 1 7 4 7 ~ 6 - PCI/IIS94/13166 E~ample 64 (Comparative example) To a 100 ml glass vial was added norbornene (5 g, 53 . I mmol) and toluene (75 ml). To this solution was added catalyst O (Molybdenum Hex-Cem in mirleral spirits) (0.016 g, 0.026 mmol) and decene-l (I ml) followed by MAO
(1.0 ml of a 10% solution in toluene). After 90 minutes the reaction waS
stopped by adding ethanol. The resulting mass was a very viscous gel, indicatinghigh conversion. A sample of the polymer was pl~ , ' from solution with methanol and then thoroughly washed with acetone and methanol and then dried in a vacuum oven. The polymer was . ~ by proton NMR methods (o-dichlulul,~,.~.,l.c solvent) to contain a high level of backbone olefinic ull~aiul cl;ull indicative of ROMP poly".~ .Liol~. Indeed the polymer '---~1)'~'` l;'''l cu,-~,u,,dcd to about 75% ring-opening (ROMP) and only 25%
addition.
Example 6~
Pr~ r~tion ~f AlF3 su~ort To a 500 ml round-bottomed flask containing dry toluene (100 ml) under an argon atmosphere was added BF3 etherate (11 g, 78 mmol). To this mixture (with stirring) was added dropwise, at ambient i I r, a 10% wt solution of L~ y' (78 mmol) in toluene. After complete addition the solvent was removed under vacuum at ambient t~,.llp~ Lul ~; to afford the aluminum trifluoride support as a free-flowing, fine powder containing small amounts of bound toluene (11~ 11 ' ' '!/ 0.5-0.6 mole toluene per mole aluminum trifluoride).
Pr~n~Atinn r f ~rnort~ AtAlySt To a flask containing (under argon) the aluminum trifluoride support (1.4g, 10 mmol) was added catalyst A ([(~l3-crotyl)(cycloocta-1,5-diene)nickel]
h.".dfluul~ r' , ' , 0.2 g, 0.5 mmol) followed by dry toluene up to a level ~p~ / 2 cm above the solids. The mixture was then stirred and then ~ WO95114048 2 1 7 ~ 7 5 6 PCT/US94/13166 al~owed to stand overnight at ambient i . ~. The mixture was then filtered, the solid washed with diethyl ether until the ether filtrate was totally - colorless and the solid dried under vacuum to afford the catalyst as a dry powder.
5 J~r,mr~rr,ly~ f nrlrb~rnPnP
To a 50 ml glass vial containing a magnetic stir bar and norbornene (3.2 g, 33.3 mmol) was added dichloroethane (25 ml) followed by the supported catalyst (17 mg suspended in I ml Jh,l~lu~ ,.hcllc). After two hours ethanol wasinjected to terminate the reaction and the polymer was washed with excess 10 acetone, filtered and dried overnight, under vacuum at 80~C. The yield of poly(l~u.l,u,,,~lc) was 1.8 g, 56%.
Example 66 Prepar~firm o~f rot~ yst Nickel e~ly" in mineral spirits (4.6 ml, 4.3 g, 6 mmol of 15 nickel) was added to a flask under a nitrogen atmosphere and diluted with toluene (about 20 ml). To this solution was added a solution of BF3 etherate (1.13 ml, 1.3 g, 9 mmol) in toluene, causing the original green solution to tum yellow-green in color. Butadiene was then bubbled through the solution for dlJ,lJII ' ' ~y 5 seconds. The flask then briefly evacuated and refilled with 20 nitrogen to remove excess butadiene. To this solution was slowly added tl;~ (10 mmol) diluted to about 10% wt in toluene while the flask was cooled in ice-water. The resulting solution was a dark-brown/black solution of the catalyst in toluene.
Hrlmrlrr,lyl,--..i,,.l;.", of nr~rbr~rnPnp 2s To a 50 ml glass vial containing a magnetic stir bar and norbornene (2.3 g, 24 mmol) was added dichloroethane (25 ml) followed by the catalyst (dl~lJlU~illl~t~,ly 0.012 mmol). After two hours ethanol was injected to telminate WO95/14048 2 1 7 ~ 7 5 6 PCT/US94/13166 the reaction and the polymer was washed with excess acetone, filtered amd dried overnight, under vacuum at 80C. The yield of poly(norbornene) was 1.6 g, 7oo/~
E~ample 67 S PrP~ratinn of r~t~lyst To the catalyst described in example 66 (I mmole of nickel) was added neat h_Adlluol~ acid (HSbF6, 0.12 g, 0 5 m-mole) to afford the catalyst as a solution or colloidal slurry in toluene Hnmnpo~ r of nr~rbnrnpnto To a 50 ml glass vial containing a magnetic stir bar and norbornene (2.3 g, 24 mmol) was added dh,hh~m,LllGI}~ (25 ml) followed by the catalyst (~p., '~ 0.012 mmol). After two hours ethanol was injected to terminate the reaction and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80DC The yield of poly(norbornene) was 2 3 g, 1s 100%.
EYamples 68 and 69 PrPr~ratirnofr~t~lyst (7~3,r~2,l~2-dodeca-2(E),6(E),lO(Z)-triene-l-ylnickel AI-I1UUI~ ) Bis(~ au~l Idlh,..c)nickel was placed in an argon-filled Kjeldahl flask 20 and cooled with dry ice Butadiene was condensed into the flask to a level Gp~)lVAilll~ 2 cm above the level of the yellow solid The butadiene was then refluxed (ambient LCII.~ ) for about 2 days after which time the yellow solid had been converted into a red oil. The mixture was filtered through a dry-ice cooled frit (under argon) to remove solid impurities, then the butadiene2s was evaporated off amd replaced with twice the volume of pentane After repeated cryct~lli7~tinnc in pentane and dh,L~Iylu;h~,. at -78C the product wasisolated as a red oil with a melting point of about - I C. This product is shown ~ wo 95/1404~ 2 1 7 ~ 7 ~ ~ PCT,'US94/13166 in the following figure and has the empirical formula Cl2Hl8Ni. To a cooled solution of Cl2HI8Ni (~ ' 'y 10 mmole) in diethyl ether (20 ml) at -78C was 810wly added L"~luul~ ' ' acid (2.3 g, 10 mmole). The resultirlg mixture comprised a light browrl solid and a reddish-brown solution.
After warming to room t.~ p~ Lu~e the etha was decanted ûffand the brown oil was cooled back down to -78C at which i , c it resolidified. Methylene chloride was slowly added and the the remaining solid was removed by filtration to afford the catalyst C~2HI9NiSbF6 as a solution. The catalyst was ,u~c~,;,u;lut. d as an orange brown solid by adding a five-fold volume excess of diethyl ether, 10 decanting and drying. The net reaction is shown in the following figure:
g Ni~ ~ SbF6-Buta~ /~
~ / HSbl-6 Hom~ )uly~ of rlnrborA.-~nP
Example 68: To a 5û ml glass vial containing a magnetic stir bar and v~hu~ e (2.3 g, 24 mmol) was added d;LIIIVIV~ (25 ml) followed by the catalyst (~ JlU~ t~ly 0.012 mmol). After two hours ethanol was injected to WO 95114048 2 1 7 4 7 5 6 PCTIUSg4/13166 terminate the reaction and the poiymer was washed with excess acetone, filtered and dried overrlight, under vacuum at 80~C. The yield of poly(norbomene) was 2.3 8, 100%.
Copoly."~ .,l of rmrborrl~nl~. an~l 5-d~.~,yl.l~
Example 69: To a 50 ml glass vial containing a magnetic stir bar and norbornene (1.8 g, 18.8 mmol) and 5-dc~,y' bu~ e (1.46 g, 6.2 mmole) was added dichloroethane (25 ml) followed by the catalyst (a~ 'y 0.012 mmol). After two hours ethanol was injected to terminate the reaction and the polymer was washed with excess acetone, filtered and dned ovemight, under vacuum at 80C. The yield of poly(norbornene) copolymer was 2.9 g, 89%.
E~ample 70 Prepar~tinn of ~t~lyst Nickel ~LIIy'' in mineral spirits (0.72 ml, I mmol of nickel) was added to a flask under a nitrogen atmosphere and diluted with toluene (about 20 ml). To this solution was added a solution of BF3-etherate (I .13 ml, ] .3 g, 9 mmol) in toluene, causing the original green solution to turn yellow-green in color. Butadiene was then bubbled through the solution for à~ y S seconds. The flask then briefly evacuated and refilled with nitrogen to remove excess butadiene. To this solution was slowly added L it:lh~' ' (10 mmol) diluted to about 10% wt in toluene while the flask was cooled in ice-water. The resulting solution was a dark-brownlblack solution of the catalyst in toluene. To this solution was added l-i.,;l~y' ' (I ml of lM solution in toluene) followed by 0.07 g (0.5 mmole) of HPF6 (60% wt in water).
ll""",".,l~",~rj7~tinn of norborn~
To a 50 ml glass vial containing a magnetic stir bar and norbornene (2.3 g, 24 mmol) was added l-decene (0.043 g, 0.31 mmole) and d;~ u~ (25 ~ wo 95114048 ~ 1 7 4 7 ~ 6 PCT/US94/13166 ml) followed by the catalyst (~ , 0.012 mmol). After two hours ethanol was injected to terminate the reaction and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of poly(l~ull,u,l~ c) was 1.71 g, 74%.
s El~mple 71 Pr~r~rArinn of rDt~lyst ll~,A~llUul~ : acid (HSbF6, 0.708 g, 3 mmole) was placed in a dry, nitrogen filled Teflon0 bottle with a Teflon0 cap/valve containing a magnetic stir-bar. The bottle was cooled in alcohol/dry ice and nickel ethylhexanoate (8% in mineral spirits, 2.3 ml, 3 mmole) was added and the contents were allowed to warm to room L~ ,, r~, Copolyrnr~ri7~tinr nf nnrhor~ n To a 250 ml glass polymerization vessel fitted with a mechanical stirrer and baffles was added a 75/25 mol/mol % mixture of norbomene and 1~ 5-d~,~yll~ulbu~ , (10 g), I-decene (Mw control agent, 0.073 ml, 0.39 mmole)and 1,2-dichloroethane (88 ml). To this stirred solution was added the above catalyst (0.016 ml, 0.019 mmole) followed by BF3-etherate (0.021 ml, 0.17 mmole) and triethylaluminum (1.7 molarin ~y~ , 0.11 ml, 0.19 mmole).
Theratioofthecatalyst-c-l~-- (Ni:B:Al)was l:9:10andtheratioofthe monomers to catalyst (nulbull~ ,D to Ni) was 4,000:1. The pol~,.,.";~Liu.l ensued L...l~ upon addition of the aluminum alkyl with an immediate exotherm from ambient t~ ,...Lul~ (20C) to almost 40C
After I hour the pol~ ;~L;ull was temminated by addition of ethanol.
The polymer was isolated by filtration and washed with excess ethanol before 21i drying at 80C under vacuum ovemight to a~fford the copolymer product (9.2 g, 92% yield).

WO 9~i/14048 PCT/US94/13166 ~
21 747~6 E~ample 72 prPr~Atinn of r~f~lyst lUU~ - acid (HSbF6, 1.126 g, 4.76 mmole) was placed in a dry, nitrogen filled Teflon0 bot;de with a Teflon0 cap/valve containing a 5 magnetic stir-bar. The bottle was cooled in alcohol/dry ice and nickel ~LIIy'' (8% in mineral spirits, 4.76 mmole) was added and the contents were allowed to warm to room ~ ..~. r .
CUI~OIJI. ,;~ of nnr~nrr~nl an~l 5-dc~,~l .. L.. --~
To a 250 ml glass ~oly i~aL;ull vessel fitted with a mechanical stirrer and baffles was added a 75125 mollmol % mixture of norbomene and 5-d~,ylllull,OIII.,1l~, (10 g) and 1,2-di~ lv~ (138 ml). To this stirred solution at 0C was added the above catalyst (0.016 ml, 0.019 mmole) followed by BF3 etherate (0.021 ml, 0.17 mmole) and trh,LIIy' ' (1.0 molar in toluene, 0.19 ml, 0.19 mmole). The ratio ofthe catalyst cu r (Ni:B:AI) 15 was l:9:1ûandtheratioofthemonomerstocatalyst(llulL~u~.,.,..~toNi)was 4,000:1. The poly,..~ aLiul) ensued ' 'S~ upon addition of the aluminum alkyl with an immediate exotheml from 0C to about 12C.
After I hour the poly....,.;~L;ull was temminated by addition of ethanol.
The polymer was isolated by filtration and washed with excess ethanol before 20 drying at 80C under vacuum ovemight to afford the copolymer product (8.7 g, 87% yield).
E~ample 73 PrP.jn~Atinn of n~t~lySt The catalyst was prepared as described in example 72.
25 Cul~ol~ ;,...ofrlorborrlPn~an~i 5-d,i~ .Lu"..
To a 250 ml glass pùly~ aL;ull vessel fitted with a mechanical stirrer and baffles wa3 added methylene chloride (88 ml). To this stirred diluent at .

