CA2156503A1 - Carbocationic catalysts and process for using said catalysts - Google Patents

Abstract

A living carbocationic catalyst composition comprising an initiator of a tertiary alkyl halide, a tertiary aralkyl halide or polymeric halide, a co-initiator of an alkyl aluminum or alkyl boron, a proton scavenger and a solvent medium with a dielectric constant between 2.5 and 3.25 is used to produce narrow molecular weight distribution polymers particularly isobutylene polymers.

Description

~094/19380 215 6 ~ ~ 3 PCT~S94/01711 Title of Invention: Carbocationic Catalysts and Process for Using Said Catalysts S

Cross Reference to Related Applications This invention is a continuation in part of United States Serial No.08/020,850 filed February 19, 1993.
Field of the invention This invention relates to living polymerization of olefins using catalysts comprising alkyl aluminum halides or alkyl boron halides.

Background of the Invention:

Living and non-living catalysts have been used to polymerize olefins. In a living polymerization, each catalyst molecule initiates a growing polymer chain that does not undergo chain transfer or termination reactions while monomer is present. By comparing the number of initiator molecules with the number of polymer chains produced in the final polymer, one can determine whether or not a living polymerization has occurred. These two numbers should be equivalent to be a true living polymerization. If there are a substantially greater number of chains, then the polymerization is not living.
., Titanium tetrachlorid~- (TiC14), boron trichloride (BCl3), tin tertachloride(SnCl4), iron trichloride (FeCl3), aluminum trichloride (AlCl3) systems and the 3S like have been described in US Patents 4,910,321 and 4,929,683, and European patent application 341,012 for use in the living polymerization of olefins. The basic vk~J9~clbO37.q~p~dlp ' ;:
~ 2 ~ 215G~3 components OL these systems include a Lewis acid, a tertiary alkyl initiator molecule cont~; n; ng a haloger., ester, ether, acid or alcohol group and an electron donor molecule such as ethyl acetate. The exact S combination o the elements -v-aries with each system.
The tertiary alkyl initiators used in these systems ar~
used for living and non-living carbocationic catalysts.
The tertiary alkvl initiators are typically represente~
by the formula:
(R2) R1 (X) ~ (R3) I n Wherein R1, R2, and R3 are a variety of alkyl o~
aromatic groups or combinations thereof, n is t~e number of initiator molecules and X is the functional group on which the lewis acid af~ects a change to bring about the carbocationic initiating site. This group i~
typically a halogen, ester, ether, alcohol or acid group depPn~i n~ on the lewis acid employed. One or two ~unctional groups per initiator tend to lead to linear polymers while thres or more tend to lead to star polymers.

As discussed in U.S. 5,169,914, the chosen electron pair donor component of the above systems directly relates to the ability o~ these catalysts to 2s stabilize the carbocation ~ormed and to generate livinc conditions. Electron pair donors have been defined as molecules capable o~ donating electron density to an electron deficient site. These molecules usually contain heteroatoms and heteroatomic functional sroups including amides, ester, ethers, sulfoxides and the like. The electron donor num3er concep~ has been used to explain the activity o~ early catalyst systems which AMENDED Stl~ET

~ /9~c1!~03~.~pp/dlp 3 - 2 1 ~ 6 3 0 3 employ ether and ester initiators It was believed that the formation of in situ electron pair donors were responsible for the catalyst characteristics. However, the role of the electron donor is still uncertain and has been challenged. See M Gyor, L. Balogh, H. C.
Wang, R. Faust, Polvm. ~re~r. ~mer. Chem. Soc. 33 (1), 1~8f19~2).

Catalyst systems based on boron trichloride and ti'anium tetrachloride using various combinations of the above components ty~ically have similar process characteristics. Firs., Lewis acid concentrations must exceed the concentration of initiator sites by 16 to 40 times in order to achieve 100 percent conversion in 30 minutes (based upon a degree of polymerization equal to 890) at -75 to -80 degroes C. These catalyst systems ars also typically used with solvents. For example, the re~erences above aisclose methyl chloride as a pre_erred solvent and that a mixed solvent may be used to avoid side reactions or to keep the pcl~mer in solution. Further the mixed solvent should provide - some degree of polarity to maintain the polymerization rate. However, even in these circumstances, an electron pair donor mus~ be present.
~5 For an industriall~ applicable process these catalysts and polymerization conditions fall short of commercial usefulness. Improvements in these systems would include elimination of boron and titanium based Lewis acids as they present h~n~l ing and purification problems. Also a reduction in the amount of catalyst used would be preferred and a reduction in polymerization time wouid be preferred.

