CA2131940A1 - Process for the preparation of ethylene polymers and products obtained therefrom - Google Patents

Process for the preparation of ethylene polymers and products obtained therefrom

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Publication number
CA2131940A1
CA2131940A1 CA002131940A CA2131940A CA2131940A1 CA 2131940 A1 CA2131940 A1 CA 2131940A1 CA 002131940 A CA002131940 A CA 002131940A CA 2131940 A CA2131940 A CA 2131940A CA 2131940 A1 CA2131940 A1 CA 2131940A1
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CA
Canada
Prior art keywords
radicals
ethylene
comprised
content
same
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002131940A
Other languages
French (fr)
Inventor
Luigi Resconi
Fabrizio Piemontesi
Maurizio Galimberti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Technology Co BV
Original Assignee
Spherilene SRL
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Filing date
Publication date
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Publication of CA2131940A1 publication Critical patent/CA2131940A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

Abstract

ABSTRACT OF THE DISCLOSURE
Homo- and copolymers of ethylene having very high molecular weights and narrow molecular weight distributions are obtained by carrying out the polymerization reaction in the presence of a metallocene-based catalyst wherein the metallocene is stereorigid and it is in its meso isomeric form.

Description

~13 ~0 PROCES8 F :)R THE PREPAR~TION OF ET~YLE~E POLYME~ ~NI) RRO~UCTS
OBTAINED THE~FROM

The present invention relate~ to a proces~ for the prep-aration of olefin polymers. In particular, it rela~es to a proces6 for the preparation of ethylene homo- and copolymeri having very high molecular weights and narrow mol~cular weight distributions .

It is known that the pr~pertie~ of ethylene homopolymers and of copol~m~r~ of ethylsne with one or more alpha olefin comonomer~ depend on their molecular weight. The use of these polymers in field~ such as, for example, the production of film~, generally requires that th~y have high molecular weights.
These ethylene polymers are generally prepared in the presence of catalysts of Ziegler-Natta type. The polymer so obtained has a wide molecular weight distribution.

More recently, in proce~ses for the preparation of poly~
miEr~ of ethylenel homogeneou~ cataly8t8 ba~ed on metallocene compound~ ha~e been used. The polymer~ obtained by working in the pre~nce of the~e cataly ts, have ia narrow molecular ,. .
2 1 3 ~

weight distribution, but their molecular weights are not always commercially acceptable.
Only when working under particular conditions and in the presence of particular metallocene cataly8t8 BUCh a8, for example, metallocene compounds of hafnium, is it possible ~o obtain ethylene polymer~ having higher molecular weights.
In the international patent application WO 91/02012, for example, there is described a proces6 for the preparation of high density linear polyethylene having high molecular weight and narrow molecular weight distribution, in the presence o~
hi~(cyclopentadienyl~hafnium compounds and a tetrakis~penta-fluorophenyl)borate salt. However, in this application only the preparation of ethylene homopoly!mers is exemplified.
Metallocer.e compounds wherein the ligands consist of two sub~titu~ed cyclopentadienyls linked between them by a bridg-ing group which gives steric rigidity to the molecule, are known to be stereospecific cataly~t components for the prep-aration of isotactic polyolefins. These metallocene~ can exlst in two aterical configurations, that i8 the racemic and the meso isomeric form. As the chiral racemic form only is stereo6pecific, the meso form is generally removed by separ~
ation from the rac~meso mixtures obtain~d from the metallocene s~nthesis, It ha3 now been surprisingly fQund that it i8 possible to ~z~-ol) - 2 -~ i 3 ~

prepare homo- and copolymers of ethylene having very high mol-ecular weight~ as well a~ narrow molecular weight di~tri-bution~ if the polymerization reaction i5 carried out in the presence of a metallocene-based catalyst wherein the metallocene is stereorigid and it i~ in its meso isomeric ~o~m .
Therefore, in one o~ its aspects, the present invention provides a process for the preparation of an ethylene polymer, which comprises the polymerization reaction of ethylene in the presence of a catalyst comprising a stereorigid metallocene compound of a transition metal belonging to the Group IIIb, IVb, Vb, VIb or of Lanthanides of the Periodic Table of the Elements, having two substituted cyclopentadienyl ligands bridge joined hetween them, characterized in that the metallo-cene compound is substantially in its meso isomeric form.
In another of its aspects, the present invention provides an elastomeric copolymer of ethylene with propylene and, optionally, with at least one polyene, obtained by the process ;~
of the invention.
In yet another of its aspects, the present invention ;
provides an elastomeric copolymer of ethylene with 1-butene and, optionally, with at least one polyene, obtained by the ~ ;
process of the invention.
In yet another of its aspects, the present invention provides an elastomeric copol~mer o~ ethylene with at least on~

.01) - 3 2 ~ 3 ~

~-olefin C3-CI2 and, optionally, with at least one polyen~, having very high molecular weight.
In yet another of its aspects, the p~esent invention provides a stereorigid metallocene compound having two substituted cyclopentadienyl ligands bridge joined between them, characterized in that it is substantially in it~ meso isomeric form.

Stereorig.id metallocene compounds which ~an b~ us~d in ths proce~s of the present invention are those of the formula ..
(I) H~ /xl R ~ 2 wher~in M is a metal selected from Ti, Zr and Hf;
Rl, ~ame or different, are C1-C20 alkyl radicals, C3-C20 cycloalkyl radicals, C2-C20 alkenyl radical~, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl radical~
and can contain Si or Ge atom~;

R2 and R3, ~ame or different, ar~ hydrogen atomR, C~-C20 alkyl j radicals, C3-C20 cycloalkyl radicals, C2-C~O alkenyl radicals, (~Z522t~ 01) _ 4 _ 2 ~ 3 ~

C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl radicals and can contain iSi or Ge atom~;
R4 is a div~len~ group selected from (CRs2)n, (SiRs2~n, (GeR52)~, NRs or PRs, wherein Rs, ~ame or different, are Cl-C20 alkyl rad-icals, C3-C20 cycloalkyl radicals, C2-C~ alkenyl radicals, C6-C20 aryl radicals, C7~C20 alkylaryl radicals or C7-C20 arylalkyl rad-ical~, and when R4 i8 ~CRs2)~, (SiRs2)~, (Ge~2)~, two substituent~
R5 on the same carbon, silicium or germanium atom can form a cycle comprising from 3 to 8 atoms;
n is an integer comprised between 1 and 4, preferably being 1 or 2, Xl and X2, same or different, are hydrogen atom~, halogen atoms, R6, oR6, SR6, NR62 or P~2, wherein substituents R6, same or different from each other, are C:l-C20 alkyl radicals, C3-C
cycloalkyl radicals, C2-C20 alkenyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 axylalkyl radicals and can contain Si or Ge atoms;
and wherein Rl and R2 on the same cyclopentadienyl ligand can form a cyole compri~ing from 5 to 8 carbon atoms.
, Met~illocene compounds particulary suitable for use in the proces~ according to the present invention are the bridged bis-indenyls of the formula (II):

..