~ wo 95/14048 2 ~ 7 ~ 7 5 6 PCT/US94/13166 0CC was added the above catalyst (0.032 ml, 0.038 mmole) followed by BF3 etherate (0.042 ml, 0.34 mmole) and Llh,;lly' ' (1.0 molar in toluene, 0.38 ml, 0.38 mmole). The ratio ofthe catalyst ~ , (Ni:B:AI) was 1:9:10. To the catalyst solution at 0C was slowly added (over 5 minutes) a s mixture of a 75/25 mol/mol % mixture of norbomene and S-dF~ lul ~u-~ .e (20g, 154.6 mmoles of nu-l,ul-.~,.lw) and l-decene (0.1 i6 ml, 0.78 mmole) such that the fnal ratiû of monomers to catalyst (llulbull.~llw to Ni) was 4,000:1.
The poly.,..,.i~Liu" ensued ' '~, upon addition of the first drops of monomer mixture with exhibition of an exotherm from 0C to about 12C.
After I hour the pOlylll~i~l;ull was terminated by addition of ethanol.
The polymer was isolated by filtration and washed with excess ethanol before drying at 80C under vacuum overnight to afford the copolymer product ( 17.5 g, 88% yield).
E~ample 74 15 Prepar~tinn of ~t~lyst Ih,.~luu-u~-L;.Ilon;~, acid (HSbF6, 1.126 g, 4.76 mmole) was placed in a dry, nitrogen filled Teflona bottle with a Teflon0 cap/valve containing a magnetic stir-bar. The bottle was cooled in alcohol/dry ice and nickel ~llyl'.~ ulua~ (8% in mineral spirits, 4.76 mmole) was added and the contents 20 were allowed to warm to room t~
C~ '~ nn nf nnrbOrrF~nF' ar~r~ S-~F YI~ UII ~
To a 250 ml glass pol~ ..a,. i~d~;ull vwsel fitted with a mechanical stirrer and baffles was added a 75/25 mol/mol % mixture of norbornene and 5-d~,~,y' bu~ le (15 g) and methylene chloride (82 ml). To this stirred solution at -10C was added the above catalyst (0.024 ml, 0.029 mmole) followed by BF3 etherate (0.032 ml, 0.26 mmole) and tri~ll-y' ' (1.0 molar in toluene, 0.29 ml, 0.29 mmole). The ratio of the catalyst ~ ~ . (Ni:B:AI) was l:9:10andtheratioofthemonomerstocatalyst(l~o-l~u-1..,..wtoNi)was WO 95114048 2 1 7~ 4 7 5 6 PCTIUS94/13166 4,000:1. The pol~ ;~Liu.. 2nsued ' ~y upon addition of the aluminum alkyl with an immediate exotherm from -10C to about 22C.
After I hour the po~ ;~L;ul~ was terminated by addition of ethanol.
The polymer was isolated by filtration and washed with excess ethanol before 5 drying at 80C under vacuum overnight to afford the copolymer product ( 12.5 g;
83% yield).
EYample 7!i Pre~aratinn r~f rD~DlySt UUIUGII~;IIIVII;~ acid (HSbF6, 0.55 g, 2.32 mmole) was placed in a 10 dry~ nitrogen filled Teflon0 bottle with a Tef~on~ cap/valve containing a magnetic stir-bar. The bottle was cooled in alcohol/dry ice and nickel ~LIly'' (8% in mineral spirits, 2.32 mmole) was added and the contents were allowed to warm to room i I dLUIt~. After 2 hours at ambient l~,llllv.lrl~ul~ the catalyst was stored at -18C.
15 Co~ùl~ ;,.ofnnrborrlPnP ' li-rl~.~yl"l~
To a 250 ml glass poly.ll~ ;ull vessel fitted with a mechanical stirrer and baffles was added a 58/42 mol/mol % mixture of norbornene and ~-d~,~,yll-ù-bu-ll~,lle (16.2 g), I-decene (0.073 ml, 0.39 mmole) and 1,2-r': " u,,LIId-l~, (146 ml). To this stirred solution at 20C was added the above catalyst (0.016 ml, 0.019 mmole) followed by BF3-etherate (0.021 ml, 0.17 mmole) and Ll;cllly' ' (1.7 molar in c~, ' ' , 0.11 ml, 0.19 mmole). Theratioofthecatalyst, I (Ni:B:Al)was l:9:10andthe ratio ofthe monomers to catalyst (I~UIbUIII~ to Ni) was 4,000:1. The poly ensued ' 'y upon addition of the aluminum alkyl with an immediate exotherm from 20C to about 33C.
After I hour the pol~ L;ul- was terminated by addition of ethanol.
The polymer was isolated by filtration and washed with excess ethanol before drying at 80C under vacuum overnight to afford the copolymer product (12.4 g, ~ WO 95/14048 2 1 7 4 7 5 5 PCTIUS94~13166 77% yield). The molecular weight of the copoiymer was measured by GPC and found to be 386,000 (Mw, the Mn was 104,000).
E~amples 76 and 77 Pr~-~ti~n r.f r~t~lySt S llw.~iuu~ - acid (HSbF6, 1.126 g, 4.76 mmole) was placed in a dry, nitrogen filled Teflon~ bottle with a Teflorl~ cap/valve containing a magrletic stir-bar. The bottle was cooled in alcohol/dry ice and nickel CLi~y;l.~_.J_-~ (8% in mineral spirits, 4.76 mmole) was added and the contents were allowed to warm to room t~ c.
10 Copoiy,,.,,~ nfm~rb~rnPnP ~ 5 ~ lr Example 76: To a S liter stainless steel pul~ Lio., vessel fitted with a mechanical stirrer and baffles was added norbornene (305 g, 3.24 Mole), 5-d.,~,yllloli~u~ c (256 g, 1.092 Mole), 1 -decene (8. i 9 ml, 43.3 mmole) and methylene chloride (to give a total liquid volume of 4.2 liters). To this stirred solution at -11C was added the above catalyst (1.05 g, 1.082 mmole) dissolved in methylene chloride (3 ml) followed by BF3 etherate (I.19 ml, 9.74 mmole) and triethylaluminum (1.0 molar in heptane, 10.82 ml, 10.82 mmole). The ratio of the catalyst ~ (Ni:B:AI) was 1:9:10 and the ratio of the monomers to catalyst (nu.i~u~ llw to Ni) was 4,000:1. The l.ul~ ;~aLiull ensued ' 'y upon addition of the aluminum alkyl and the reaction was killed after I hour by addition of ethanol. The resulting polymer was washed twice with an excess of ethanol, filtered and dried overnight under vacuum at 80C.
The polymer yield was 510 g which represents a conversion of 91%. The polymer molecular weight was determined by GPC methods to be 204,000 (Mw, Mn = 97,100).
Example 77: To a SûO ml glass pol), vessel fitted with a mechanicai stirrer amd baffles was added norbornene (43.5 g), 2~ 747~,~

5-d~ lUlll~ilC (36.5 g), I-decene (I.17 ml) and methylene chloride (to give a total liquid volume of 40û ml). To this stirred solution at 0C was added the above catalyst (0.146 g, 0.15 mmole) dissolved in methylene chioride (2.~ ml) followed by BF3-etherate (0.17 ml, 1.35 mmole) and L ;., ~..r' ' (1.0 5 molar in heptane, 1.5 ml, 1.~ mmole). The ratio of the catalyst I
(Ni:B:Al)was l:9:10andtheratioofthemonomerstocatalyst(llulbul-.~"1 to Ni) was 4,000:1. The poly~ Ld~;ull ensued ' '~ upon addition of the aluminum alkyl and the reaction was killed after I hour by addition of ethanol.
The resulting polymer was wa3hed twice with an excess of ethanol, filtered amd dried ovemight under vacuum at 80C. The polymer yield was 79.5 g which represents a conversion of 99%.
I~amples 78 and 79 Prei~ar~ti~ nf r~t~ st IICAdrilUI~ ~ acid (HSbF6, 1.42 g, 6 mmole) was placed in a dry, nitrogen filled Teflon~ bottle with a Tefion0 cap/valve containing a magnetic stir-bar and nickel eLlly" (8% in mineral spirits, 6 mmole) was added at ambient ~el~lJ. e and the contents (red-brown in color) were aliowed to stir at room L~ .,l dLUI 1~ for 3 hours. The mixture was then dilutedwith 1,2 dichloroethane to a of 0.3 Molar and transferred to a glass vessel for storage.
i_xample 78: ~ m~nlyln~ tir~n nf llntbûrr~ n~
Tri~t~ min~-m ~c Co~ stslYst To a 100 ml gla3s vial equipped with a magnetic stir-bar was added norbomene (5 g, 53.1 mmol) and 1,2 ih,hl~lu~,LII~l~, (40 ml). Thereafter was added the catalyst (0.026 mmol) ' 'y followed by Ll;.,Lil~LIlL,II.;II.IIII (2.6 ml ûf 0.5 Molar solution in hexanes, 1.3 mmol). There ensued a very rapid and exothemmic poly ;Ld~;Oll with quantitative conversion of the monomer.
-~ `
~ WO95/14048 2 1 7 4 7 5 ~ PCTIUS94113166 Example 79: TT 2l,~ ri7~tinn nf rlnrbnrr~

D;. ~ hlnrifl~ ~c Cor~t~¦yst To a 100 ml glass vial equipped with a magnetic stir-bar was added .............. r (5g,53.1mmol)and1,2d~ lul~iLallc(40ml). ThereafterwaS

S added the catalyst (0.026 mmol) - ' 'S followed by Jh,~

chloride (neat, 0.65 mmol). There ensued a very rapid and exothermic pul ~ r~iion with ~ , conversion of the monomer within 5 minutes.

The molecular weight of the isolated polymer (Mw) was 694,000.

E ample 80 10 pr~r~r~tinn of r~lt~lyst II~,~luu~ - acid (HSbF6, 1.29 g, 5.45 mmole) was placed in a dry, nitrogen filled Teflon0 bottle with a Teflon0 cap/valve containing a magnetic stir-bar and nickel ellly" (8% in mineral spirits, 5.45 mmole) was added at ambient ~tlll~ d~UI e and the contents (red-brown in color) were allowed to stir at room t~ ule for 2 hours. BF3 etherate (6.28 ml, 49.05 mmol) was added and the mixture was allowed to stir for a further 2 hours.

C,~ of norborr,rn~ An~l 5 ,~

Tri-~lllylAI.. ;,.I~lll AC Cnr:-t:.lySt To a 100 ml glass vial equipped with a magnetic stir-bar was added norbornene (3.7 g), S-.lc.,ylllo,l,~.,l,~,.,c (3.6 ml) and 1,2 dichloroethane (40 ml).
Thereafter was added the catalyst (0 013 mmol) ' 'S, followed by l.i.,~l,.~' ' (0.26 ml of 0.5 Molar solution in hexanes, 0.13 mmol). There ensued a rapid and exothermic polymeri_ation which was terminated with methanol after 2 hours. The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum. The polymer (4.8 g was recovered) showed a molecular weight of 467,000 (Mw, M,, = 147,000).
-21 7~756 ~ ~\

E~ample 81-8~
Pr~.t~n~r~tirn of r~t~lyst II~luùlua~lLilllu~;c acid (HSbF6, 1.8 g, 7.6mmole) was placed in a dry, nitrogen filled Teflon0 bottle with a Teflon 0 cap/valve containing a 5 magnetic stir-bar followed by nickel ~LIIy'' (8% in mineral spirits, 5.06 mmole) and the resulting mixture mixture was stirred at ambient ~ for 2.5 hours.
Cu,uoly~ of r~r)rh-~rn~ne anrl 5-de..,~ ..,l.,u.... r Example 81: With Llh,l~yl~lull~ ulll as cocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added norbornene ~3.7 g), 5-dc~,y' I,ull.~nc (3.6 ml) and 1,2 dichloroethane (40 ml).
Thereafter was added the catalyst (0.016 mmol) ~ ' '~/ followed by tricLlly' ' (0.1 ml of 0.5 Molar solution in hexanes, 0.05 mrnol). There ensued an extremely rapid and exothemmic pulyl..~ Liul~ which was temminated 5 with methanol after I hour. The polymer was washed with methanol and then acetone and dried ovemight at 80C under vacuum. The polymer (6.1 g was recovered) showed a molecular weight of 738,000 (Mw~ Mn = 172,000).
Example 82: With ~ Lllyl~dlllllillu~ll as cocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added 20 norborrlene (3.7 g), 5-dl,~,y' I,.,.~.. ,nc (3.6 ml) and 1,2 dh,l~lul~ ' (40 ml).
Thereafter was added the catalyst (0.0073 mmol), BF3 etherate (0.015 ml, 0.117 mmol) ' '~/ followed by triethylaluminum (0.26 ml of 0.5 Molar solution in hexanes, 0.13 mmol). There ensued a very rapid and exothemmic polymerization which was temminated with methanol after I hour. The polymer 2s was washed with methanol and then acetone and dried ovemight at 80C under vacuum. The polymer (6.05 g was recovered) showed a molecular weight of 674,000 (Mw, Mn = 197,000).

WO 95/14048 2 1 7 4 7 ~ 6 PCTNS94/13166 .