AMENDED St~EET

~ dbOi-.~pp/dlp _ 4 2I~6303 Summaxv or ~ne Invention In accordance with this invention, there is provided a iiving carbocationic polymerization ~atalyst sys.em compxising an initiator o~ one of a tertiarv alkvl halide, a tertiary aralkyl halide or a tertiary polvmeric hzlide, wherein each alkyl is independently a straight or branched chain alkvl and each aralkyl is subs.ituted or unsubstituted, a co-initiator o_ an alkvl aluminum or an alkyl boron, a proton scavenger, anc a solven~ medium having a dielectric constant between 2.5 and 3.25. Another aspect of the invention comprises a Drocess o,~ using this catalyst sys~Pm ~or the polymerization of olefins and ~or producing narrow 15 molecular weight distribution polymers. Another aspec~
Of this inven~ion provides methods of making block copolvmers and polymers with a comb like structure.

~risr Descri~tion of the Drawinqs Figure 1: Gel Permeation Chromotography traces of polvmers prepared in dif~ering solvent compositions.
Figure 2: A comparison or boron and titanium based catalysts with diethylaluminum chloride(DEAC) liYing ~5 catalyst.
Figure 3: A plot of molecular weight distr-bution (Mw/Mn) versus the calculated dielectric constant o the polymerization solvent.
Figure 4: A plot of Mn vs. Weight of the polymer prepared(Wp) ror DEAC polymerization at -75 degrees C
ina solvent solution of MeC12 and MCH whre the MeC12 is present at 20 parts by volume and the MCH is present at 80 parts by volume (20/80 v/v MeC12/MCH) and of the calculated values for these reactions under living 35 polymerization conditions.
Figure ~: ~ plot of number of polymer ch~
divided by the n~mber of initiator sites versus the AMENl~Er S.~'~

v~ C~G' .4~dlP
~ - 5 - 21~fi~3 wieght of the polvmer prepared (Np/NI vs. Wp) ~or DEAC
polymer~zation at -75 degrees C in 20~80 v/v MeCl2iMCH
and o- ~he calculated values ~or these reactions under living polymerization conditions.
Desc~;~tion of ~re~rred Fmhodime~ts.

This invention relates to a living carbocationic polymerization catalyst composition and process based upon a catalyst composition comprising: (1) an initiatOr of a tertiary alkyl halide, a tertia_y aralkyl halide or a tertiary polymeric halide, wh2rein each alkyl group is independently a straight or branc~ed chain zlkyl, pre~erably cont~in;ng 1 t~ 1 15 carbor. atoms, each aralkyl is substituted or unsu~stituted and wherein the polymeric unit is an olefin polymer; (2) a co-initiator o,~ an alkyl aluminum or alkyl boron wherein the alkyl is a straight or branched chain alkyl, pre~erably o~ l to 15 car30n atoms; ~3) a pro~on scavenger; and (4) a solvent medium with a dielectric constant between 2.5 and 3.25. This catalyst system can be used, among other things, lor the polvmerization of ole~ins, particularly isobutylene. The system has the benefit of producing 25 polymers with narrow molecular weight distribut on, particularly narrow molecular weight distribution polyisobutylene. The system also provides a method to produce block polymers and polymers with a comb like structure.
The initiators include tertiary alkyl or aralkyl halides represented by the formula below:
(R2) R, (X) \ (R3) I n '- S!~E~

clbO3- .~p/ap ~ - - 6 21~6~03 Wherein X is a halogen, preferably chloride and Rl, R2 and R3 are independently any straight or branched chain alkyls, aryls or aralkyls, preferably cont~i n; Tlg 1 to 15 carbon atoms, more preferably 1 to 8 carbon atoms, even more prererably 1 to 2 carbon atoms. n is the numbe_ of initiator sites and is a number greater than or eo~al to 1, pre~erably 1 to 6. The aralkyls may be substituted or unsubstituted. Preferred examples include 2-chloro-2,4,4-trimethyl pentane (T~Cl), 1,3,5 tri (l-chloro-l-methyl ethyl) benzene and 5-tert-butyl-1,3-di( l-chloro-l-methvl ethyl) benzene (TBDCC).
Other suitable initiators can be ound in US patent 4,946,899, which is herein incorporated by reference.
1~ For the purposes of thi invention and any claims thereto, aralkvl is defined to mean a compound cont~-ining both aromatic and aliphatic structures.