(;~iZ5220-EP-0~ - 5 -~ "~

9 ~ 0 3 ~
~ xl M ~
\ / ~2 R3 ~7 ~ .

and the bridged bis-tetrahydroindenyls of the formula (III):

~ Xl ( m ~
~3 ~ ~:
p37)q wherein M~ R3, ~4, Xl and XZ are defined as above;
R7, 6ame or different, are hydrogen atoma, Cl-C10 al~yl radical~, C~-C~O cycloalkyl radicals, C~-C~O alk~nyl radicals, C6-CI~ alkylaryl radicals or C7-C10 arylalkyl radicale and can contain Si or Ge atoms;
p and q, same or different, are integers comprised between 1 and 4;
and wherein two adjacent ~ubs~ituents R7 on the i~ame ligand can form a cycle comprising from 5 to 8 carbon atoms.

~z~.ol) - 6 -~ ~3:~9~Q

Metallocene compounds of the formula (II) or (III) particulary suitable are tho~e wherein M is ~r, R3 are hydro-gen atom~, methyl or ethyl groups, R7 are hydrogen atoms or mPthyl groups, Xl and x2 are chlorine or methyl group~ and R4 is a ethylidene or dimethyl-silyl divalent radi~al.
Non-limiting examples of metalloc~nes suitable for use in the process according to the present invention are:
me60-C2H4~ Ind)2NCl2 meso-C2H4( Ind)2~IMe2 meso-C2H4(Ind~2M(NMe2)2 meso-C2H4(H4Ind)2MCl2 me~o-C2H~tH4InCI)2MMe2 meso-C2H,~(H4Ind)2M(NMe2~0Me meao-Me2Si(Ind)2MCl2 me~Ro-Me2Si~Ind)~Me2 me 5 o-Ph ( ~Ie ) Si ~ Ind ) 2MC12 meso-Ph2Si ( Ind ) ~MC17 mlsso-C~Me4( Ind)2MCl2 meso-Me~2SiCH2( Ind)2MCl2 meso-C2H4 ~ 2 -MeIn~ ) 2MC12 meso-C2,H~ ( 4, 7 -Me2Ind ) 2MC12 m~o-C zH4 ~ 5, 6-Me2Ind ) 2~C12 me~o-C2]~4 ( 2 t 4, 7-Me3Ind ) ~MCl2 :
meso-C2H4(2-MeH4Ind)~Cl2 meso-C2H4(4,7-Me2H4Ind)2MCl meso~C2H4( 2 t 4, 7-Me3H4Ind)2MCl2 meso-Me2Si ( 2-MeInd)2MCl2 me~o-Me2Si ~ 4, 7-Me2Ind ) 2MCl2 meso-Me2Si ( 5, 6-Me2Ind ~ 2MCl me ~ o-Me2S i ~ 2, 4, 7 -Me3I nd ) 2MC 12 me so-Me2Si ( 2 -MeH4I nd ) 2MCl2 meso-Me2Si ( 4, 7 -Me2H~Ind 3 2MCl2 meao-~e2si ( 2, 4, 7 -Me3H4Ind ) 2MCl2 wherein Me=methyl, Ph=phenyl, Cp=cyclopentadienyl, ~ :
Ind=indenyl, H4Ind=4,5,6,7-tetrahydroindenyl, M can be Ti, Zr or Hf, preferably it i8 Zr.
The me80 iPomeric form of metallocene compound~ useable in the proceRs of ~he invent1on can be separated from th~ cor-.
~ ol) - 7 -2 1 3 ~
.

responding racemic form by the common separation method~ such as, for example, fractionated crystallization and extraction with solvents.
A particularly preferred me~allocene compound for use in the process according to the present invention i8 the meso-ethylene-bis(4,7-dimethyl-1-indenyl~ zirconium dichloride. In fact, the s~paration of the racemic and meso isomer~ is particulary simplified, because of the remarkable difference of solubility of the two isomers in solvents ~uch as, for example, CH2Cl2, toluene or dimethoxy ethane. ~`
¦ The process for the pr~parati.on of ethylene polymers according to the pre5ent invention il3 generally carried out in ~he presence, as cocatalyst, of one or more organometallic compounds of aluminum, or of one or more coMpounds able to form a metallocene alkyl cation. In the case of metalloceneæ
of metals of the Group III or of the Lanthanide3 of the Peri-odic Table of Elements, it ifi possible to carry out the polymerization reaction in the abs~nce of cocatalyst.
~ he molar ratio b~tween th~ aluminum and the metal of the metallocene compound is generally compri~ed between about 10:1 and about 10000:1, and preferably between about 100:1 and about 5000:1.
Organometallic comp3unds of aluminum useable in the pro-ce~ according to th~ invention are, for example, the linear, branched or cyclic alumoxanes, containing at least one group ?~

213~ 9~
..

of the type ~IV)-R8 ~a \ Al__O Al/ (IV~
R8/ \ R8 wherein R8, Bame or different, are R9 or a group -O-Al(R8)2 and, optionally, some Ra can be halogen atoms, R9 being defined a R~
In particular, alumoxanes which can be ~uitably used aa cocataiysts in the process of the present invention are those of the formuls (V): _ _ \ Al - O ~ ~ 0-~ -Al / ~V) R9 L _ R9 , for linear compound~, and those of thle formula (VI~

i~l--O _ (VI) m for cyclic compound~, wherein m i5 0 or an integer comprised ~;
between 1 and 40, being an integer comprised between ~ and 40 in the ca~e of cyclic compound~.
Non limiting examples of alumoxanes suitabl~ for use as cocatalyst6 in the proces~ of the pre&ent inv~ntion are those in which tha R9 group~ are 6elected among methyl, ethyl and i~o~utyl radical~, particularly methylalumoxane ~MhO~ and ~:
: i~obutylalumoxane ~TIBAO).
~;:
~Z~-OI) - 9 ~

~3~9~
. .