3~xample 83: Witb triethylaluminum as cocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added norbornene (3.7 g), 5 J~,yll...,l,..",. I~r (3.6 ml) and 1,2 dh,hlu~ ' (40 ml).
Thereafter was added the cahlyst (0.027 mmol), BF3 etherate (0.015 ml, 0.117 s mmol) i~ ,J;d~ely followed by triethylaluminum (0.26 ml of 0.5 Molar solution in hexanes, 0.13 rnmol). There ensued a very rapid and exothermic poly which was terminated with methanol after I hour. The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum The polymer (6.3 g was recovered, 93%) showed a molecular weight of 723,000 (Mw, Mn = 141,000).
Example84: Withtriell,y' ' ascocahlyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added IIUIbUIII~ (3.7 g), 5-d~,~,yll~ul~ul~ e (3.6 ml) and 1,2 ' " . . ' - (40 ml).
Thereafter was added the catalyst (0.015 mmol), BF3-etherate (0.03 ml, 0.234 mmol) 1 ~S/ followed by ~ ly~ ~ (0.26 ml of 0.5 Molar solution in hexanes, 0.13 mmol). The ratio ofthe cahlyst . (Ni:B:AI) was 1:15:17 and the ratio of the monomers to catalyst (llU~bUII~II~ to Ni) waS
3,600:1. There ensued a very rapid and exothermic pol~ iùl. which was terminated with methanol after I hour. The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum. The polymer (6.2 g was recovered, 92%) showed a molecular weight of 1,350,000 (Mw, ML =
3 1 0,000).
Example85: Withd;~ y' ' chlorideascocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added norbornene (3.7 g), 5-d~,~,yll~ulbulll~,.le (3.6 ml) and 1,2 dichloroethane (40 ml).
Thereafter was added the catalyst (0.018 mmol), BF3-etherate (0.015 ml, 0.117 mmol) ~ ,followedbyneatdi;~ y'' chloride(0.13mmol).
There ensued a very rapid and exothermic IJUIyl...,.;~dtiUII which was terminated WO 9~il14048 PCT/US94/13166 with methanol after 1 hour. The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum. The polymer (5.1 g was recovered) showed a molecular weight of 238,000 (MWI Mn = 103,000).
E~amples 86 and 87 S PrPp:~ratinn of ~"'t~lySt ll~,.~diluul~ acid (HSbF6, 1.92 g, 8.1 Immole) was placed in a dry, nitrogen filled Teflon~9 bottle with a Teflon~ caplvalve containing a magnetic stir-bar followed by nickel ~LIIy'' (8% in mineral spirits, 4.05 mmole) and the resulting mixture mixture was stirred at ambient t~,llllJ.,lll~Ule for 10 2 hours.
Cuvolyll .i,..l;....~ nf~nrbnrnPnP an.l 5-~r ~ I,u,......
Example 86: With Llh,illy' ' as cocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added norbomene (3.7 g), S-dc.,ylllull,ul,l.,.,c (3.6 ml) and 1,2 dh,lllulu~illa.le (40 ml).
Thereafterwasaddedthecatalyst(0.013mmol),BF3etherate(0.015ml,0.117 mmol) ;I..I~ Lely followed by triethylaluminum (0.26 ml of 0.5 Molar solution in hexanes, 0.13 mmol). There ensued a very rapid and exothermic polyll.~ i;oll which was terminated with methanol after I hour. The polymer was washed with methanol and then acetone and dried overnight at 80C under 20 vacuum. The polymer (6.3 g was recovered, 93%) showed a molecular weight of 1,270,000 (Mw, Mn = 262,000).
Example 87: With Ll;.,illy' 11 as cocatalyst:
To a 100 ml glass vial equipped with a magnetic stir-bar was added norbornene (3.7 g), 5-d~,~,ylllulbùll..,ll~, (3.6 ml) and 1,2 ~' ' ' u. ' (40 ml).
Z5 Thereafter was added the catalyst (0.013 mmol) ' ' 1~ followed by Llh,illy~-~ (0.52 ml of 0.5 Molar solution in hexanes, 0.26 mmol). There ensued an extremely rapid and exothermic poly,ll~ L;ull which was terminated WO 95tl4048 ~ '~ 7 4 7 5 PC ItUS94/13166 witb methamol after I hour. The polymer was washed with methanol and then acetone and dried ovemight at 80C under vacuum. The polymer (6.2 g was recovered) showed a molecular weight of 931,000 (Mw~ Mn = 224,000).
Elample 88 S Pr!~.r~atinn nf r~tAlyst IUUIU~IIUI.U.Ih~ acid (HSbF6, 0.45 g, 1.90 mmole) was placed in a dry, nitrogen filled Teflon~ bottle with a Teflon~ cap/valve containing a magnetic stir-bar and the contents were cooled to -27C. Thereafter was added nickel ~L;Iylh~A~uluGLe (8% in mineral spirits, 1.9 mmole) and the resulting 10 mixture was allowed to warm to ambient i . ~lLuie and was then stirred at ambient i I -Lul = for 2 hours.
TT..,....~n~,....;~AI;I~II nfiAnrbr,riA~nf~
To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 d;.,lllolu~,LllAI.. (40 ml), norbornene (~ g, 53.1 mmole). Thereafter was added the catalyst (0.012 mmol), TiCI4 (0.013 ml) I!t fOllOWed by Llh,;.llyl.~ ...illu..l (1.3 ml of 0.1 Molar solution in heptane, 0.13 mmol). There ensued a slow polymerization which wa3 terminated with methanol after 12 hour. The polymer was washed with methanol amd then acetone and dried overnight at 80C under vacuum. The polymer yield amounted to 0.9 g (18%).
20 E~ample 89 Prepar~tinn nf r~ lyst Nickel ethylhexanoate in mineral spirits (I mmol of nickel) was added to a flask under a nitrogen atmosphere and diluted with toluene (about 20 ml).
To this solution was added a solution of BF3-etherate (1.13 ml, 1.3 g, 9 mmol) in 2s toluene, causing the original green solution tû turn yellow-green in color.
Butadiene was then bubbled through the solution for ~lnuA.;I~lAL=ly 5 seconds.
The fla3k then briefly evacuated and refilled with nitrogen to remove excess WO 95/14048 :, PCT/US94/13166 0 2 1 7 4 7 ~ 6 butadiene. To this solubon was slowly added triethylaluminum (15 mmol) diluted to about 10 % wt in toluene while the flask was cooled in ice water. To this solution was added neat HSbF6 (0.48 g, 2 mmol). The resuiting solution/slurry was a dark-brown/black solution or colloidai slurry of the s catalyst in toluene.
Cogoly., .;,rl;~11 nfr~nrhnrr~ anrl5-~ln~l..v~ 1 I)UII~
To a 50 ml glass Yial containing a magnetic stir bar norbomene (1.8 g, 18.8 mmol) and 5-d~ ' bU~ IC (1.46 g, 6.25 mmol) was added d;_l~lu~u~,Ll~c (32 ml) followed by the catalyst (,~ 'y 0.008 mmol).
10 After one hour ethanol was injected to terminate the reaction and the polymerwas washed with excess acetone, filtered and dried overnight, under vacuum at 80~C. The yield of polymer was 2.52 g (77%).
EYample 90 Pn~r~ation of r~tolySt Nickel cLi~y" - in mineral spirits (I mmol of nickel) was added to a flask under a nitrogen atmosphere and diluted with toluene (about 20 ml).
To this solution was added a solution of BF3 etherate (I .13 ml, 1.3 g, 9 mmol) in toluene, causing the original green solution to tum yellow-green in color.
1,5-~,yl ': ' - (3 mmol) was then added. To this solution was slowly added 20 J i~. il,~' ' I ' (1 O mmol) diluted to about 10% wt in toluene while the flask was cooled in ice water. To this solution was then added neat HSbF6 (0.48 g, 2 mmol). The resulting solution/slurry was a dark-l"u...0~14~ solution or colloidal slurry of the catalyst in toluene.
Copoly".... i~.o;~llnfrlnrhorn~n~an~i5-~ U~
To a 50 ml glass vial containing a magnetic stir bar norbornene (1.8 g, 18.8 mmol) and 5-dc~,~l.lull.ul~.~,..e (1.46 g, 6.25 mmol) was added ihlllul~ ' - (34 ml) followed by the catalyst (~~ ' 'y 0.008 mmol).

~ WO 95/lqOq8 2 1 7 4 7 5 6 PC~nJSg4JI3l66 After one hour ethanol was injected to terminate the reaction and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of polymer was 2.26 g (69%).
Example 91 S Pr~.r^-atinn of ~ lyst Il~4nuulu4llL;ulu~l;c acid (HSbF6, 0.68 g, 2.85 mmole) was placed in a dry, nitrogen filled Teflon6 bottle with a Teflon0 cap/valve containing a magnetic stir-bar and the contents were cooled to -21C. Thereafter was added nickel eLh~" (8% in mineral spirits, 1.9 mmole) and the resulting 10 mixture was allûwed to warm to ambient ~ 4~UI~ and was then stirred at ambient t~ for 2 hours.
T~ ~ elfnnrl~nrn.on~
To a 250 ml glass reaction flask fltted with mechanical stirring was added l~ulhu~ (10 g, 106 mmol), used as received without any ~u~ir~ iul~, 15 and d;"l.lc,., ' - (188 ml). The flask was cooled to 0C and thereafter was added the catalyst (d~ S/ 0.019 mmol), BF3-etherate (0.171 mmol) and L h~LLy~ ' (0.19 mmol). Polymer formed ~ Iy upon addition of the final catalyst ~-nmrnn~t. the t~ 4Lul~; rising to 4~ , 20C.
After one hour ethanol was injected to terminate the reaction and the polymer 20 was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of polymer was 9.6 g (96%).
E~amples 92 ~nd 93 Pre~ar~tinn of r~t!-lvst IL,,.4nuulu4llL;Illullic acid (HSbF6, 0.608 g, 2.57 mmole) was placed in 2s a dry, nitrogen filled Teflon~ bottle with a Teflon6 cap/valve containing a magnetic stir-bar and the contents were cooled to -27C. Thereafter was added nickel ethylhexanoate (8% in mineral spirits, 2.57 mmole) and the resulting WO 95/14048 PCT/[JS94113166 mixture was allowed to warm to ambient i . ~ and was then stirred at ambient i . ~Ul~ for 2 hours.
CUVCII~ `nfrlnrbnrr~PIlP1 ~tll~y~ ul/. ~\f Example 92: To a 250 ml gla3s reaction flask fltted with mechanical 5 stirring was added a 90:10 mol:mol mixture of norbomene and cLllyl;d~ bùl~ e(10g, 103mmolesoftotalllulbull.~,..~)and di~ lu~ ' (138 ml) at ambient i ~ ~. Thereafter was added the catalyst (al,l,., 'y 0.052 mmol), BF3 etherate (0.47 mmol) and tric~ yl~dul~ u~l (û.52 mmol). Polymer fommed -~ / upon addition of 10 the final catalyst component. After one hour ethanol was injected to temminate the reaction and the copolymer was washed with excess acetone, filtered and dried ovemight, under vacuum at 80C. The yield of polymer was 6.7 g (67%) Example 93: In a second experiment identical conditions were employed except that l-decene (0.52 mmol) was added as chain transfer agent.
5 The copolymer yield was 6.5 g (65%).
E~smples 94 and 9S
Prepamtinn of r~t~llySt II~,Adlluulua~lLilllullic acid (HSb~6, 0.851 g, 3.59 mmole) was placed in a dry, nitrogen filled Teflon0 bottle with a Teflon0 cap/valve containing a 20 magnetic stir-bar and the content3 were cooled to -28C. Thereafter was added cobalt . i (12% in mineral spirits, 3.59 mmole) and the resulting mixture was allowed to wamm to ambient i , ~UI~ and was then stirred at ambient t~lllp~ Ul ~ for 2 hours.
Mnmnrnly".. .;~ nf rnrbnrrPn~
Example 94: To a 100 ml glass vial containing a magnetic stir bar was added norbornene (5 g, 53 . I mmol) and di~ ùlu~ e (45 ml). At ambient ~ WO 95114048 2 1 7 ~ 7 5 6 PCT/U594/13166 Lcn~ ulc was added the catalyst (~ oAIu~ cl~ 0.013 mmol, dissolved in 1,2 lih,LI~lU~ , 3 ml), BF3-etherate (0.117 mmol) and I~ L~ .II;IIUUII (0.13 mmol) There was an immediate, highly exothermic reaction on adding the last catalyst romrnnPnt After one hour methanol was injected to terminate the s reaction and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of polymer was 4.1 g (82%) The GPC showed a weight average molecular weight (Mw) of 424,000.
Example 95: The above reaction was repeated identically except that l-decene (0.2 ml) was added as a chain transfer agent. The polymer yield was 10 4.3 g (86%) NMR indicates the presence of olefinic end groups and the GPC
showed a weight average molecular weight (Mw) of 233,000.
E~ample 96 PrPr~r;~tinn c f r~t~lyst IIcAdfluulu~liilllull;c acid (HSbF6, 0.575 g, 2.23 mmole) was placed in 15 a dry, nitrogen filled Teflon0 bottle with a Teflon0 cap/valve containing a magnetic stir-bar and the contents were cooled to -28C. Thereafter was added iron napthenate (6% in mineral spirits, 2.23 mmole) and the resulting mixture was allowed to warm to ambient i , c and was then stirred at ambient ~CllliJ.,. c for 3 hours.
20 J~ r~ AI;...~ ~fnnrbOmr-n~
To a 100 ml glass vial containing a magnetic stir bar was added ~VIb.)lll~ (5 g, 53.1 mmol) and .Ih,lllul, ' (45 ml). At ambient ~CII.~ was added the catalyst (~ 'y 0.013 mmol, dissolved in 1,2 dichloroethane, 3 ml), BF3-etherate (0.117 mmol) and 11i~,L;Iy' ' (0 13 25 mmol). After one hour methanol was mjected to terminate the reaction and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of polymer was O.S g (10%).

wo gs/l4048 2 1 7 4 7 5 6 PCTNS94113166 E~ample 97 Pr~ atinn nf r~t~lySt A~IUU~ '' ' ' acid (HSbF6, 0.666 g, 2.81 mmole) was placed in a dry, nitrogen filled TefloD~ bottle with a Tef~on~ cap/valve containing a s magnetic stir-bar and the contents were cooled to -28C. Thereafter was added palladium eLIlylll~A~lllUdLC (in mineral spirits, 2.81 mmole) and the resulting mixture was allowed to wamm to ambient i , r, and was then stirred at ambient L~II~ UI c for 2 hours.
Hnmn,polyl"...i, l;.,., nfn-~rborr.~ne To a 50 ml glass vial containing a magnetic stir bar was added norbomene (5 g, 53 . I mmol) and dichloroethane (40 ml). At ambient L~ laLul~ was added triethylaluminum (0.13 mmol) followed by the catalyst )A;lll~Lcly 0.013 mmol, dissolved in 1,2 dh,lllul~ " , 3 ml). After one hour methanol was injected to temminate the reaction and the polymer was 15 washed thoroughly with excess acetone, filtered arld dried overnight, under vacuum at 80C. The yield of polymer was 1.5 g (30%).
Example 98 IJ~ ;"" of rlnrborr~ne To a 50 ml glass vial containing a magnetic stir bar and norbomene (5.0 20 g, 53 . I mmol) was added isooctane (3 ml) followed by the cobalt n, (0.053 ml of a 1.0 molar solution in toluene, 0.053 mmol) and eLIly' I
dichloride (50% in hexanes, 0.265 mmol). After one hour ethanol was injected to temminate the reaction, the polymer was ~ , ' from solution by adding the solution to an excess of ethanol and the polymer was filtered and washed 25 with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of poly(norbomene) was 2.6 g, 52%. The polymer was ~h~ u;~,l ;L~J by proton NMR methods (in CDCI3) to be the addition polymer of norbornene (resonances between 0.8 and 2.6 ppm, no indication of, ' ~ll;Ull) -Esample 99 rT~ ly~ ;n.~ of nnrbnrrl~ne ;n h~nt~no - To a 50 ml glass vial containing a magnetic stir bar and norbomene (Sg, 53.1 mmol) was added heptane (35 ml) followed by nickel ~LIl~lllw~l s (0.026 mmol) and ~LIlyl~llul~ ul~l dichloride (0.13 mmol). ~fter one hour ethanol was injected to the viscous polymer solution to terminate the reacion.
The polymer was then 1,l t~ dLtd from solution using an excess of ethanol, filtered and the polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The yield of poly(norbornene) was 3.75 g, 75%. The GPC data was as follows: Mv, 235,000, M~ 90.000.
E~cample 100 C~l~o~ ;nn nfnnrbOrn~n.~ 5 ,~, yl"".l"""~ ,~
To a 100 ml glass vial containing a magnetic stir bar and a mixture of nulbùll,~ and 5-d~,~,yll~ulbul,.~ (75/25 mol/mol, 53 mmol total IIU~bUIII~
1s was added heptane (35 ml) followed by nickel ~:LI.~" (0.013 mmol) and ~LIly' ' dichloride (0.065 mmol). After one hour ethanol was injected to the solution to terminate the reaction. The polymer was ~JlG_ r ' with excess ethanol, washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The polymer yield was 4.75 g, Mw 458,000, M" 174,000.
E~mp1e 101 To a 50 ml glass vial containing a magneic stir bar and norbornene (5 g, 53.1 mmol) was added 1,2-di~.lllu~u~,Llldlle (35 ml) followed by nickel ~LIly~ ulo~L~ (0.026 mmol) and ethylaluminum dichloride (0.13 mmol). After one hour ethanol was injected to the slurry to terminate the reaction. The 2s polymer was washed with excess acetone, filtered and dried overnight, under vacuum at 8ûC. The yield of poly(norbornene) was 4.6 g, 92%.