When the initiator is a tertiary polyme-ic h21ide, one of Rl, R2 or R3 is an olefin polymer and the r~m~; n ng R groups are a~ined as above. Pre~er~ed olefir polymers include polyisobutylene and . . .
polyp-opylene. The pol~meric initiator may have halogenated tertiarv ca~bon positioned at the chain end or along or within the backbone of the polymer. h~hen the olefin polymer has multiple halogen atoms at tertiary carbons, either pendant to or within the polyme_ backbone, the product polymer may have a com~
like structure and/or side chain branching depending on the number and placement of the halogen atoms in the olefin polymer. Likewise, the use of a chain end tertiary polymer halide initiator provides a method for producing block copolymers. Monomer added to the polymeric ini~iator will ~orm a second block.
3~ Successive blocks can be formed by sequential monomer addition.

AMENDED SHEET

~094/19380 21~ fi 5 ~ 3 PCT~S94/01711 The co-initiator can be any dialkyl aluminum chloride or dialkyl boron chloride. Each alkyl is independently a straight or branched alkyl, preferably containing l to 15 carbon atoms, more preferably l to 8 carbon atoms even more preferably l or 2 carbon atoms.
A preferred example of the co-initiator is diethyl aluminum chloride. The alkyl of the co-initiator group should not contain any aromatic groups.

The solvent medium can be a single solvent or a mixture of solvents such that: (l) the polarity has been adjusted to match or resemble that obtained from a solvent mixture of 40 to 80 parts methyl cyclohexane to 60 to 20 parts methylene chloride, by volume; (2) has a 15 calculated dielectric constant of between 2.5 and 3.25 units; or (3) has a measured dielectric constant between 2.5 and 3.25 plus or minus ten percent error.
The dielectric constant is calculated by the following method:
The polarizability (P) of a solvent or mixture of solvents is defined by:

E-l M
P =
E+2 d where E is the dielectric constant of the solvent or solvent mixture, d is the density of the solvent or solvent mixture and M is the number average molecular weight of the solvent or solvent mixture. E, d and M
- are all known values that can be obtained from the CRC
Handbook of Chemistry and Physics, 71st Edition, CRC
Press, Inc., Boca Rotan, Florida. Furthermore, the polarizability of a mixed solvent (Pl2) is defined by:

Pl2 = PlXl + P2X2;

WO94/19380 PCT~S94/01711 2~5~3- 8 -where Pl and P2 are the polarizabilities of the pure solvents and Xl and X2 are the mole fractions of solvents 1 and 2 in the mixture. Thus, by calculating Pl and P2 from known values and calculating Xl and X2 from the composition of the mixed solvent, P12 is determined. The dielectric constant of the mixed solvent (E12) is then calculated using d and M of the mixed solvent (M12 and d12) by solving for E12 in the following equation:

P12 =
E12+2 dl2 where Ml2 (MlXl)+(M2X2) dl2 (dlXl)+(d2X2) The dielectric constant may also be measured by measuring the capacitance of the solvent or solvent mixture and the capacitance of air with a conductivity bridge with an appropriate conductivity cell and then determining the ratio of the capacitance of the solvent to the capacitance of air. This ratio is the dielectric constant.

Suitable solvents include hydrocarbons, especially hexanes and heptanes, halogenated hydrocarbons, especially chlorinated hydrocarbons and the like.
Specific examples include but are not limited to methyl cyclohexane, ethyl cyclohexane, propyl cyclohexane, methyl chloride, methylene chloride, ethyl chloride, propyl chloride, butyl chloride, chloroform and the like.

~094/19380 PCT~S94/01711 - 9 - 21~630~

For the purposes of this invention and the claims thereto a proton scavenger is defined to be a composition capable of reacting with free protons and not producing a new species of catalyst or if it does produce a new species of catalyst, that catalyst is substantially inactive when compared to the catalyst system of this invention. Preferred proton scavengers are 2,6-di-tert-butylpyridine (DTBP), 4-methyl-2,6-di-tert-butyl-pyridine, 1,8-bis(dimethylamino)-naphthalene or diisopropylethylamine used alone or in combination.

The active co-initiator is preferably present in the polymerization feed at a mol ratio of up to 8 times the number of initiator sites, preferably O.OOl to 8 times the number of initiator sites, even more preferably 0.5 to 6 times the number of initiator sites.