The alumoxanes us~ful in the process of the present inYentiOn can be obtained by reacting aluminum alkyls or aluminum alkyl-hydridre~ with water. Non limitative example~
of useable aluminum alkyls or alkyl-hydridres are:
Al(Me)3, Al(Et)3, AlH(Et)2, Al(iBu)3, AlEI(iBu~z, Al(iHex)3, Al~C6H5)3, Al(CH2C6H5)3, Al(CH2CMe3)3, Al~CH2SiMe3)3, Al(Me)2iBu, Al~Me)2Et, AlMe~Et)2, AlMe(iBu)2, Al~Me)2iBu, Al(M~2Cl, Al(Et)2Cl, AlEtCl2, Al2(Et)3Cl3, wherein Me=methyl, Et=ethyl, iBu=iaobutyl, iHex=isohexyl. The trimethyl aluminum ~TMA) and the tr.iisobu~ylaluminum (TIBAL) are preferred.
A particular class of organo-metallic compounds o~ alu-minum u~eful as cocatalysts in the process ac~vrding to the in~ention i~ that of compound~ obtainable by rea~tion of alu-minium alkyls or alkylhydrides with water in molar r~tio com-prised between 1:1 and 100:1 reBpectively. Compounds of thi~
type are de~cribed in European patent application EP-575 875, the conten~ of which is incorpora~ed in the present de6cription.
Moreover, organom~tallic compounds of aluminum useful as cocatalysts in the proces~ of the invention are tho6e of the ormula (VII):
R9 Rl Al - N - Al / (VII) (ZZ5220 EP-OI) -- 1 0 ~` 2~3~9~

and those of the formula (VIII):
R9 ~ R9 \ Al _ S - Al (VIII) R9/ ~¦ \ R9 wherein R9 i8 defined a~ above.
Non-limiting examples of compounds able to form a metallocene alkyl cation are compound~ of the formula Y+Z~
wherein Y~ i8 a Bronsted' 8 acid, able to give a proton and to react irreversibly with a sub~tituent X~ or X2 of the compound of the formula ~I) and Z is a compatible anion, which does not coordinate, able to stabiliize the active catalytic 6pecie~
which i~ ~ufficiently labile to be ~hifted from an olefinic ~ubstrate. Preferably, ~he anion Z comprise3 one or more boron atom~. More preferably, the anion Z- i8 an anion of the ~ormula B~r4, wherein ~he subctituent~ Ar, same or diffPrent from each other are aryl radical~ such a~ phenyl, pent~fluoro-phenyl, bis(trifluoromethyl)phenyl. Particulary preferred is thc tetrakis-pentafluorophenyl-borate. Furthermore, compounds of the formula BAr3 ean be suitably used. Compound6 of this type are descri.bed for example in the Published International Patent Application WP 92/00333, the content of which is incorporated in the present de~cription.
The catalysts used in the proces~ of the present inven~
tion can be al~o u~sd on inert ~upports. Thi6 can be obtained by deposing the metallocene compound (A), or the product of (ZZ52~EP-OI) 2~3:~9~0 the reaction of the same wi~h the component (B3, or the compo-nent (B) and subsequently the metallocene compound (A), on inert ~upports such as for example ~ilica, alumina, 6tyren~-divinylbenz~ne copolymers or polyethylene.
A particular class of iner~ support~ suitable for the use according to the present inven~ion are the porou~ organic sup-port~ funzionalized with groups having active hydrogen atoms, which axe de~cribed in the ~uropean Patent Application No.
94110168.5. Particularly preferred are tho~e wherei~ the organic support iB a partially crosslinked styrenic polymer.
The so obtained ~olid compound, in combination wi~h a further addition of the aluminum alkyl compound either a~ 6uch or pre-reacted with water, can be u~ed in the ga~ phase polymerization proce~e~.
The proce~ for the ethylene polymerization according to the present invention can also be carried out in liquid phase, preferably in ~he pre~ence of an iner~ hydrocarbon solvent which c~n be aromatic ~uch a~, for example, toluene, or aliphatic ~uch as, for example, n-hexane.
The ~olymerization temperature i~ generally compris~d between 0 C and 150 C, in particular between 20 ~C and 100 C, and more particulary between 30 C and ao oc.
The molecular weight of the polymer~ obtained can be remarkably high. In particular, pol~m~rs can be obtained with higher than 1.106 and preferably, comprised between 2.106 ~l) - 12 ~ :

2~3~9.~
. .

and 6 .1 06 .
The molecular weight of the polymers can be varied merely by varying the pol~merization temperature, the type or the concentra~ion of the catalytic componentR or by usin~ molecu-lar weight regulators such as, for example, hydrogen.
The polymers of the invention have a narrow molecular weight distribution. An index of the molecular weight di6tribution i6 represented by the ratio M~ which, for the copol~ner of the invention, i~ generally lower than 4, preferably lower than 3.5 and, more preferably, lower than 3O
The molecular weight distribution can be varied by using mixture~ of different metallocene compound~, or by carrying out the polymerization in many steps differing as to the polymeri~ation temperatures and/or the concentrations of the molecular weight regulator.
The polymerization yield~ depend on the purity o~ the metallocene components of the catalyst. Therefore, the metallocen~ compounds can be used either a~ such, or they can be subject2d to purification treatments.
! The components of the catalyst can be contacted among them before the polymerization. The contact time is generally compris2d between 1 and 60 minutes, preferably between 5 and ~0 minute~.
¦ According to another embodiment of the present invention, ¦ the proce~s for the preparation of ethylene polymers can be ~Z~-OI) - 13 -213~9~

carried out in the presence of one or more olefins selected from the alpha-olefins of the formula (IX):
CH2 r~ - R (IX) wherein R i6 an alk~l radical containing from 1 to 20 carbon atom~, and the cycloolefins.
The copolymers obtained are characterizPd by valuable properties, Ruch a6 the low content of ashe~ and the uniform-ity of di~tribution of the comonomexR in the copolymeric chain.
In particular, LLDPE copolymers can be prepared, having a content of comonomer units comprisc~d between 1 and 20~ by moles, preferably between 5 and 15% by mole~, density comprised between 0.87 and 0.95 g/cm3 and characteriæed by an uniform distri~ution of the comonomer along the polymeric chain.
Non limitative example~ of olefins useable as comonomers are propylene~ 1-butene, 1-pentene, 4-methyl-1-pentene, l-hex-ene, l-octene, 1-decene, 1-dodecene, 1-tetracene, 1-hexa-decene, 1-cctadecene, 1-eicosene, allylcyclohexane, cyclo~
pentene, cyclohexene, norbornene, 4,6~dimethyl-1-hept~ne, allyl-trimethyl-silane.
These copolymers can al80 contain unit6 deriving from polyene6~ in particular from conjugated or not conjugated, linear or cyclic dienes, such a~ for example 1,4~
hexadiene, i~oprene, 1,3-butadiene, 1,5-hexadiene, 1,6-hepta-. '.