Esamples 102-104 CUVOIYI~ f f rlf~rborr~f~nf ' S-flf y~ lbul~ .fi To a 100 ml glass vial containing a magnetic stir bar and a mixture of norbomene and 5-dc~,rlllo-~o~ , (75/25 moUmol, 53 mmol total liUlbUIII.~Il~) s was added halollydlu.,O.l,ul. (30 ml) followed by metal cLIIy-' ' (0.026 mmol in the case of nickel, 0.013 mmol in the case of palladium) amd eLllyl~lulll;llulll dichloride (0.13 mmol). After one hour ethanol was injected to the slurry to temminate the reaction. The polymer was washed with excess acetone, filtered and dried ovemight, under vacuum at 80C. The polymer 10 yields are tabulated below:
E?;. Pol er conversion, Metal 1~ , ~, ym Mw M
vield O %
102 Nickel 12- ' ~ . 5.8 85 602,000 73,800 103 Niclcel . 6.0 88 992.000 96.500 15 1~)4 PaDadir~ 1.2 :' ' ' . ' 6.4 94 149.000 74.100 Ex~tmple 105 Cu~olyll. ~ of rlf~rbon-f~nf~ anfl 5-d To a 50 ml glass vial containing a magnetic stir bar and a mixture of norbomene and 5-dc~,ylllulbull~ L (75/25 mol/mol, 53 mmol total llull,ulll~l~,.,) was added ~y, ' ' - (30 ml) followed by nickel ~LIIy'' (0.013 mmol) and ~so-butylaluminum dichloride (0.02 ml). After one hour ethanol was injected to the solution to temminate the reaction. The polymer blend was then , 'f ' with excess ethanol and was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The polymer yield was 4.8 g. The 2s GPC data was as follows: Mw 416,000, Mn 160,000.

~ WO 95/1~048 2 1 7 ~r 7 5 6 rCT/VS94J13166 EYample 106 Copolvr~ri 7~ti fm of r orborrl ~n ~ ar~ r~ 5-d~,~ 1". " 1,. " ". - --To a 50 ml glass vial containing a magnetic stir bar and a mixture ofnorborrlene and 5-di,~,yl~ l)u~ ,.i6 (75/25 mol/mol, 53 mmol total ~u~l~u"~,..~) s was added heptane (30 ml) followed by nickel ~ (û 013 mmol) and dh,Ll~ lu.~ululll chloride (0.065 mmol) After 5 days ethanol was injected to tbe solution to terminate the reaction. The polymer was dissolved in toluene arld then l~e~,;p;ul~td with excess ethanol and was washed with exc6ss acetone, filtered and dried overnight, under vacuum at 80C The polymer yield was 6 1 0 g The GPC data was as follows: Mw 377,0ûO, Mn 136,000 E~amples 107-109 ~om~olym! ri7~1tir)ne of rnrhr)rn~n~
To a 100 ml glass vial containing a magnetic stir bar and norbornene (5 g, 53 1 mmol) was added 1,2-di.,lllol~ ' - (60 ml) and l-decene (0.2 ml, 2 15 mole %) at the t~ Ull~ indicated in the following table followed by palladium r~Lil ~ " (0 088 ml of a 0 2 molar solution) and ~ lu~
dichloride (û û53 ml of a 3.4 molar solution). After 60 minutes the reaction washalted by adding to excess methanol, followed by filtration and washing with excess methanol, and drying overnight, under vacuum at 80C. The polymer 20 yields are tabulated in the following table:
Reaction Polymer Conversion Example # Temperature, Yield, De,rJree C
101 40 3.62 72.4 108 55 3.73 74.6 - 109 70 3.70 74.0 E~amples 110-130 mf~r~lyl,.. .;,..1;.~1l of ~
To a 100 mL vial, equipped with a TeflonI' septum and a stirbar, was added llùlbu~ (5.0 g, 53 mmol) in 1,2-J;~,l-lu~ (60 mL). To this s solutiûn was added a I ,2-J;~ u~ ~ ' solution of Ni(II) 2-~LIly-' (0.66 mL of a 0.032 M solution), a toluene solution of ui.,l~' ' (0.45 mL of a 0.22 M solution)~ and a toluene solution of chloranil (0.21 mL of a 0.10M solution). The polymerization was allowed to continue for I hour. The slurry was poured into methanol, stirred, filtered, and dried in a vacuum oven 10 overnight at 80C.
Yield = 3.06 g (61%), MW = 585,000, Mn - 215,000.
The following llu~l~olmlyl,..,~ ;Ulli were carried out as in Example 110 above except that the activator (third component) differs as well as the amounts of catalyst. cocatalyst, and activator. The results of the 15 llull~upulylllcrizations are presented in the following table:
Homopoly~ IiUII of Nv~u~ll~,l.., Ex3mple NiHEX CEM TEAI Mn Mw MJ
(mmol Ni) trieth-l Aeth~ator Yicld (xlO ~) (xlO i) M.
15mg 11.4mg chlornil 3.06g 215 585 2.72 (0.021mmol) (O.lOmmol) (0.021mmol~ (61%) 15 mg 11.4mg HCA 3.83 g 20 111 (0.021mmol) (U.lOmmol) (0.021mmol) t77~) 32.5 87.1 2.68 15mg 11.4mg BPCC O.lOg 112(0.021mmol) (O.lOmmol) (0.021mmol) (2%) 70.6 194 2.74 15mg 11.4mg HFIPA 0.7g 596 3.13 (0.021mmol) (O.lOmmol) (0.021mmol) tl4%) 15 mg 23.9 mg chlor.mll 2 (0.021 mmol) (0.21 mm~l) (0.021 mmol) (56/,) 71 ~ 17~ 2.49 15 mg 23.9 mg HCA 2.51 g 76 205 2.68 (0.021mmol) (0.21mmol) (0.021mmol) (50%) .

~ WO95114048 2 1 7~7~ PCT/US94/13166 TEAI
Ex mple NiHE~ CEM t/iethvI Ar,ivirlor Yield Mr Mv. MJ
~mmolNi~ i~ (xlO~) (xlO'`) M~
15mg 23.9mg BFCC 0.50g 65.9 203 3.08 ~0,021mmo) ~0.21mmol) (0.021mmol) (10/~
15mg 23.9mg HFIPA 3.17g 117(0.021mmol) (0,21mmol) (0.021mmol) (63~) 176 441 2.51 11815mg 239mg HCA 4.48g 408 2.94 (0.021 mmol) (0,21 mmol) (0.21 mmol) (90Yo) 15mg 23.9mg BPCC 4.00g 41 79,7 1,94 (0.021 mmol) (0,21 mmol) (0.21 mmol) (80%) 15mg 23.9 5 120 (0.021mmol) (0,21mmol) (0.21mmol) (48257o/og) 240 610 254 12115mg 23.9mg HF~TA 3.288 (0.021 mmol) (0,21 mmol) (0,21 mmol) (66%) 2215mg 23.9mg 4.22g 96.6 366 3.79 (0.021mmol) (0.21mmol~ (84~) 15mg 23.9mg 4.41g 123(0,021 mmol) (0.21 mmol) (88%) 12g 3.04 15mg 23.9mg HCA(0.2 1 4.51 g 124(0.021 mmol) (0.21 mmol) mmol) (90, ) 13 125 lOmg 15,9mg ohlorimil 2.69g 239 639 2.68 (0.014mmol) (0 14mmol) (0.14mmol) (54%) 126lOmg 15,9mg HCA 4.31g 124 2.8 (0.014mmol) (0.14mmol) (0,~4mmol) (86/~) lOmg 15.9mg BPCC 4.11g 127(0.014mmol) (0.14mmOI) (0.14mmol) (82o) 60,1 130 2.16 10mg 7.9mg chlor oil 4.00g 128(0.014mmol) (0.07mmol) (0.014mmol) (80-~) 117 276 2.36 129lOmg 7.9mg HCA 3.50g 125 330 2.64 (0.014mmol) (oo7mmol) (0.014mmol) (70,o) lOmg 79mg B
15 130 ~0.014~ 007 '` ~0014~ 28/~ 97'7 314 3.22 ?.--HCA ~ .a~ uludC~,tOI~, BPCC=3-butenoic acid-2,2,3,4,4-~r~r~t- ' ' Ub HFGTA h~"~alluului~luLal;c acid, HFIPA h~".anuu~u;i~u~JIu~du~

2 1 747;)6 E~mples 131-145.
COPOIY~ f r~u,~ nrl S--D~ l ,.. A~
To a 100 mL vial, equipped with a Teflon0 septum amd a stirbar, was added llulbu~ c (3.74 g, û.40 mol) and 5-d~,~,yli.JI~o~ , (3.10 g, 0.013 mol) S in 1,2-dichloroethame (60 mL). To this solution was added a 172-d;~,llo solution of Ni(lI) 2-~LL~l~ .. (0.66 mL of a 0.032 M solution), a toluene solution of trietbylaluminum (1.76 mL of a 0.24 M solution), and a toluene solution of hexachloroacetone (2.2 mL of a 0.10 M solution). The pOIyll~ iUll was allowed to continue for I hour. The slurry was poured into 10 methanol, stirred, filtered, and dried in a vacuum oven overnight at 80C.
Yield = 6.04 g (88%), Mw = 71,500, M~ = 32,300.
The following ~UI)UIYI.A~ ;UII~ were carried out as in Example 131 above except that the amounts of catalyst, cocatalyst, and activator differ and tbe type of cocatalyst differs. The results of the copoly.~ -- are presented in 15the following table:
Cu!~olyll..,l;~_l;oll of Norbornene and S-D~"y' bUII.~I~.
Al ~x le ~ Alkvl I~CA Yitld M. M~ M M
mp (mm~l) (mmol) (Xl~) (xlO') J ^
IEAI 6.04 131 0.021 0.21 32.3 71.5 2.21 0.42 (88.3~o~
132 0.021 lEAI l.OOg 0.21 (14.6 TEAI 1.84 20 133 0.021 0.42 (26.9/o) TEAI S.98 134 0.021 0.21 g 31.8 66.9 2.11 0.42 (B7.4%
0.011 IEAI 3.55 135 0.2 4 63 6 127 1.99 lEAI 0.21 5.90 136 0.021 g 42 5 83.1 1.95 0.32 (86.3/~) ~ WO 95114048 2 1 7 4 7 5 6 PCT/US94/13166 N IIC~
rX3mplc~ ~ Alk I Yicld Mn M~ MJM
(mmol) ~mmol) (xlO ') (xlO'~) (mm~l) .021 0.2 0.21 (79.5o,c) 226 .0211 oDr3~2Ac 021 (807%) 92.3 2.
.021 ns~ 0.21 4.20 g 83.3 158 1.9 0.42 (61.
nBAI 5.47 0.021 0.21 121 234 1.93 0.32 (80.0 ns~l 5.50 g s 141 0.021 0.2 0.2~ (gO4O~) 105 253 2.41 .021 nBAI 99.5 236 237 0.2 (82.0o,.) 43e 0.021 nBAI o.lo 6.40 g 66.6 216 3.24 0.2 (93.
ns~ 3.
.021 o.lo 68.2 144 2.
0.32 (48.4/o) nB~I
145 0.021 o.ll (04383O,go~ 43.2 93.2 2.16 10 Polymerization run for 7 hrs.
TEAI=triethylaluminum, DEAC-d;~ y'~' chloride, TIBAI~ vl/u~yL~luminum E~ample 145-146 Cùv~ Iy~ , of 1~ n~i S~ YIIIOI~ r 11 ' ~ Oth~r c~t3lysts 15 Polyll.. ,. i~liu.. , were run as example 131.
Copvl,~,...~,.;~";vl,ofNvll)ull.~ candD~ u.l)ull.~,..c(75:25)UsingPdand Co with Hexachlu.ua~,~tvl~ (HCA).