2~3~o ~. :
.... . .

diene.
Furkhermore, the process of th~ pr~sent invention can be advantageously usPd for the preparation of elastomeric copolym~rs of ethylene with alpha-olefins of the formula (IX):
CH2=CH-R (IX) wherein R i5 an alkyl radical containing from 1 to 10 carbon ~toms, optionally containing lower proportions of units deriv-ing from a polyene.
The ~aturated elastomeric copolym2r~ have a content of ethylene units comprised between 15~ and 85% by moles, prefer-ably between 40% and 80~ by moles, more preferably between 55~
and 75~ by moles, the complement to 100 being constituted by unit~ of one or more alpha olefin~ and/or of a non conjugated diolefin able to cyclopolymerize.
The unsaturated elastomeric copolymers contain, b~sides the unit~ deriving from the polymerization of ethylPne and alpha-olefins, also lower proportions of unsaturated units deriving from the copolymerization of one or more polyenes.
The content of unsaturated units can vary rom 0.1 to 5~ by moles, preferably it is compri6ed between 0.2 and 34 by mol~s.
Non limiting example o~ alpha-olefins us2ful as comonomers in the elastomeric copolym~rs of ethylena are propyl~ne, 1-butene, l-hexene, 4-methyl-1-pen~ene.

Non-limi~ing examples of non-conjugated diolefins able to cyclopolyerize useful as comonomers in the elastomeric .' ~ ol) - 15 -~ ~ 3 '1 ~ ~ V

copolymers of ethylene are 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,5-hexadiene.
Non-limiting examples of polyenes u~eful as comonomers in the elastomeric copolymers of ethylene are:
- polyenes able to give un6aturated units, such a~
- non conjugated linear diene~ such as 1,4-hexadiene trans, 1,4-hexadiene cis, 6-methyl-1,5-heptadiene, 3,7-dimethyl-1,6-octadiene, 11-methyl-1,10-dodecadiene;
- monocyclic diolefins such a~ for example ci6-l, 5-cyclo-octadiene and 5-methyl-l,S-cyclooctadiene;
bicyclic diolefins such ~8 4,5,8,9-tetrahydroindene and 6 and/or 7-methyl-4,5,8,9-tetrahyclroindene;
- alkenyl or alkyliden norbornenes ~uch a~, for example, 5-ethyliden-2-norbornene, 5-i~opropyliden-2-norbornene, exo-5-i~opropenyl-2 norbornene;
- polycyclic diolefin~ such as, for example, dicyclopenta-diene, trisyclo-[6.2.1.0Z7]4,9-undecadiene and the 4-methyl derivative thereof;
- non conjugated diolefins able to cyclopolym rize, such as ¦ 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,5-hexadiene;
- conjugated dienes such as butadiene and isoprene.
In particular, by the proces~ of the ~re~ent invention it is possible to prepare elastomeric copol~ner~ of ethylene with propylene and, optionally, one or more polyene~, having con~
tent of unit6 deriving from ethylene comprised between about :.

~ no-~ol) - 16 -2~3~ 9~Q

35~ and 85% by moles, content of units deriving from propylene comprised b~tween about 10~ and 60~ by moleR and content o unit3 deriving from one or more polyenes comprised between 0 and 5% by moled, having the following characteristics~
- content of propylene units in form of triads comprised between 0 and 8%, preferably between 0.5% and 6% and, more preferably, between 1% and 4%;
- le~s than 50%, preferably le~ than 45~, of the above mentioned propyliene triads having i80tactic structure;
- product of the reactivity ratios r1.r2 lower than 0.5, pre~erably comprised between 0.1 and 0.45 and, more pre-ferably, comprised between 0.3 and 0.4.
The conten~ by mole~ of monomeric unit~ deriving from ethylene i~ preferably comprified b~stween about S0% and 80 and, more preferably, betwe~n about 60~ and 75%.
The content by moles of monomeric units deriving from propylene i~ preferably compriied between about 15% and 50%
and, more preferably, between about 20% and 40%.
The content by molei~i of monomeric units deriving from polyene or polyenes iB preferably comprised between 0% and 4% ~:
and, more preferably, between about 0% and 3%. ~-~
The above indicated elastomeric copolymers of ethylene have intrinsic visco6ities which are generally higher than 2.0 dl/~- .
The analyais of the distribution of the propyl~ne units ~Z~OI) - 17 -, ~ -" ~, ", ,..", ' ` ' ', ~ -, ~ '' ., '''"'' . ' ''' ~ '' ` ' 2~3~0 :

has been carried out by l3C-NMR. The a6signments have been carried out as described by M. Kakuyo et al. in "Macromolecules 15, 1150-1152, (1982)". The distribution of the triads i8 calculated by the following relations:
EPE - T~ PPE = T~ PPP = ~
where EPE, PPE and PPP represent respectively the sequences ethylene/propylPne/ethylene, propylene/propylene/ethylene and propylene/propylene/propyl~ne in the copolymer. The value~ are normalized. ~he higher i9 the number of i301ated propylene unit~ in the chain, the nearer i8 to unity the value of the ratio EPE/(EPE~PPE+PPP).
The product o~ the reactivity r,atios r,.r2, wherein r1 i8 the reactivity ratio of propylene and r2 iB that of ethylene, is calculated a~cording to the following formula:
r, r2 - 1 + f (X + 1) - (f ~ l) (X + I)~, wherein f= ratio betw~en the mols of ethylene units and the moles of propylene units in the copolymer, and X= ~PPP~PPE)/EPE.
Other parameters obtainable from the di~tribution of the propylene units are the values B and M, which are calculated a~cording to the following formula~
B = 4 EE PP/EP2 :
M - EEP2 PPP EPE/(PP~ EEE PEP) The ethyl~ne ~ ropylene elastomeric copolymers of the in~ention have B value~ generally lower than 0.5, and M ~aluea generally zzszo EP-o~

Q

lower than 1.5.
Furthermore, by the proces6 of the present invention it i6 possible to prepar~ elastom~ric c~polymers of ethylPne with l-bu~ene and, optionallyt one or more polyenes, having con~ent of units deriving from ethylene comprised between about 35%
and 85% by molei3, content of units deriving from l-butene com-pri ed between about 10~ and 60% by moles and content of unit~
deriving from one or more polyenes comprised between 0 and 5%
by moles, having the following characteristics:
- content of 1-butene units in form of triad equal to 0;
- product of the reactivity r~tio~ r1. r2 higher than 0.1, prefer~bly comprised between 0.1 and 1.0 and, more pre-ferably, compri~ed between 0.2 land 0.4;
- le~6 than 2~ and, preferably, less than 1~ of the CH
groups in the polymeric chain contained in 6equences (CH2)~ comprised between two tertiary carbon atom~, where- ~::
in n i~ an even number.
The contant by moles of monomeric units deriving from ethylene i~ preferably comprised between about 50% and 80%
and, more preferably, between about 60% and 75%.
Th~ content by molei of monomeric units deriving from 1-butene i6 preferably comprised between about 15~ and 50~ and, more preferably, between about 20% and 40%.
The con~nt by mole6 of monomeric unit~ deriving from polyene or polyenes i8 preferably compri~ed between about 0 ~zs22~eP ol) - 1 9 2~3~

and 4% and, more preferably, between 0% and 3%.
The analysis of the di~tribution of the monomeric unit~
o~ l-butene has been carried out by ~C-NMR. The assignments have been carried out a~ described by J.C. Randall in "Macromolecules ~1982), 15, 353-360". The spectrum iB ~ubdi-vided into the following eight areas:
(Al) from 40.0 to 38.9 ppm, (A2) form 37.2 ppm, (A3) from 34.8 to 34.16 ppm, (A4) from 34.16 to 33.5 ppm, (A5) from 31.0 to 29.0 ppm, (A6) from 27.5 to 26.8 ppm, .
~A7) from 26.8 to 26.5 ppm, ~ ~
(A8) form 25.0 to 24.0 ppm. ~:
The concenkration (molar fraction) of diads i3 obtained by th~ following equations:
EE = 0.5[A5+0.5lA6-~)]/Z
EB = 0.5~Al+A3~A4-~Q.5(A6-A2~A8]/2 BB = 0.5~A23/Z
withZ=0.5[A5+0.5(A6-A2)]+0.5[Al+A3+A4~Q.5~A6-A2)+A8~+0.5(A2), wherein EE, EB and BB represent respectively the sequences ethylene/ethylene, ethylene/l-butene and l-butene/l-butene in the copolymer.
The product of the reactivity ratic~ r,.r2, wherein Rl i~
the reactivity ratio of l-butene and r2 ~hat of ethylene, i~
..
(ZZ5220-EP-01) ~ 2 0 2 ~ 3 ~

calculated according to the following formula:
rl.r2 = 4~EE)(BB)/(EB)2 wherein EE, BB and EB represent respectively the sequence~
~thylene/ethylene, butene/butene and ethylene/butene.
The elastomeric copolymer~ obtained from the proce s of the invention are substantially free of crystallinity. Their melting enthalpy (oHf) iS lower than about 20 J/g and, prefer-ably, lower than 10 J/g. Generally, they can be considered completely amorphous, having non detectable melting enthalpies. However, the copolymers in which the content of units deriving from ethylene is clol3e to the upper limit of 85% molar, have melting enthalpies which can be higher than 20 The structure of the mentioned copolymers re~ult~ to be highly regivregular. In fact, by the ~C-NMR analysi~, signals relating to sequences (CH~)D compri~ed between two tertiary carbon a~oms, wherein n i8 an even number, are generally not detectable.
Th~ ela6tomeric copolymers obtainable by the process of the present invention have intrinsic viscositie~ which are generally higher than 1.0 dl/g, preferably higher than 2.0 dl/g. However, by the process of the inv2ntion it is pQSsible to obtain elastomeric copolymers of ethylene endowed with very high molecular weights.
Accordingly~ in another of its aspects~ the present ~o~) - 21 -2~3~ 9~ V

invention provides an elastomeric copolymer of ethylene with at lPast one ~-olefin of the formula (IX):

wherein R i~ an alkyl radical containing from 1 to 10 carbon atom~, and at least one polyene, having content of units deriving from ethylen~ comprised between about 35% and 8~ by mole~, content of units deriving from a-olefins comprised between about 10% and 60% by moleæ and content of units deriv-ing from polyenes compri~ed between 0 and 5% by moles, having the following characteristic~:
- intrin~ic visc06ity higher than 6.0 dl/g, preferably higher th~n 8.0 dl/g and, more preferably, higher than 10.0 dl/g;
- les~ than 2% and, preferably, lo~s th~n 1% of CH2 group~
in the polymeric chain containecl iDi sequences (CH2)~ com~
pri~ed between two tertiary carbon atom~, wherein n i8 an even numb~r.
~ he preferred a-olefin for this very high molecular weight ela~tomeri~ copolymer of ethylene iB propylene.
These vexy high molecular weight elastomaric copolymeræ
of ethylen~ have the advantag~ that they can be extended with large amount~ of oil, much larger with respect to the c~mounts usually employed in the copolymer~ known at the date of the inv~ntion. The very high molecular weight o~ the elastomers provides for high strength properties in highly ~xtended formulations.

(zz5220 eP41~ - 22 2 ~ 31 ~ ~

According to a further advantageous embodiment of the present invention, the very high molecular weight ela6tomeric copolymers of ethylene according to the invention have a very low content of crystallinity even when the content of u~it~
deriving from ethylene is aB high as 85~ by mole~0 In fact, the meLting enthalpies of these copolymers are generally lower than 20 J/g, preferably lower than 15 J/g and, m~re preferab-ly, lower than 10 J/g. ., This ~ac1: is not at all expected, since the knowncopolymers have much higher cry~tallinities at a parity of content of ethylenic units.
The elastomeric copolymers of e~thylene according to the pre~nt invention are generally ~oluble in the co~non solvents such as, for example, hexane, heptane~ and toluene. ~-TheRe copolymeræ can be vulcanized u~ing formulation and methods known for EPM and EP~M rubbers, working, for example, in the pre~ence of peroxide~ or of sulphur. Rubbers endowed with valuable elastomeric propertie~ are obtained. :~
The rubbers obtained from these copolymers can be transformed into manufactured article~ by conventional processes for thermoplastic materials (moulding, extrusion, injection, etc.~. The relative manufactured articles are endowed of interesting ela5tic properties and are used in all the typical applications of alpha-olefinic elastomers.
. ., ~EP~I) -- 23 2 ~