WO 95114048 2 ~ 7 4 7 5 ~ PC'I;'IJS94/13166 Catalyst Al Alkyl HCA M" M~
~-xar~ple# (r~m301) (mmol) (rnntol) 103 10 Co IIBAI 0.31 145 - 0.11 g 21.3 161 0.021 0.2 (4.5%) Pd I~AI 5.43 146 0.11 66.9 213 0.02 1 0.2 (79.3%l E~sntples 147-157.
S T~nm~nlyrnl~ri7~tinn nrNv~ "~ With vanmlc sySt.
k~ .~.1.1...,.~,.~."~ ,lc l~rtiYatnr~
The following example3 were run according to the procedure used in example 1 1 0 except that a~ c were carried out using hexachloroacetone as activator (ratio metal c~ll h..,.. hl. ", ~
trir,ll-y'~ 0:10), for I hr, in ' " v~ ~ , at room ~.llp~ JlCi.
rx l~ ~ C kl sl Norbomer~ Con~ersion mp y c~ vs~ l O ~ l o l 7 NiH-xc~m 2500:1 E4~,i l03 44.3 NiC~(PPh~k zsoo:l 88o,i 420 65.9 NiCI (PPh~CH~ 2500:1 43~,i 82.9 5.57 lso 2~00.1 9l% 423 64.4 t~tr hvd~k :l 88%
dihvdr.te Ni(ll)-ciLitetrshydr l~ 2500:1 7l% 453 t2.t 153 ~ PdC~(PPh~k 2500:l 60 Pd 11 l54 ( 2500:l sso~L 411 9.96 20 l55 Pd(ll) 2500:1 84o/i 384 3.44 ) 156 Pd Hexcem 3800:1 80~,6 157 Pdr~c~ (pph~- 2500:1 33%

~ WO 95114048 2 1 7 4 7 5 6 PC'rlUS94~13166 E amples 158-160 EY~n~ el58: Copoly~ Iof~nrl~nml~n~ af~-l5-d ~y;l.lbulll f To a 50 ml glass vial containing a magnetic stir bar and a mixture of norbornene (3.7 g), 5-d~,~,yL~ulbulll~ (3.6 ml) and l-decene (0.1 ml) was S added ~ ,lol.~le (35 ml) followed by nickel cLl.y" (0.013 mmol) and ethylaluminum dichloride (0.065 mmol). ~fter two hours ethanol was injected to the solution to temminate the reaction. The polymer blend was then diluted with toluene amd IJ~c~ J;La~cd with excess acetone and was washed with excess acetone, filtered and dried overnight, under vacuum at 80C. The polymer yield was 5.4 g. The GPC data was as follows: Mw 254,000, Mn 100,000.
FY~n~plfc 159. 160: }~nnnnpoly~ of norhnrrn~nf To a 100 ml glass vial equipped with a magnetic stir-bar was added ~w~bu-..~ (5 g, 53 . I mmole) and an equimolar amount of the olefins listed in 15 the table below. The vial and its contents were cooled to -20C. Thereafter was added the nickel elllylll."~ G (0.026 mmole) and ethylaluminum dichloride (0.13 mmole). There ensued a rapid and exothermic lJuly...e~ Liul. which was temminated with methanol after I hour. The polymer was warmed to amhient ~, dissolved in cyclohexane and .c~.~ . ' with methanol. The 20 polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum. The polymer yields and MW data are listed below:

wo 9~14048 2 1 7 4 7 56 PCT/U~94/13166 0 Example ield Olefin, type Y ~ M Mn 4-methyl-pentene- l 159 5 7,300 3,6~0 (4MP 1 ) 4-mt:LI.~ ne 160 5 139,000 37,300 (4MC) Each of the homopolymers showed the presence of olefinic end groups as witnessed by the presence of resonances in the proton NMR
(o-~i~l.lolul,~. "lle) in the region 5-6 ppm (5.3-5.5 in the case of 4MPI, 5.2-5.7 in the case of 4MC).
E~ample 161, 162 10 IT~ ;l.ofrlnrbornen~ with jcnh~ pn~c eh:~intr;lrcfer a~eent Example 161: To a 50 ml glass vial equipped with a magnetic stir-bat were added norbornene (5 g) and isobutylene (5.0 g). At -30C tue catalyst (catalyst A ([(l13-crotyl)(cycloocta-1,5-diene)- nickel] IL..,~dnU~JII r' , ~ ' ~4 6 mg, 0.013 mmol) dissolved in 1,2-dichloroethane (2 ml) was added. The 1s reaction was allowed to continue at -30C for 3 hours and was then kept at -20C
overnight (15 houts). The reaction was then tetminated by adding ethanol. The polymer was dissolved in toluene, I ~ ' with methanol, washed extensively with acetone and dried under vacuum, ovetnight, at 80C. The polymer yield was 2.8 g (56%). The moleculat weight was 27,400 (Mw, Mn =
13,800). Evidence that the polymer is tetminated with ~ ~uL~ '' (i.e., methylene groups, -CH2C(CH3)=CH2) end groups is to be found in the proton N~ (deuterated chloroform) which shows resonances attributed to the methylene protons at 4.7-4.8 ppm. The ptoton NMR spectrum also indicates the -~ WO 95/14048 2 1 7 4 7 5 6 PCTIUS94J1316~;

polymer to be essentially devoid of isobutylene in the backbone.
Example 162: To a 100 ml glass vial equipped with a magnetic stir-bar were added 1,2-di~ lul~ ' (40 ml), norbomene (5 g) and isobutylene (5.0 g). At ambient t~ e the catalyst (catalyst A ([(Tl3-crotyl)(cycloocta-1,5-diene)nickel] ~.~,Ad[luul~r' , ' , 9.2 mg, 0.026 mmol) dissolved in 1,2-d;~Llù~ ' (2 ml) was added. The reaction was temmmated after ~ hour by adding ethanol. The polymer was dissolved in toluene, ~ ' with methanol, washed extensively with acetone and dried under vacuum, ovemight, at 80C. The polymer yield was 2.9 g (58%). The molecular weight was 17,400 1û (Mw, Mr = 9,580). Evidence tba~ the polymer is temminated with "isobutylene"
(i.e., methylene groups, -CH2C(CH3)=CH2) end groups is to be found in the proton NMR (deuterated chlorofomm) which shows resonances attributed to the methylene protons at 4 7-4.8 ppm. The proton NMR spectrum also indicates the polymer to be essentially devoid of isobutylene in the backbone.
Esampie 163 Prepar~ti- n nf r~t~lySt Nickel elLy~ (8% in mineral spirits) and dimel;.y' tetrakis(~ ~ u~ l)- borate (C6H5N(CH3)2H+(C6F5)4B-) were premixed in equimolar quantities in 1,2-dichloroethane to give a 0.125 Molar solution.
20 11~ oly ~ ;,-rlf ~l~rbonlpnp with isobl~tylPnP ;Ic ch~in trancfer ~.
To a 50 ml glass vial equipped with a magnetic stir-bar were added ulLul~ e (5 g) and isobutylene (5.0 g). At -30C the catalyst (0.104 ml, 0.013 mmol) was added followed by neat triethylaluminum (0.088 ml, 0.65 mmol).
There ensued a very rapid and exothemmic reaction which was temninated after I
hour by adding ethanol. The polymer was dissolved in toluene, I ~
with methanol, washed extensively with acetone and dried under vacuum, overnight, at 80C The polymer yield was 4.6 g (92%). Evidence that the polymer is temminated with "isobutylene'' (i.e. methylene groups, 21 74756 ~12 -CH2C(CH3)=CH2) end groups is to be found in the proton NMR (deuterated o-~i;.,l iului~ nc) which shows a resonance attributed to the methylene protons at 4 8 ppm Apart from the isobutylene end-group the polymer showed resonarlces ~ttrih~ le to poly(norbornene) I ~ . The proton NMR
spectrum aiso indicates the polymer to be essentially devoid of isobutylene in the backbone E~ample 164-167 pr~r~tinn of ~ ~t~l-Yst llw~dfluùl~ acid (HSbF~, 0 557 g, 2 35 mmole) was placed in a dry, nitrogen filled Teflon~ bottle with a TeflonX cap/valve containing a maenetic stir-bar and the contents were cooled to -28C Thereafter was added nickel ~LilY;~ OGL~ (8% in mineral spirits, 3 52 mmole) and the resultine mixture was allowed to warm to ambient L,lllp~,.GLul~ and was then stirred at ambient Lclll!J~I GLul ~ for 2 hours Coi~oly" ;, ~ of rlnrborrl~n~n~l 5 ~
To a 100 ml glass vial equipped with a magnetic stir-bar was added a 75 25 mole/mole mixture of norbornene and S-d.,~ u~bu~ , (totai 7 95 mi, 53 mmole of IlUfl)UIII.,.~ >) and 1,2 ~ih,lllulu~,LllGlle (32 ml) Then differinglevels of l-decene (M~" control agent) were added (see table below) Thereafter was added the catalyst (0 012 mmol), BF3-etherate (0 03 ml, 0 234 mmol) , followed by ~ ,Llly' ' (0 26 ml of 0 5 molar solution in hexanes, 0 13 mmol) There ensl~ed a very rapid and exothermic polr which was terminated with methanol after I hour The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum The polymer yields and MW data are listed below 2~ 74756 WO 9S/14048 PCTrU594/13166 Example l-Decene Polymer MM
# added, ml. vield, o w n 1640,03 6 556,000 181,000 1650.1 6 212,000 65,500 1660.2 5.7 144,000 54,600 1670.5 5.5 69,800 29,700 S E~amples 168-169 Pr~r~ratirJn nf r~lt~lyst II.,Adfluùludl~L;Il~vllic acid (HSbF6, 0.45 g, 1.90 mmole) was placed in a dry, nitrogen filled Teflon0 boKle with a Teflon~ cap/valve containing a magnetic stir-bar and the contents were cooled to -27C. Thereafter was added 10 nickel cLII~'- (8% in mineral spirits, 1.9 mmole) and the resulting mixture was allowed to warm to ambient t~ p.,ld~UIr and was Klen stirred at ambient ~,lllp.,l dLul t~ for 2 hours.
TT~ of rlnrhnrr~nr To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 t' ' ' ~ ' ~ (35 ml), norbornene (5 g, 53.1 mmole) and an equimolar amount of the olefins listed in the table below. Thereafter was added the catalyst (0.012 mmol), BF3-etherate (0.015 ml, 0.117 mmol) ' ~y fûllowed by L-h~ ' ' irl~rn (1.3 ml of 0.1 molar solution in heptane, 0.13 mmol). There ensued a very rapid and exoKhermic pul~ iu~l which was 20 terminated with methanol after I hour. The polymer was washed with methanol and then acc.one and dried overnight at 80C under vacuum. The polymer - yields and MW data are listed below:

WO95114048 2 1 7~ ~ 5 PcrluS94113166 Example Polymer Olefin Used M M
Yield, ~ w n 1684-nlL;l~ ,y. ~ 5 126,000 35,800 1694-methyl-1-pentene 4.8 11,600 4.920 EYamples 170,171 Pn~r~tinn of r~t~ lyst dlluùl~ ' ' acid (HSbF6, 0.45 B, 1.90 mmole) was placed in a dry, nitrogen filled Teflon~ bonle with a Teflon0 cap/valve contdining a magnetic stir-bar and the contents were cooled to -27C. Thereafter was added nickel ~:Llly" (8% in mineral spirits, 1.9 mmole) and the resulting mixture was allowed to warm to ambient L~ dLulc~ znd was then stirred at ambient t~ .,.dLul~ for 2 hours.
H- m~r~ly.,.~ of r~-rborrl.~nr To a ] 00 ml glass vial equipped with a magnetic stir-bar was added 1,2 dh,lllulu. ' (50 ml), norbornene (5 g, 53.1 mmole) and zl'~lhh,Ll.u,~y~ilane a3 shown in the table below. Thereafter was added the catalyst (0.012 mmol), BF3 etherate (0.015 ml, 0.117 mmol) '' '~, followed by triethylaluminum (1.3 ml of 0.1 molar solution in heptane, 0.13 mmol). There ensued a rapid and exothermic pOIyl,~ Liull which was terminated with methanol after I hour.
20 The polymer was washed with excess acetone and dried overnight at 80C under vacuum. The polymer yields and MW data are listed below. In each case the proton NMR spectra indicated that one mole of the allylLIh.Lllu~.y '' - was located on each polymer chain as a reactive end-group.

~ WO 91i/14048 2 i 7 4 7 5 6 PCT/USg4/13166 EY~ ple A i~ `t ' ~ ' Po~rier Coriversio~, M", Mn # (mmol. mol %~ ~ield~ ~ %
170 1.06. 2% 4.4 88 43.560 17,500 171 3.18.6% 2.1 42 27.770 12.720 .3 E~ mple 172 To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 Jh,~iJIu., ilil..e (40 ml), norbornene (5 g, 53.1 mmole) and l..cLi~ylll~.,Ll (I ml). Thereafter was added nickel ethyihexanoate (0.013 mmol) ir~
followed by ~. fh~l",l.;.. ~'1~ (1.9 mmol). The reaction mixture was allowed to stir at arilbient ~CI~ d~UlC for 2 hours after which it was terminated with methanol. The polymer was washed with acetone and dried overnight at 80C
under vacuum. The yield of polymer wa3 1.3 g (26%), the proton NMR
indicated that the polymer was terminated with a -CH=C(CH3)(CO2CH3) group originated from the methyl II.~,Llli ,ly' chain transfer agent, The GPC data was as follows: Mw, 142,000, Mn~ 50,700.
EYamples 173-175 To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 d~ lulu~,L~ (60 ml), norbornene (S g, 53,1 mmole) and l-decene (amounts shown in the following table). Thereafter was added palladium Liinuolu~ e~ale (0,66 ml of a O,032 1 molar solution), ' 'y followed by l~
(0.54 ml of a 0,386 molar solution) and hexachloroacetone (1,63 ml of a 0.129 molar solution). The reaction mixture was allowed to stir at ambient Lcll~iJ~ Lulc for I hour after which it was terminated with methanol. The polymer was washed with methanol and dried overnight at 80C under vacuum.

2 1 7 4 7 5 ~ PCTIUS94113166 ~1 E~xample l-Decene l-Decene Polymer # (ml) (mol %) Yield ~ Mw M~, 173 0 0 4.15 779,000 133,000 174 0.2 2 4.49 628,000 154,000 s 175 1 10 3.06 135.000 34,000 Esample 176 To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 dlchloroethane (60 ml), norbornene (5 g, 53.1 mmole) and allylL.;."~.JA~a;lane ( 1,2 ml, 1.085 g). Thereafter was added palladium Ll inuuluàl~eLaL~ (0.66 ml of a 0 0.0321 molar solution), i ' 'y followed by triethylaluminum (0.54 ml of a 0.386 molar solution) and L,A~.,l,lu-ua~,etu.l~ (1.63 ml of a 0.129 molar solution). The reaction mixture was allowed to stir at ambient i I ,:Lu.
overnight after which it was terminated with methanol. The polymer was washed with methanol and dried overnight at 80C under vacuum. The polymer yield was 1.88 g, M~" 33,000, M~ 19,300.
Examples 177-187 Pre. paratinn of ~t~lyst Il~,A;,nuul~ ~ acid (HSbF6, 0.45 g, 1.90 mmole) was placed in a dry, nitrogen filled Teflon~ bonle with a Teflon0 cap/valve containing a 20 magnetic stir-bar and the contents were cooled to -27C. Thereafter was addednickel ~LIl~ ,A~..JaL~ (8% in mineral spirits, 1.9 mmole) and the resulting mixture was allowed to warm to ambient i , ~L...~ and was then stirred at ambient ~ Lu.~ for 2 hours.