In particular, the products obtained from copolymers hav-ing a high contPnt of ethylene units can be advantageously u~ed as coatings for wire~ and cables.
A further advanta~eous use of the process of the invention is for the preparation of cycloolefin pslymer~. Monocyclic or polycyclic olefinic monomer~ can be either homopolymerized or copolymerized, al~o with non cyclic olefinic monomer~
Non--limiting examples of cycloolefinic polymer~ which can be prepared by the procesa of the invention are describ~d in European Patent Application EP-501,370 and EP-407,870, the content of which is incorporated in the preent description. :
The following Examples are given to illustrate and not to limit the invention.
~ a~T~ Q~
The intrinsic visco~ity [~] wa~ measured in tetrahydro-naphthalene at 135C. Molecular weiyhts (~) are calculated by the following equation~
[~] = 3.8 104 ~~
The measurements of Differential Scanning Calorimetry (~.S.C.) were carri~d out on an instrument DSC-7 by Perkin Elmer Co. Ltd. according to the following method. About 10 mg of sample obtained from the polymerization were cooled to -25 C and then heated to 200 C with a scanning rate equal to 10 C/min. The ~ample wa8 kept at 200 C for 5 minute~ and there-after cooled with a ~canning rate equal to 10 C/min. There-~-OI~ - 24 2 ~

after, a second scanning was carried out according to the same modalities of the first one. The value~ reported are those obtained in the first scanning.
The 13C-N.M.R. analy~i~ of the elastomeric copolymers have been carried out with a Bruker AC200 in~trument, at a tempera-ture of 120C, on sample~ prepared by dissolving about 300 mg of polymer in 2,5 cc of a 3-1 mixture of triehlorobenzene/C2D2Cl4~ The spectra have been regi~tered with the following parameters:
- Relaxation delay - 12 sec - Number of acannings = 2000.2500 P~P~R~TIO~ OP $N~ CaT~YTIC C~PO~
~E~Q-~HY~E~E~IS(4~7-~IMETHYL-I~ YL~ZI~CONI~M ~ICHLORIDE

~A) The synthesi~ wa~ carried out according to the method described in "OrganomPtallics, 1990,9,3098" (yield 54% from p-xylene).
~B3 ~re~a~ion ~ 2~bis~4.7-dimethyl-in~nyl)e~h~
38.2 g (265 mmol) of 4,7-dimethylinden were dis~olved in 350 ml of te~rahydrofuran and the temperature of the solution wa~ cooled to 0 C. Then, 165 ml of n-butyllithium (1.6 M in hexane, 264 mmol) wer~ added, dropwise for 2.5 hour6. After having again heated up to room temperature and ~tirred the whole for 4 hour~, a purple-red solution of 4,7-dimethyl-:

",~

~3~

indenyl-lithium was obtained. This ~olution was cooled to -70 C and treated, dropwise for 35 minutes, with 25.3 g of 1,2-dibromoethane (135 mmol) in 15 ml of tetrahydrofuran . After having heated up to room temperature, a sliyht yellow solution w~s obtained ~o which water was added. The organic phase wa~
collected ed dried on Na2S04. The solvent was then evaporated under vacuum and 20 g of product were obtained (yield 48~3.
tC) Preparation of meso-e~hyl~n~-ki~,7-~imethyl-1=in~enyl)-zircQnium~ hlo~ide ; .
A su~p~nsion of 10 g of 1,2-bis(4,7-dimethyl-3-indenyl)-ethane (31.8 mmol) in 80 ml of tetrahydrofuxan waa added by a small pip2 ~o a 801ution of 2.82 g o KH (70.3 mmol) in 160 ml of tetrahydro~uran , kept under Btirring. Af ter the forma-tion of hydrogen ceased, the resulting brown solution was ~ep-arated from excess KH. This solution and a solution of 12 g of Zrcl4(THF)2 (31.8 mmol) in 250 ml of tetrahydrofuran were added, dropwi~ for 3 hours, via cannula, to a round-bottomed 1ask containing 50 ml of tetrahydrofuran and kept undPr quick ~tirring . A yel low solution and a precipitate were formed. After having removed the solvent under vacuum, the yellow-orange residue (mixture of racemic and meso isomers in ratio 2.33:1 at the IH-N.M.R. analysi~) was subjected to extraction with CH2Cl2 until all the orange product wa6 completely dis601ved. 1.7 g (yield 11.3%) of a yellow solid wa~ obtained, which at the IH-N.M.R. analysi~ re~ulted (zz522o Ep-0l) - 26 2~3~

con6isting of the pure meso stereoisomer.
METHYL~LUMLXANE (MAQ~
A commercial product ~WITC0) in a 30~ b.w. toluene sol-ution was used. After having removed the volatile fractions under vacuum, the vitreou~ material wa6 ground until a white powder wa~ obtained; this wa~ further treated under v~cuum (O.1 mm Hg~ for 4 hours at the temperature of 40 C.
I~QE~yLa~uMQ~A~ (TI~A0) ~:
A commercial product (WITC0) in 1.55 M (on Al) cyclo-hexane solution was u~ed.
~M~ 1 5 pre~a~tiQn o~ ethyl~ne ho~E~ly~ç~
Into a 1 litre B~chi autoclave having glass body, provided with ~acket, elicoidal ~irrer and thermoresi~tance, and joined to a thermostat to control the temperature, wash~d with a solution of trii60butyl aluminum in n-hexane and dried in warm under anhydrou~ nitrogen stream, 0.4 1 of n-h~xane ~purified by pa~sage on alumina columns) were introduced under nitrogen. The temperature was rai~ed to a value of 7-8 C
below the polymerization temperature and the nitrogen was sub-tituted by ethylene.
The catalyst 601ution~ u~ing either MA0 (a) or TIBA0 (b) was prepared as follow~.
(a) To a quantity of MA0 toluene olution tlO mg/ml ..
toluene~ containing the required quantity of MA0, a quantity ~.,",,,,,,.,,"-...........

of a toluene solution of meso-ethylene-bis~4,7-dimethyl-1-indenyl) zirconium dichloxide (0.6 mg/ml toluene~ containing th~ required quantity of metallocene was added and the whole wa~ kept at room temperature for 10 minutes.
(b) To a 601utio~ containing TIBA0 (1 mmol of Al) in 10 ml of toluene, a quantity of a toluene solution of meso-ethylene-bia-(4,7-dimethyl-1-indenyl)zirconium dichloride in toluene (0.6 mg/ml toluene~ containing the required quantity of metallocene was added and the whole was kept at room tem-perature for 5 minutes.
The ~olution wa~ injected into the autoclave by a ~light ethylene overpres~ure. The temperature and pre~sure were then raised to the Yalue required for the polymerization and kept conetant ~or a~l the duration of the polymerization. The pres-6ure was kept con~tant by supplying lethylene. The reaction wa~
then cea~ed by removing th~ ethylene overpressure and inject-ing a small guantity of methanol. The polym~r obtained was dried in oven at 60 C under nitrogen ~tream.
The polymerization conditionR and the data relating to the characterizations on the obtained polymers are reported in . Table 1.

. A 2.5 1 ~te~l autoclave equipped with a blade magnetic ~tirrer, manometer, temperature indicator, ~y~tem for loading '.~
~ a~ .o~ - 2~ -~ 3~0 the catalyst, feed line for the monomer and a thermostating jacket, was purged through propane washing at 70C. 1260 ml of propane, and the amounts of ethylene and 1-butene reported in Table 2 were introduced at room temperature and then the reac-tor wa3 heated to 45C. The catalytic suspen6ion was prepared in a Schlenck tube with a discharge tap at the bottom. 4.2 mmols of MAO in 5 ml of toluene was added at a temperature of 25C and followed by 1.0 mg of meso-ethyl~ne-bis(4/7-dimethyl-1-indenyl)zirconium dichloride. The reagent~ were contacted for 5 minute6 and then the suspension wa8 introduced into the autoclave by ethylene overpressure. The temperature was then raised to 50C and maintained con~tant during the polymerization. The total pressure WaB kept constant by feed-ing a mixture of ~thylene/1-butene. The polymerization was interrupted by introducing 0.6 NL of CO into the autoclave after rapid cooling to 30C. The reactor wa6 then left to 910wly degas and the polymer obtained was dried at 60C under vacuo.
The polymerization conditions and the data rel~ting to the characteri2ation of the obtained polymer are reported in Table 2.

_~ .

The methodology described in Example 6 was repeated, but using triisobutyl aluminum (WITCO) instead of :ZZS221) EP-OI) - 2 9 ~'`"`''''~'':' ~'; " ''`

. .

MAOt and introducing 2.1 mmoles of H20 into the autoclave ¦ before the introduction of propansO
The polymerization conditions and the data relating to the characterization of the obtained polymer are reported in Table 2.

ratiolL o:~ an ethylene~1-bu~e~e cQ~ly~n~
The methodology described in Example 5 was r~peated, but introducing 0.7 bar of hydrogen into the autoclave.
..
.~ The pol~merization conditions and the data rela~ing to . the characteriæation of the obtained polymer are rep~rted in . Table 2.
~ ~Q
~las~m~ o~Y~U}L_i~

Intv a 4.25 litre stainles~ steel autoclave, provid~d with ætirrer, manometer, temperature indicator, sy~tem for the ~upplying of the cataly~t, feeding lines for monomer6 and thermo~tating jackets, degased by washing with ethylene at 80C, 2 litres of n-hexane (measured at 20C) and th~ quanti-ties of propylene and ethylene reported in Table 3 wer~

introduced at room temperature. Th~ t~mperature of the autoclave was then raised to 5C below the polymerization tem-perature. The solution of the catalyst was prepared as ~ollows.

` ~' . (2Z522~ 01> - 3 0 To a toluene solution of meso-ethylene-bls(4,7-dimethyl-1-indenyl)zirconium dichloride (3 ml toluene/mg metallocene)~ a methylalumoxane (MAO) solution in 10 ml of toluene waa added.
The contents were kept stirred at the temperatur~ of ZOC for 5 minutesl then the solution was injected into the autoclave under pres6ure of ethylene/propylene mixture in such a ratio to maintain in ~olution the above reported corresponding con-centration. The temperature was then quickly raised to the value required for the polymerization. The polymerization con-dition~ are reported in Table 3. The polymer obtained was sep-arated by ramoving the solvent and the unreacted monomers and then dried under vacuum. The data relating to the characteriz-at.ion of the obtained polymers are reported in Table 4. In the l3C-N~ no peak revealing the preaence of ~equences -(CH2)~-comprised between two ~ertiary carbon atoms, wherein n is an even number, wa~ obeerved.
~ P~ 3 P~ r~tion o~ ethy.lene/p~opylene ela~tomeric cQ~ol~mer6 in sl~ry ..~Ql~ne~iz~ion The methodology described in Examples 9-10 was repeated, but oper~ting with lower amounts of n-hexane.
The polymerization condition~ are reported in Table 3. ~he data relating to the characterization of the obtained polymer~
are reported in Table 4~

2~3~ 9~

EXAMPL~ 14 Prepa~ati.on of an ethylene/1-butene elastomeric cQpoly~ in ~olu~ Qn ~olymerization The methodology describsd in Examples 9-10 was repeated, but using 1-butene instead of propylene. The polymerization condition~ are reported in Table 3. The data relating to the characterization of the obtained polymer are reported in Table 5. In the l3C-NMR zpectrum no peak revealing the presence o~ sequences -(CH2)n- compri~ed between two terti-ary carbon atoms, wherein n i8 an even number, was observed.

2~3~9~a r r I
~=~_ = _3 _ 1 1-I ~ I ~, 0~ ~Y ~ oo I j~ l l l ~ I
i ''-- _ _-- i' "'--' --' 1~ ~ 2s ~ ~ h~ ~

~ ~ , ", ~ ~ ~

~ ~y -3 y y ~

I ~ I ~ ~ ~ ~ r~ ~ I
. _ __ I

~; ~ 3 ~
,_ G` _ o __ `^ _ ~ ~ ~ I V~ , ~ _ o o I

_ _ . . I
I ~L ~1 ~5 ~5 ~ ~ 3 ~ I
I ,a _ _ _ _ ~ I
~ I ~ ~ ~ ~ ~ ~1 . . _ _ _ _ ~ 1 . ~ ~ o v ~ ~ ~ 1 :.~ _ _ _ __ ~ ~ OD, ~ ~ ~ ~1 .. _ __ _ . _I
~ ~ ~N f`~ ~`I I` ¦
O _ . __I ~ ~
aa ~ _N _ _ ~ __ _ I ` ~
~ ~ o_ _ ~ _ (z~s22o-Ep4l) ~ 34 -2~
., ~ l = , _ =
I ~ ~ L~ l o ~ o i~
I . _ 1- '- ~
:5 ¦ o o d a ~ l ~ o ¦

. ~ o o ~ a ci ~ o . . __ _ - . I _ .
I ~
~ ~ __ ___ ~n I @ 1~ I .,-~ :~ ~ ~I d 'I:i ~ ¦ Z 1~1 r~

Z __ ____ _ l __ _ I

~ o o a d a l ~1 o : ~ ~ o ~ ~:i ~ ~ ~, ~;
. . . __ . _ ___ _ --~3 ~0 ~1 a o ~ l ¦ .
. _ __ O O _ a _ ~3 9 ~ ~ ¦

a ~ r ~ r . ~ _ ~,: . ___ ll ~ _ _ 3 o~ ~ 1~l ~1 r = = = =
~`
-. (~ 3 5 -

Claims (17)

1. A process for the preparation of an ethylene polymer, which comprises the polymerization reaction of ethylene in the presence of a catalyst comprising a stereorigid metallocene compound of a transistion metal belonging to the Group IIIb, IVb, Vb, VIb or of Lanthanides of the Periodic Table of the Elements, having two substituted cyclopentadienyl ligands bridge joined between them, characterized in that the metallocene compound is sub-stantially in its meso isomeric form.
2. The process according to claim 1, wherein the metallocene compound is represented by the formula (I):