-~ WO95114048 2 1 7 4 7 5 5 PCT/rl594~1316~

Tlnmnrnlyl,...i, I;-,..~fnnrborT~Pn~
To a ] 00 ml glass vial equipped with a magnetic stir-bar wa3 added 1,2 ~' ' ' u~,~llallc (60 ml), norbomene (5 g, 53 . I mmole) and varying amounts of the olefins listed in the table below. Thereafter was added the catalyst (0.018 S mmol), BF3 etherate (0.02 ml, 0.162 mmol) ' 'y followed by Llh,;~ h....illUIII (0.18 mmol). The reactiorls were temminated with methanol after I hour. The polymers were washed extensively with methanol and dried overnight at 80C urlder vacuum. The polymer yields and MW data are listed below:
1û Example Olefm Pol er Conv.
Olefm TYpe Ym # (mol %) Yield. ~ %
1~7 allyl chloride 2 3.s 70 68sPoo 201.000 allyl chloride 5 3.3 66 458.000 186.000 179 allylchloride 10 3.15 63 351.000 163.000 15 180 ~ 2 4.65 93 77.000 29.000 2 2.1 42 271.000 112DoO
alcohol 2 4 80 79.000 35.000 all~l bromide 2 3.35 67 599,000 204.000 184 allylr,lYcidvlether 2 1 20 159.000 83.000 20 185 ~ . ! 2 4.4 88 I l I .ooo 49,000 2-allYlpherlol 2 1 20 116.000 59.000 187 ~.. 2 3.15 63 638.000 220.000 E~ample 188 Prpr~ratinn of ~t~lySt 2s Hexafluo.~,allLIll,ull;c acid (HSbF6, 1.126 g, 4.76 mmole) wa3 placed in a dry, nitrogen filled Teflon~9 bottle with a Teflon~9 caplvalve containing a magnetic stir-bar. The bottle was cooled in alcohol/dry ice arld nickel (8% in mineral spi}its, 4.76 mmole) was added and the contents were allowed to warm to room t.,.l.~J.,.aLul~.
Cu,uol~ I of rlnr~nrnPnean-l5d~ y1~ "1,1,.....
To a 250 ml glass poly vessel fitted with a mechanical stirrer S and baffles was added a 75/25 mol/mol % mixture of norbomene and 5-d~,ylllulbull.~,llc (lOg), I-decene (0.073 ml, 0.39 mmole) and methylane chloride (88 ml). To this stirred solution at -14C was added the above catalyst(0.016 ml, 0.019 mmole) followed by BF3 etherate (0.021 ml, 0.17 mmole) and triethylaluminum ( 1.0 molar in toluene, 0.19 ml, 0.19 mmole). The ratio of the 10 catalyst: . (Ni:B:Al)was l:9:10andtheratioofthemonomersto catalyst (l~ulbu~ to Ni) was 4,000:1. The polymerization ensued i~"l~ t~,ly upon addition of the aluminum alkyl with an immediate exothemm from -14~C to about 60C, ultimately the i . a~ul~ rose to 13C. ~
After one hour the POIYII~ ;VII~ which was in the fomm of an easily 15 stirrable slurry of polymer particles in the diluent, was temminated by addition of ethanol. The polymer was isolated by filtration and washed with excess etbanol before drying at 80~C under vacuum overnight to afford the copolymer product (9.03 g, 90% yield) The resulting polymer contained ~ 'y 8 ppm of aluminum and less than 3 ppm of nickel.
20 Example 189 The same catalyst waS used as in examples 177-187. To a 100 ml glass vial equipped with a magnetic stir-bar was added 1,2 dichloroethane (40 ml) and norbornene (5 g, 53.1 mmole). Thereafta was added the catalyst (0.013 mmol), BF3-etherate (O.OIS ml) i--- ' 'y followed by triethylaluminum 25 (0.48 mmol) that had been prereacted at ambient i r ~: with l-hexenol (1.06 mmol) in dh,l~lulu~ e (4.8 ml). The reaction was temminated with methanol after one hour. The polymer was washed extensively with methanol ~ WO95114048 2 1 7 4 7 ~ 6 PCT/US94/13~66 and dried overnight at 80C under vacuum. The polymer yield was 3.2 g (64%), the GPC indicated a molecular weight (MW) of 244,000: MD was 104,500).
E~ample 190 To a 50 ml glass vial equipped with a magnetic stir-bar was added 1,2 S fl~ (20 ml) and norbornene (2.34 g, 24.8 mmole) and B-5-hexenyl-

9-bvl~h,yl,LJLtu..tLIlc Thereafter was added catalyst A (0.006 mmol). The reac~ion was terminated with methanol after one hour. The polymer was washed extensively with methanol and dried overnight at 80~C under vacuum. The polymer yield was I . 8 g (77%), the GPC indicated a molecular weight (Mw) of 186,000: Mn was 61,500).
E~amples 191-193 Pol~ ,LI;ml~ were carried out according to the procedures in example 110, except that the catalyst component ratios were different and 1-decene was used as a CTA.
1!; rXLrnple C:lblyst AlAlxyl HCA l-Dec~ne ~i-ld M"(xlO~) M.,(xlOl) (ntrnol~ (nttnol) ~nttnol) ~mtnol) 191 NiO.011 IEAL 0.21 0 3944 69.9 163 0.21 (790,,~) 192 NiO.021 7EAL 0.21 0.27 3.52æ 68.1 143 0.21 (70%~
193 NiO.021 7EAL 0.21 1.59 4.07~ 27.6 60.1 0.21 (81%) Examples 194 and 195 pr~r~rarinn of r~tnlyst To a clean, dry, nitrogen-purged 20 ml serum bottle containing a magnetic stir-bar was added nickel eLh~;~ (8% in mineral spirits, 5 mmole). The bottle was then cooled to -78 C and l .; ll . ,. " h . .~ acid (CF3CO2H, 0.39 ml, 5 mmole) was added. The resulting mixture was allowed to warm to ambient Lt~ ..d~ul~; and was then stirred at ambient i r ' ~: for one hour.
H-~mn,pr)ly~ ;. ".~ t)f n~rl~orn~n~ ~
s Example 194: To a 100 ml glass vial containing a magnetic stir bar was added norbomene (5 g, 53.1 mmol) and ~' ' ' u~ c (50 ml). At ambient dlUI~ was added the catalyst (~ y 0.013 mmole, dissolved in 1,2 Jh l~lulu. lllo~lc, 3 ml), BF3 etherate (0.117 mmole) and LI;~ lull,;..u..l (0.13 mmole). There was an immediate, highly exothemmic reaction on adding the last catalyst component. After one hour methanol was injected to terminate the reaction and the polymer was washed with excess acetone, filtered and dried ûvernight, under vacuum at 80DC. The yield of polymer was 4.8 g (96%).
Example 195: The above reaction was repeated identically except that l-decene (0.5 ml) was added as a chain transfer agent. The polymer yield was 3.2 g (64%).
Example 196 Prepar~ n of ~t:llyst To a clean, dry nitrogen-purged 20 ml serum bottle containing a magnetic stir-bar was added nickel ~ " (8% in mineral spirits, 5 mmole). The bottle was then cooled to -78~C and ~;nuull ' ~ acid (CF3SO3H, 0.44 ml, 5 mmole) was added. The resulting mixture was allowed to warm to ambient L~lll,V~,id~ulc and was then stirred at ambient i . ~ for one hour and diluted with 1,2-dh,lllu,o. ' - (20 ml).
tl. ", .... ~oly~ l ;l " . rlf rl~-rborr~n~
To a 100 ml glass vial containing a magnetic stir bar was added norbomene (5 g, 53.1 mmol) and di~,lllul~ ' - (50 ml). At ambient WO 95114048 2 ~ 7 4 7 5 ~ PCT/VS94113166 Ltiu~ d~ulc was added the catalyst (~ U~ L~,'y 0.013 mmol), BF3-etherate (0.~17mmol)andi.h,Ll.ylc,lu.uiuluu.(0.13mmol) Therewasanimmediate, - hightly exothermic reaction on adding the last catalyst component. After one hour the poly had obviously reached very high conversion and so s methanol was injected to terminate the reaction.
E~an~ple 197 pr~DQqratinn r~f rqtDlyst To a clean, dry, nitrogen-purged 20 ml serum bottle containing a magnetic stir-bar was added ,~-tr)l. 1.... -. I r. ,. ,;. acid ~7-CH3C6H4SO3H, 0.95 g, 5 1û mmole) and .I.Iu.ub~..c (5 ml). This mixture was heated to about IOO~C to cause dissolution/melting of the acid. Nickel utlly" (8% in mineral spirits, 5 mmole) was then added and the mixture was allowed to stir for 10 minutes while cooling to ambient t....,u.,. ~.
~U~ of r n-borr~nP
To a 100 ml glass vial containing a magnetic stir bar was added ~ull,u.ll~.~ (5 g, 53.1 mmole) and dh,lllulu~ le (50 ml). At ambient was added the catalyst (~JIl '9 0.013 mmol), BF3-etherate (0.117 mmol) and L.l~ ylalu..~llu~ll (0.13 mmol). There was ~n immediate, highly exothermic reaction on adding the last catalyst component. After one 20 hour the ~ul y ...~,1 ;LaLio.~ had obviously reached very high conversion and so methanol was injected to terminate the reaction.
Examples 198 and 199 pr,Drqr,qtinn of rqtqlyst dlluulu~ illlùl~ic acid (HSbF6, 0.45 g, 1.90 mmole) was placed in a 2s dry, nitrogen filled Teflon~ bottle with a Teflon~ cap/valve containing a magnetic stir bar and the contents were cooled to -27~C. Thereafter was added nickel ~ y" (8% in mineral spirits, 1.9 mmole) and the resulting mixture was allowed to warm to ambient ~ d~Ul C: and was then stirred a ambient i , ~ for 2 hours.
T~nlnnrnlyl,...;,,.~ nfr~nrhnrr~ne Example 198: To a 100 ml glass vial equipped with a magnetic stir bar s was added 1,2 dh,lllvlv~ all~, (50 ml) and norbornene (5 g, 53.1 mmole).
Thereafter was added the catalyst (0.013 mmol), BC13 (0.017 ml) ' 'y followed by Ll i.,lly' ' in .,y, ' ~ ' (0.13 mmol). There ensued a very rapid ~oly --i7:1itnn which WB terminated with methanol after one hour. The polymer was washed with methanol and then acetone and dried overnight at 80C under vacuum. The polymer yield amounted to 4.2 g (84%).
Example 199: To a 100 ml glass vial equipped with a magnetic stir bar was added 1,2 d;~lllv,~l,alle (50 ml) and norbornene (5 g, 53.1 mmole).
Thereafter was added the catalyst (0.013 mmole), B(OEt)3 (0.02 ml) :~ I Iy followed by triethylaluminum in ~,yl ' ' - (0.13 mmol). There 15 ensued a very rapid pvly ;~:al;ull which was terminated with methanol after one hour. The polmer was washed with methanol and then acetone and dried overnight at 80~C under vacuum. The polymer yield amounted to 5g ~100%).

-

Claims (121)

WE CLAIM:

1. An addition polymer consisting essentially of repeating units derived from one or more norbornene-functional monomers, and optionally one or more monocyclomonoolefins, terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto, wherein the moiety derived from said chain transfer agent is exclusively lûcated at a terminal end of said polymer

2. The addition polymer of claim 1 wherein said norbornene-functional monomer is selected from a compound represented by the formulae:

wherein R4, R4', R5, and R5' independently represent hydrogen, halogen, branched and unbranched (C1-C20) alkyl, (C1-C20) haloalkyl, substituted and unsubstituted cycloalkyl, (C1-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl,(C7-C15) aralkyl, (C7-C15) haloaralkyl, (C2-C20) alkynyl, vinyl, (C3-C20) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula -CnF2n+1, wherein n is 1 to 20, R4 and R5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or double bond, and "z" is 1 to 5, when R4, R4' R5, and R5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R4 to R5 cannot be alkylidenyl.

3. The addition polymer of claim 2 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornene selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkyldenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene;
(f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

4. The addition polymer of claim 1, 2, or 3 wherein said monocyclomonoolefin is selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, and mixtures thereof.

5. The addition polymer of claim 1 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, branched or unbranched (C7-C40) araalkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R''' -Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
wherein R''' is branched or unbranched (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, substituted or unsubstituted (C6-C15) aryl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

6. The addition polymer of claim 5 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

7. The addition polymer of claim 6 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

8. The addition polymer of claim 1 having a molecular weight in the range from about 500 to about 2,000,000.

9. The addition polymer of claim 8 wherein the molecular weight is in the range of about 3,000 to about 1,000,000.

10. The addition polymer of claim 9 wherein the molecular weight is in the range of about 50,000 to about 500,000.

11. An addition oligomer consisting essentially of 4 to 30 linked repeating units derived from one or more norbornene-functional monomers, and optionally one or more monocyclomonoolefins, terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacentcarbon atoms has two hydrogen atoms attached thereto, wherein the moiety derived from said chain transfer agent is exclusively located at a terminal end of said oligomer.

12. The addition oligomer of claim 11 wherein said norbornene-functional monomer is selected from a compound represented by the formulae:

wherein R4, R4' R5, and R5' independently represent hydrogen, halogen, branched and unbranched (C1-C20) alkyl, (C1-C20) haloalkyl, substituted and unsubstituted cycloalkyl, (C1-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl,(C7-C15) aralkyl, (C7-C15) haloaralkyl, (C2-C20) alkynyl, vinyl, (C3-C20) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula -CnF2n+1, wherein n is 1 to 20, R4 and R5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or doublebond, and "z" is 1 to 5; when R4, R4' R5, amd R5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R4 to R5 cannot be alkylidenyl.