(I) wherein M is a metal selected from Ti, Zr and Hf;
R1, same or different, are C1-C20 alkyl radicals, C3-C20 cycloalkyl radicals, C2-C20 alkenyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl rad-icals and can contain Si or Ge atoms;

R2 and R3, same or different, are hydrogen atoms, C1-C20 alkyl radicals, C3-C20 cycloalkyl radicals, C2-C20 alkynyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl radicals and can contain Si or Ge atoms;
R4 is a divalent group selected from (CR52)n, (SiR52)n, (GeR52)n, NR5 or PR5, wherein R5, same or different, are C1-C20 alkyl radicals, C3-C20 cycloalkyl radicals, C2-C20 alkenyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl radicals, and when R4 is (CR52)n, (SiR52)n, (GeR52)n, two substituents R5 on the same carbon, silicium or germanium atom can form a cycle com-prising from 3 to 8 atoms;
n is an integer comprised between 1 and 4, preferably being 1 or 2, X1 and X2, same or different, are hydrogen atoms, halogen atoms, R6, OR6, SR6, NR62 or PR62, wherein substituents R6, same or different from each other, are C1-C20 alkyl rad-icals, C3-C20 cycloalkyl radicals, C2-C20 alkenyl radicals, C6-C20 aryl radicals, C7-C20 alkylaryl radicals or C7-C20 arylalkyl radicals and can contain Si or Ge atoms;
and wherein R1 and R2 on the same cyclopentadienyl ligand can form a cycle comprising from 5 to 8 carbon atoms.
3. The process according to claim 2, wherein the metallocene compound is represented by the formula (II):

(II) wherein M, R3, R4, X1 and X2 are defined as in claim 2;
R7, same or different, are hydrogen atoms, C1-C10 alkyl radicals, C3-C10 cycloalkyl radicals, C2-C20 alkenyl rad-icals, C6-C10 alkylaryl radicals or C7-C10 arylalkyl radicals and can contain Si or Ge atoms;
p and q, same or different, are integers comprised between 1 and 4;
and wherein two adjacent substituents R7 on the same ligand can form a cycle comprising from 5 to 8 carbon atoms.
4. The process according to claim 3, wherein the metallocene is the ethylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride.
5. The process according to claim 2, wherein the metallocene compound is represented by the formula (III):

(III) wherein M, R3, R4, X1 and X2 are defined as in claim 2;
R7, same or different, are hydrogen atoms, C1-C10 alkyl radicals, C3-C10 cycloalkyl radicals, C2-C10 alkenyl rad-icals, C6-C10 alkylaryl radicals or C7-C10 arylalkyl radicals and can contain Si or Ge atoms;
p and q, same or different, are integers comprised between 1 and 4;
and wherein two adjacent substituents R7 on the same ligand can form a cycle comprising from 5 to 8 carbon atoms.
6. The process according to claim 1, wherein the catalyst comprises at least one compound selected between the organometallic compounds of aluminum, and the compounds able to form a metallocene alkyl cation.
7. The process according to claim 6, wherein the organo-metallic compound of aluminum is a linear, branched or cyclic alumoxane, containing at least one group of the type (IV):
(IV) wherein R8, same or different, are R9 or a group -O-Al(R8)2 and, optionally, some R8 can be halogen atoms, R9 being defined as R1.
8. The process according to claim 1, wherein the polymerization reaction of ethylene is carried out in the presence of at least one olefin selected from the alpha-olefins of the formula (IX):
CH2=CH-R (IX) wherein R is an alkyl radical containing from 1 to 20 carbon atoms, and the cycloolefins.
9. The process according to claim 8, wherein the olefin is selected from the alpha-olefins of the formula (IX) wherein R is an alkyl radical containing from 1 to 10 carbon atoms, to obtain an elastomeric copolymer of ethylene.
10. The process according to claim 9, wherein the polymerization is carried out in the presence of minor amounts of a polyene.
11. An elastomeric copolymer of ethylene with propylene and, optionally, one or more polyenes, having content of units deriving from ethylene comprised between about 35% and 85% by moles, content of units deriving from propylene comprised between about 10% and 60% by moles and content of units deriving from one or more polyenes comprised between 0 and 5% by moles, having the following charac-teristics:
- content of propylene units in form of triads comprised between 0% and 8%;
- less than 50% of the above mentioned propylene triads having isotactic structure;
- product of the reactivity ratios r1.r2 lower than 0.5.
12. The elastomeric copolymer of ethylene according to claim 11, having intrinsic viscosity higher than 2.0 dl/g.
13. An elastomeric copolymer of ethylene with 1-butene and, optionally, one or more polyenes, having content of units deriving from ethylene comprised between about 35% and 85% by moles, content of units deriving from 1-butene comprised between about 10% and 60% by moles and content of units deriving from one or more polyenes comprised between 0 and 5% by moles, having the following charac-teristics:
- content of 1-butene units in form of triads equal to 0;
- product of the reactivity ratios r1.r2 higher than 0.1;

- less than 2% of the CH2 groups in the polymeric chain contained in sequences (CH2)n comprised between two tertiary carbon atoms, wherein n is an even num-ber.
14. An elastomeric copolymer of ethylene with at least one .alpha.-olefin of the formula (IX):
CH2=CH-R (IX) wherein R is an alkyl radical containing from 1 to 10 carbon atoms, and at least one polyene, having content of units deriving from ethylene comprised between about 35%
and 85% by moles, content of units deriving from .alpha.-olefins coprised between about 10% and 60% by moles and content of units deriving from polyenes comprised between 0 and 5% by moles, having the following characteristics - intrinsic viscosity higher than 6,0 dl/g;
- less than 2% of the CH2 groups in the polymeric chain contained in sequences (CH2)n comprised between two tertiary carbon atoms, wherein n is an even num-ber.
15. The elastomeric copolymer of ethylene according to claim 14, wherein the a-olefin is propylene.
16. A stereorigid metallocene compound of a transistion metal belonging to the Group IIIb, IVb, Vb, VIb or of Lanthanides of the Periodic Table of the Elements, having two substituted cyclopentadienyl ligands bridge joined between them, characterized in that it is substantially in its meso isomeric form.
17. Ethylene-bis(4,7-dimethyl-1-indenyl)zirconium dichloride substantially in its meso isomeric form.
CA002131940A 1993-09-13 1994-09-13 Process for the preparation of ethylene polymers and products obtained therefrom Abandoned CA2131940A1 (en)

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