13. The addition oligomer of claim 12 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornene selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene;
(f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof

14. The addition oligomer of claim 13 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R''' -Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO

wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

15. The addition oligomer of claim 14 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

16. The addition oligomer of claim 15 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

17. An addition polymer or oligomer of norbornene or substituted norbornene derived repeating units having a 13C-NMR spectrum for a non-bridgehead CH group showing resonances at 45 - 55 ppm with a narrow multiplet centered at 47.5 to 48 ppm and 13C and 1H-NMR resonances of olefinic end groups.

18. A reaction mixture for forming an addition polymer comprising at least one norbornene-functional monomer, a solvent, a single or catalyst system each comprising a Group VIII transition metal ion source and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacentcarbon atoms having two hydrogen atoms attached thereto.

19. The reaction mixture of claim 18 wherein said single component catalyst system consists essentially of a cation of a Group VIII metal complex, and a weakly coordinating counteranion; said cation having a hydrocarbyl group directly bound to said Group VIII metal by a single metal-C .sigma.-bond, and by not more than three .pi.-bonds, to a weakly coordinating neutral donating ligand.

20. The reaction mixture of claim 19 wherein said metal is selected from the group consisting of nickel, palladium, and cobalt.

21. The reaction mixture of claim 20 wherein said single component catalyst system is represented by the formula:

wherein M represents Ni or Pd, L1, L2 and L3 represent ligands of M;
only one ligand having a .sigma.-bond, and all the ligands together having 2 or 3 .pi.-bonds; and, CA- represents a counter anion chosen to solubilize said cation in said solvent.

22. The reaction mixture of claim 21 wherein M represents Ni, and said weakly coordinating neutral donating ligand is selected from the group consisting of a cyclo(C6-C12)alkadiene, norbornadiene, cyclo(C10-C20)triene, benzene, toluene, xylene, and mesitylene.

23. The reaction mixture of claim 21 wherein said weakly coordinating counteranion is selected from the group consisting of BF4-; PF6-;
AlF3O3SCF3-; SbF6-; SbF5SO3F-, CF3SO3-; B[C6F5]4-; and B[C6H3(CF3)2]4-.

24. The reaction mixture of claim 18 wherein said solvent is a halohydrocarbon solvent.

25. The reaction mixture of claim 18 wherein said multicomponent catalyst system comprises a Group VIII transition metal compound, an organoaluminum compound, an optional third component selected from the group consisting of Lewis acids, strong Br?nsted acids, halogenated compounds, electron donating compounds.

26. The reaction mixture of claim 25 wherein said Lewis acids are selected from the group consisting of BF3-etherate, TiCl4, SbF5, BCl3, B(OCH2CH3)3, and tris(perfluorophenyl) boron, said strong Br?nsted acids are selected from the group consisting of HSbF6, HPF6, CF3CO2H, FSO3H-SbF5, H2C(SO2CF3)2, CF3SO3H and paratoluenesulfonic acid, and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; wherein said electron donating compounds are selected from aliphatic and cycloaliphatic diolefins, phosphines and phosphites, and mixtures thereof

27. The reaction mixture of claim 25 wherein the organoaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and mixtures thereof.

28. The reaction mixture of claim 25 wherein the Group VIII
transition metal compound comprises a Group VIII transition metal ion bonded0 to one or more moieties selected from the group consisting of monodentate, bidentate, and multidentate ionic or neutral ligands, and mixtures thereof.

29. The reaction mixture of claim 28 wherein said Group VIII
transition metal is selected from the group consisting of Ni, Co, Pd, Pt, Fe andRu.

30. The reaction mixture of claim 28 wherein the Group VIII
transition metal compound is selected from the group consisting of: nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, cobalt neodecanoate, iron napthenate, palladium ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2, nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, trans-Pd Cl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate. iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, bis(allyl)nickel. bis(cyclopentadienyl)nickel, palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, platinum bis(triethylphosphine) hydrobromide, ruthenium tris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine) hydrido chloride, ruthenium trichloride, ruthenium tetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris(triphenylphosphine) trichloride.

31. An essentially anhydrous reaction mixture in which a processable addition polymer is formed, said reaction mixture comprising, (a) one or more norbornene-functional monomers, and optionally one or more monocyclomonoolefins;
(b) a pre-formed single component complex metal catalyst of a Group VIII metal which initiates and maintains chain growth of a polymer by an insertion reaction in combination with;
(c) a predetermined amount of a terminal olefinic chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto, in the absence of an organometal cocatalyst;

said pre-formed single component catalyst consisting essentially of (i) a cation of said organo Group VIII metal complex, and (ii) a weakly coordinating counteranion;
said cation having a hydrocarbyl group directly bound to said Group VIII
metal by a single metal-C .sigma.-bond, and by not more than three .pi.-bonds, to a weakly coordinating neutral donating ligand, and (d) a hydrocarbon or halohydrocarbon solvent in which said cycloolefin monomer, said catalyst and said chain transfer agent are soluble.

32. The reaction mixture of claim 31 wherein said pre-formed single component organometal complex catalyst is represented by wherein M represents Ni or Pd, L1, L2 and L3 represent ligands of M;
only one ligand having a .sigma.-bond, and all the ligands together having 2 or 3 .pi.-bonds; and, CA- represents a counter anion chosen to solubilize said cation in said solvent.

33. The reaction mixture of claim 32 wherein M represents Ni, and said weakly coordinating neutral donating ligand is selected from the group consisting of a cyclo(C6-C12)alkadiene, norbornadiene and cyclo(C10-C20)triene, benzene, toluene, xylene, and mesitylene.

34. The reaction mixture of claim 33 wherein said weakly coordinating counteranion is selected from the group consisting of BF4-; PF6-;
AlF3O3SCF3-; SbF6-; SbF5SO3F, CF3SO3-; B[C6F5]4-; and B[C6H3(CF3)2]4-.

35. A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising, (a) a Group VIII transition metal ion source;
(b) an organoaluminum compound;
(c) an optional third component selected from the group consisting of Lewis acids, strong Br?nsted acids, electron donating compounds selected from aliphatic and cycloaliphatic diolefins, and mixtures thereof, and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.

36. The reaction mixture of claim 35 wherein the Group VIII
transition metal ion source is selected from a compound represented by the formula:
Cc, c[Mm'mXx'xYy'yLl]
wherein C represents a cation;
M represents a Group VIII transition metal selected from the group of iron, cobalt, nickel, ruthenium, palladium, and platinum;
X and Y independently represent anionic ligands;
L represents a neutral ligand;
x', y' and l are 0 to 15 with the proviso that x', y' and l cannot all be zero at the same time;
c is 0, 1, 2 or 3;
c' is the charge of C

m is 1 to 4;
m' is the oxidation state of the Group VIII transition metal M which is determined by the equation = x' is the absolute value of the charge of X;
y' is the absolute value of the charge of Y;
wherein C, if present, represents a cation selected from the group consisting oforganoammonium, organoarsonium, organophosphonium and pyridinium ligands; X and Y independently represent ligands selected from the group consisting of hydride, halides, pseudohalides, (C1-C40) branched and unbranched alkylanions, (C6-C24) arylanions, cyclopentadienylide anions, .pi.-allyl groupings, enolates of .beta.-dicarbonyl compounds, carboxylates, halogenated carboxylates,nitrates, nitrites, bisulphate, aluminates, silicates, phosphates, sulfates, amides, imides, oxides, phosphines, sulfides, (C6-C24) aryloxides, (C1-C20) branched andunbranched alkoxides, hydroxide, hydroxy (C1-C20) branched and unbranched alkyl, PF6-, AlF3O3SCF-3, SbF-6, and ligands selected from compounds of the formulae:
Al(R7)4-, B(X)4-wherein R7 and X independently represent halide, or a branched or unbranched hydrocarbyl group, or X represents 3,5-trifluoromethylphenyl; and L represents a neutral ligand selected from the group consisting of acetylenes, (C2-C12) mono-, di-, and triolefins, (C5-C12) cyclomono, di-, tri-, and tetraolefins, carbon monoxide, nitric oxide, ammonia, pyridine, pyridine derivatives, 1,4-dialkyl-1,3-diazabutadienes, amines, ureas, nitriles, organic ethers, tetrahydrofuran, furan, organic sulfides, arsines, stibines, phosphines, phosphites, phosphinites, phosphonites, phosphorus oxyhalides, phosphonates, ketones, and sulfoxides.

37. The reaction mixture of claim 35 wherein said organoaluminum compound is represented by the formula:
AlR123-x Qx wherein R12 independently represents branched and unbranched (C1-C20) alkyl, (C6-C24) aryl, Q is a halide or pseudohalide selected from the group consisting of chlorine, fluorine, bromine, iodine, branched and unbranched (C1-C20) alkoxy, and (C6-C24) aryloxy; and x is a number from 0 to 2.5.

38. The reaction mixture of claim 37 wherein the organoaluminum compound is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, and isobutylaluminum sesquichloride.

39. The reaction mixture of claim 35 wherein the said Lewis acids are selected from the group consisting of BF3-etherate, TiCl4, SbF5, BCl3, B(OCH2CH3)3 and tris(perfluorophenyl) boron, said strong Br?nsted acids are selected from the group consisting of HSbF6 and HPF6, CF3CO2H, FSO3H-SbF5, H2C(SO2CF3)2; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

40. The reaction mixture of claim 18, 19, 21, 25, 31, 32, or 35 wherein said norbornene-functional monomer is selected from a compound represented by the formula:

wherein R4, R4' R5, and R5' independently represent hydrogen, halogen, branched and unbranched (C1-C20) alkyl, (C1-C20) haloalkyl, substituted and unsubstituted cycloalkyl, (C1-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl,(C7-C15) aralkyl, (C7-C15) haloaralkyl, (C2-C20) alkynyl, vinyl, (C3-C20) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula -CnF2n+1, wherein n is 1 to 20, R4 and R5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or doublebond, and "z" is 1 to 5; when R4, R4' R5, and R5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R4 to R5 cannot be alkylidenyl.

41. The reaction mixture of claim 40 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornene selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene;
(f) tetracyclododecadine; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

42. The reaction mixture of claim 40 further comprising a repeating unit derived from a monocyclomonoolefin selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, and mixtures thereof.

43. The reaction mixture of claim 18, 19, 21, 25, 31, 32 or 35 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R--Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2)n-X
wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

44. The reaction mixture of claim 43 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms; isobutylene; 1,7-octadiene, and 1,6-octadiene.

45. The reaction mixture of claim 44 wherein said chain transfer agent is ethylene or isobutylene.

46. A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising:
(a) a Group VIII transition metal compound wherein said Group VIII
transition metal is selected from the group consisting of nickel, cobalt, and palladium;

(b) an organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and (c) optionally, a third component selected from the group consisting of Lewis acids, strong Bronsted acids, halogenated compounds, electron donating compounds selected from (C1-C12) conjugated dienes and (C6-C12) cycloaliphatic diolefins; and mixtures thereof, and wherein said reaction mixture excludes aluminoxane cocatalysts.

47. The reaction of claim 46 wherein said third component is present and is selected from the group consisting of BF, etherate, TiCl4, SbF3, BCl3, B(OCII2CH3)3 and tris(perfluorophenyl) boron, HSbF6 and HPF6, CF3CO1II, FSO3H-SbF3, H2C(SO2CF3)2,CF3SO3H, paratoluenesulfonic acid, and mixtures thereof.

48. The reaction mixture of claim 46 wherein said third component is present andis selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, chloranil, and mixtures thereof.

49. The reaction mixture of claim 46, 47 or 48 further comprising a chain transfer agent selected from a compound represented by the formla:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R--Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2)n-X
wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

50. The reaction mixture of claim 49 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms; isobutylene, 1,7-octadiene, and 1,6-octadiene.

51. The reaction mixture of claim 50 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, and 1-decene, 1-dodecene, and mixtures thereof.

52. A reaction mixture for an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising:
(a) a nickel ion source;
(b) an organualuminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum chlorides, and mixtures thereof, and (c) a component selected from the group consisting of BF3'etherate, HSbF6' butadiene, cyclooctadiene, and mixtures thereof, and wherein said reaction mixture excludes aluminoxane cocatalysts.

53. The reaction mixture of claim 52 wherein said nickel ion source is a nickel salt selected from compounds selected from the group consisting of: nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh3CH2)2, nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II)trifluoroacetylacetonate dihydrate, nickel (Il) acetylacetonate tetrahydrate, nickelocene, nickel (II) acetale, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate.

54. The reaction mixture of claim 53 wherein said organoaluminum compound is selected from the group consisting of triethylaluminums, diethylaluminum chlorides, and mixtures thereof.

55. The reaction mixture of claim 54 wherein said component (c) comprises BF3-etherate and HSbF6.

56. The reaction mixture of claim 55 wherein the molar ratio of aluminum metal:
BF3-etherate: nickel metal: HSbF6 is 10:9.1:1 to 2.

57. The reaction mixture of claim 52, 53, 54, 55 or 56 further comprising a chain transfer agent selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

58. The reaction mixture of claim 57 wherein said chain transfer agent is selected from the group ethylene, propylene, 4-methyl-1-pentene, and 1-decene, 1-dodecene, and mixtures thereof.

59. The reaction mixture of claim 46, 47, 48, 52, 53, 54, 55 or 56 wherein said solvent is a halohydrocarbon and said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substitutednorbornene selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene;
(f) tetracyclododecadine; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

60. The reaction mixture of claim 49 wherein said solvent is a halohydrocarbon and said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornenes selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkyledenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkyledenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene; (f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

61. The reaction mixture of claim 59 wherein said halohydrocarbon solvent is selected from the group consisting of methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, perchloroethylene, chlorobenzene, dichlorobenzene and trichlorobenzene.

62. In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one or more norbornene-functional monomers, a solvent for said monomer, a Group VB, VIB, VIIB, or VIII
transition metal compound, and all alkylaluminoxane in an amount effective to convert said at least 50% by weight of said monomer into said addition polymer, the improvement consisting essentially of, a minor molar amount relative to the moles of said monomer, of an olefinic chain transfer agent selected from the group consisting of ethylene and a compound having a terminal olefinic doubie bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least oneof said adjacent carbon atoms having two hydrogen atoms attached thereto, said chain transfer agent being present in a predetermined amount correlatable with adesired number average molecular weight Mw in the range from about 20,000 to about 500,000, of said addition polymer.

63. The reaction mixture of claim 62 wherein said chain transfer aBent is selected from a compound represented by the following formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, branched or unbranched (C7-C40) araalkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R''' -Si(OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
wherein R''' is branched or unbranched (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, substituted or unsubstituted (C6-C15) aryl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

64. The reaction mixture of claim 63 wherein said monomer is a first monomer selected from the group consisting of norbornene and substituted norbornenes; said polymer is a homopolymer; and, said chain transfer agent is present in an amount less than 50 mole % relative to said multi-ringed monomer.

65. The reaction mixture of claim 63 wherein said monomer is a first monomer selected from the group consisting of norbornene and substituted norbornenes present in a major amount relative to a second monomer; said polymer is a copolymer of said first and second monomers; and, said chain transfer agent is present in an amount less than 50 mole % relative to said multi-ringed monomer.

66. The reaction mixture of claim 65 wherein said second monomer is selected from the group consisting of a multi-ringed cyclomonoolefin structure derived from at least one norbornene unit, said structure including upto four fused rings; a cyclodiolefin having one norbornene unit; a mono(C4-C8)cycloolefin; norbornadiene; and trimer of cyclopentadiene.

67. The reaction mixture of claim 66 wherein one of said rings has a substituent selected from the group consisting of an acyclic (C1-C20)alkyl, (C3-C20)alkenyl, or (C1-C6)alkylidene substituent.

68. In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one norbornene-functional monomer, a solvent for said monomer, and, a Group VB, VIB, VIIB or VIII metal compound in combination with an alkylaluminoxane co-catalyst in an amount effective to convert said at least one monomer into said addition polymer, wherein said metal is selected from the group consisting of chromium, cobalt, molybdenum, tungsten, manganese, nickel, palladium and platinum, the improvement consisting essentially of, said solvent being a halohydrocarbon solvent;
whereby the conversion of monomer to polymer is at least 100% higher than when said reactants are polymerized in an essentially non-polar solvent.

69 The reaction mixture of claim 68 wherein said halohydrocarbon solvent is halo(C1-C4)alkyl or haloaryl solvent.

70. The reaction mixture of claim 69 wherein said halohydrocarbon solvent is selected from the group consisting of methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, perchloroethylene, chlorobenzene, dichlorobenzene and trichlorobenzene.

71. The reaction mixture of claim 69 wherein said metal is nickel.

72. The reaction mixture of claim 19 wherein said catalyst is present on an active catalyst support.

73. The reaction mixture of claim 72 wherein said active catalyst support is selected from the group consisting of aluminum trifluoride and an alkylaluminoxane on silica.

74. The reaction mixture of claim 18 wherein said solvent is selected from the group consisting of non-polar hydrocarbons, and halohydrocarbons.

75. The reaction mixture of claim 18 wherein said solvent is a halohydrocarbon solvent selected from the group consisting of halo(C1-C4)alkanes and haloaromatics.

76. A reaction mixture for the polymerization of an addition polymer comprising one or more norbornene-functional monomers, a halohydrocarbon solvent, and a multi-component catalyst system comprising:
(a) a Group VIII transition metal ion source, (b) an aluminoxane; and (c) a component selected from the group consisting of BF3-etherates, TiCl3, SbF5, BCI3, B(OCH2CH3)3 and tris(perfluorophenyl) boron, said strong Br?nsted acids are selected from the group consisting of HSbF6 and HPF6, CF3CO2H, FSO3HSbF5, H2C(SO2CF3)2, CF3SO3H, paratoluenesulfonic acid;
and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

77. The reaction mixture of claim 76 further comprising a chain transfer agent selected from a compound having a terminal olefinic bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one said adjacent carbon atoms has two hydrogen atoms attached thereto.

78. The reaction mixture of claim 77 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R''' -Si(OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2)n-X
wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

79. The reaction mixture of claim 78 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

80. The reaction mixture of claims 79 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

81. A reaction mixture for forming an addition polymer comprising at least one norbornene-functional monomer, a solvent selected from the group consisting of a non-polar hydrocarbon solvent, a halohydrocarbon solvent, and mixtures thereof and a multicomponent catalyst system consisting essentially of a Group VIII transition metal compound wherein said Group VIII transition metal is selected from the group consisting of nickel, palladium, and cobalt; and an alkylaluminum compound, wherein said reaction mixture excludes aluminoxane cocatalysts.

82. The reaction mixture of claim 81 wherein said Group VIII transition metal compound is selected from the group consisting of nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, cobalt neodeconoate, palladium ethylhexanoate, NiCl2(PPh2)2, NiCl2(PPh2CH2)2, nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, trans- Pd Cl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride.

83. The reation mixture of claim 82 wherein said Group VIII transition metal compound is selected from the group consisting of nickel ethylhexanoate, palladium ehtylhexanoate, and cobalt neodecanoate.

84. The reaction mixture of claim 81 wherein said non-polar hydrocarbon solvent is selected from the group consisting of hexane, cyclohexane, heptane, isooctane, toluene, xylene, and methylcyclohexane.

85. The reaction mixture of claim 81 wherein said polar hydrocarbon solvent is selected from the group consisting of 1,2-dichloroethane, dichloromethane, chlorobenzene, and o-dichlorobenzene.

86. The reaction mixture of claim 81 wherein said alkylaluminum compound is selected from a monoalkylaluminum dihalide, and mixtures thereof.

87. The reaction mixture of claim 87 wherein said monoalkylaluminum dihalide is selected from the group consisting of ethylaluminum dichloride, isobutylaluminum dichloride, and mixtures thereof.

88. The reaction mixture of claim 81, 82, 83, 84, 85, 86, or 87 further comprising a chain transfer agent selected from a compound represented by the formula:

wherein R' and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R''' -Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2)n-X
wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

89. A process for appending an olefinic end-group onto a terminal end of an addition polymer having repeating units derived from at least one norbornene-functional monomer wherein said olefinic end-group is exclusively located at a terminal end of said addition polymer and not copolymerized into the backbone thereof, said process comprising reacting a reaction mixture comprising one or more norbornene-functional monomers, a solvent for said monomer(s) and an effective amount of a single or multicomponent catalyst system each comprising a Group VIII transition metal source and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.

90. A process for controlling the molecular weight of an addition polymer comprising repeating units derived from one or more norbornene-functional monomers, said process comprising reacting a reaction mixture comprising at least one norbornene-functional monomer, a solvent for said monomer and an effective amount of a single or multicomponent catalyst system each comprising a Group VIII transition metal source and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.

91. The process of claim 89 or 90 wherein said single component catalyst system consists essentially of a cation of a Group VIII metal complex, and a weakly coordinating counteranion; said cation having a hydrocarbyl group directly bound to said Group VIII metal by a single metal-C .sigma.-bond, and by not more than three .pi.-bonds, to a weakly coordinating neutral donating ligand.

92. The process of claim 91 wherein said metal is selected from the group consisting of nickel, palladium, and cobalt.

93. The process of claim 92 wherein said single component catalyst system is represented by the formula:

wherein M represents Ni or Pd, L1, L2 and L3 represent ligands to M;
only one ligand has a .sigma.-bond, and all the ligands together have 2 or 3 .pi.-bonds;
and, CA- represents a counter anion chosen to solubilize said cation in said solvent.

94. The process of claim 93 wherein M represents Ni, and said weakly coordinating neutral donating ligand is selected from the group consisting of a cyclo(C6-C12)alkadiene, norbornadiene, cyclo(C10-C20)triene, benzene, toluene, xylene, and mesitylene.

95. The process of claim 93 wherein said weakly coordinating counteranion is selected from the group consisting of BF4-; PF6-; AlF3O3SCF3-;
SbF6-; SbF5SO3F-, CF3SO3-; B[C6F5]4-; and B[C6H3(CF3)2]4-.

96. The process of claim 89 or 90 wherein said solvent is a halohydrocarbon solvent.

97. The process of claim 89 or 90 wherein said multicomponent catalyst system comprises a Group VIII transition metal compound, an organoaluminum compound, an optional third component selected from the group consisting of Lewis acids, strong Br?nsted acids, halogenated compounds, and electron donating compounds, and mixtures thereof.

98. The process of claim 97 wherein said Lewis acids are selected from the group consisting of BF3-etherate, TiCl4, SbF5, BCl3, B(OCH2CH3)3, and tris(perfluorophenyl) boron, said strong Br?nsted acids are selected from the group consisting of HSbF6 and HPF6, CF3CO2H, FSO3HSbF5, H2C(SO2CF3)2 and paratoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

99. The process of claim 97 wherein the organoaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and mixtures thereof.

100. The process of 97 wherein the Group VIII transition metal compound comprises a Group VIII transition metal ion bonded to one or more moieties selected from the group consisting of monodentate, bidentate, and multidentate ionic or neutral ligands, amd mixtures thereof.

101. The process of claim 100 wherein said Group VIII transition metal is selected from the group consisting of Ni, Co, Pd, Pt, Fe and Ru.

102. The process of claim 101 wherein the Group VIII transition metal compound is selected from the group consisting of: nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, cobalt neodecanoate, iron napthenate, palladium ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2, nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II)trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, trans-PdCl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(Pph3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetate, cobalt (II) stearate, cobalt (II) tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, platinum bis(triethylphosphine) hydrobromide, ruthenium tris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine) hydrido chloride, ruthenium trichloride, ruthenium tetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris(triphenylphosphine)trichloride.

103. The reaction mixture set forth in claim 81, 89, or 90 wherein said norbornene-functional monomer is selected from a compound represented by the formula:

wherein R4, R4' R5, and R5' independently represent hydrogen, halogen, branched and unbranched (C1-C20) alkyl, (C1-C20) haloalkyl, substituted and unsubstituted cycloalkyl, (C1-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl,(C7-C15) aralkyl, (C7-C15) haloaralkyl, (C2-C20) alkynyl, vinyl, (C3-C20) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula -CnF2n-1, wherein n is 1 to 20, R4 and R5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or doublebond, and "z" is 1 to 5; when R4, R4' R5, and R5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R4 to R5 cannot be alkylidenyl.

104. The reaction mixture of claim 103 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornenes selected from the group consisting of branched and unbranched (C1-C20) alkylnorbornenes, branched and unbranched (C1-C20) haloalkylnorbornenes, (C1-C6) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C1-C20) alkyltetracyclododecenes, (C1-C6) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene;
(f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

105. The reaction mixture of claim 104 wherein said reaction mixture further comprises: a monocycloolefin selected selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, and mixtures thereof.

106. The process of claim 89 or 90 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R and R'' are independently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR-''' -CO2-R''' -Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH2(CH2)n-OH
-CH2(CH2)n-NCO
-(CH2)n-X

wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

107. The process of claim 106 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

108. The process of claim 107 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

109. A reaction composition comprising a Group VIII metal complex comprising at least one metal-hydride .sigma.-bond; a solvent; at least one norbornene functional monomer; and a chain transfer agent selected from a compound having a terminal olefinic non-styrenic, non-vinyl ether double bond between adjacent carbon atoms (excluding conjugated dienes) and at least one said adjacent carbon atoms has two hydrogen atoms attached thereto.

110. The composition of claim 109 wherein said Group VIII metal of said Group VIII metal-hydride is selected from the group consisting of Ni, Pd, and Co.

111. The composition of claim 110 wherein said solvent is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and mixtures thereof.

112. The composition of claim 110 further containing an alkylaluminum compound.

113. The composition of claim 112 wherein said alkylaluminum compound is an alkylaluminum halide.

114. The composition of claim 112 or 113 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and mixtures thereof.

115. The composition of claim 112 further containing a component selected from the group consisting of Lewis acids, strong Br?nsted acids, halogenated compounds electron donating compounds selected from aliphatic and cycloaliphatic diolefins, phosphines, phosphites, and mixtures thereof.

116. The composition of claim 115 wherein said Lewis acids are selected from the group consisting of BF3-etherate, TiCl4, SbF5, BCl3, B(OCH2CH3)3, and tris(perfluorophenyl) boron, said strong Br?nsted acids are selected from the group consisting of HSbF6 and HPF6, CF3CO2H, FSO3HSbF5, H2C(SO2CF3)2, partoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

117. The composition of claim 109, 110, 111, or 116 wherein said chain transfer agent is selected from a compound represented by the following formula:

wherein R' and R'' are idependently hydrogen, branched or unbranched (C1-C40) alkyl, (C1-C40) branched or unbranched alkyl, branched or unbranched (C3-C40) alkenyl, halogen, or the group -CH2(CH2)n-OR''' -CO2-R-''' -Si (OR''')3 -(CH2)n-Si(OR''')3 -(CH2)n-OSi(R''')3 -CH(CH2)n-OH
-CH(CH2)n-NCO
-(CH2)n-X
wherein R''' is (C1-C10) alkyl, branched or unbranched (C3-C40) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

118. The composition of claim 117 wherein said chain transfer agent is selected from the group consisting of an .alpha.-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

119. The composition of claim 118 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

120. The composition of claim 119 wherein said norbornene functional monomer is selected from a compound represented by the formulae:

wherein R4, R4' R5, and R5' independently represent hydrogen, halogen, branched and unbranched (C1-C20) alkyl, (C1-C20) haloalkyl, substituted and unsubstituted cycloalkyl, (C1-C6) alkylidenyl, (C6-C40) aryl, (C6-C40) haloaryl,(C7-C15) aralkyl, (C7-C15) haloaralkyl, (C2-C20) alkynyl, vinyl, (C3-C20) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula -CnF2n+1, wherein n is 1 to 20, R4 and R5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or doublebond, and "z" is 1 to 5; when R4, R4' R5, and R5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R4 to R5 cannot be alkylidenyl.

121. A process for preparing an addition polymer wherein said olefinic end-group is exclusively located at the terminal end of said addition polymer and not copolymerized into the backbone thereof, said process comprising reacting a reaction mixture comprising one or more norbornene-functional monomers, a solvent for said monomer(s) and an effective amount of a single or multicomponent catalyst system each comprising a Group VIII transition metal source and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.