The proton scavenger, the total amount of initiator sites and the residual water all play a role in influencing the amount of active co-initiator present. Proton scavengers are known to act with the residual water in catalyst systems similar to that described above in a one to one type ratio. In these 2s systems the proton scavenger is usually present at a concentration greater than or equal to the water. In the present invention it has been discovered that proton scavenger present in a concentration greater than the concentration of residual water acts to affect the co-initiators. While not wishing to be bound by - any theory, it appears that the proton scavenger acts with the co-initiator to "inactivate" a portion of the co-initiator present. Thus, it appears that active co-initiator is present at a concentration over and above the amount of free proton scavenger left over after acting with the residual water. Therefore, the concentration of both the residual water and the proton WO94/19380 PCT~S94/01711 al~65~ -10 scavenger must be taken into account when calculating the number of active co-initiator sites for determining the amount of co-initiator desired. Therefore, in a preferred embodiment, the concentration of the proton S scavenger is greater than or equal to the concentration of the residual water, and the concentration of co-initiator is greater than the concentration of proton scavengers not acting upon residual water.

The concentration of active co-initiator is calculated by the following formula: [total amount co-initiator] - ([proton scavenger] - [water]) = [active co-initiator]. The concentrations of the proton scavenger and the total amount of co-initiator are calculated by dividing the number of moles of scavenger or co-initiator by the volume of liquid present, respectively. The concentration of the water in the system is calculated by solving for I in the following equation [M]/tI] = DP, where M equals monomer, I equals initiator and DP equals the degree of polymerization for a water initiated polymerization. Degree of polymerization is calculated by dividing the number average molecular weight of the polymer by the weight average molecular weight of the monomer(s). (For example, 0.268 mol/l of TiC14 and 2.8 mol/l of isobutylene in a 60/40 mix of methylcyclohexane /methylene chloride at -75 degrees C for 21 minutes yielding 89% polymer with a Mn of 69,lO0 and an Mw/Mn of l.32, means DP = 1232 and the water concentration =
2.8/DP: therefore [I] = 2.3 x 10-3 mol/l.) This value is calculated for a batch of dried solvent or solvent mixture and then the value is used when that solvent is the reaction media. For the purposes of this invention it is assumed that the concentration of water in a given system of the same solvent batch does not vary in a statistically significant manner. (Even though the WO94/19380 PCT~S94/01711 - 11 - 21S6503' exact concentration may vary, the concentration is usually between 10-3 a to 10-4 M.) The polymerization reaction is typically run at or below -30 degrees C preferably below -75 degrees C.
Typical monomers which may be polymerized by this system include one or more of: olefins, alpha-olefins, isoolefins, styrenics, disubstituted olefins or mixtures thereof. Preferred monomers include isobutylene, 2-methyl-butene, 2-methyl-pentene, styrene, alpha-methylstyrene, para-methylstyrene and the like. In a preferred embodiment para-methylstyrene is copolymerized with isoolefin, such as isobutylene.
The polymerization is typically performed in a solution phase reactor by methods known in the art. The polymerization is typically complete in lO minutes, however, may run from less than one minute to an hour.
However, longer polymerization times are still within the scope of this invention.
The polymers produced by this invention have a narrow molecular weight distribution (Mw/Mn), preferably less than 2.0, even more preferably less than l.75. Polyisobutylene and other isobutylene based polymers having a narrow molecular weight distribution are preferred polymers produced by this catalyst system. Furthermore, when tertiary polymeric halide initiators with the tertiary carbon at the chain end or along or with in the polymer backbone are used, block copolymers and/or polymers with one or more side chain - branches including comb copolymers are produced, respectively.

WO94/19380 PCT~S94101711 ~,~.5GSO~
Examples For the examples of this invention, the method described above was used to calculate the concentration of water in the solvents. For all the examples it is assumed that the water concentration was 2.3 x 10-3 mol/l. Once this concentration was determined above solvents from the same batch of dried solvents were used so as to minimize any variation in water concentration.
Molecular weight (Mw and Mn) were measured by Gel Permeation Chromotography using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector. The numerical analyses were performed using the commercially available st~n~rd Gel Permeation package, run on an HPl000 computer.

~xample l:
In a nitrogen box with a water content of approximately 5 parts per million, a resin kettle was charged with 0.018g of (5-tert-butyl-l,3-di(l-chloro-l-methyl ethyl) benzene (TBDCC), 6.6 ml anhydrous methylene chloride, 26.4 ml of anhydrous methyl cyclohexane (20/80 ratio of MeCl2:MCH), and 200 micro liters of DTBP. The solution was cooled to -75 degrees C whereupon 3 milliliters of isobutylene was added.
Once the solution stabilized at this temperature, 0.4 ml of a 2.5 molar solution of diethyl aluminum chloride and methylene chloride were added to begin the polymerization. After l0 minutes the reaction was stopped with the addition of 3 ml of chilled methanol.
The polymer product was isolated by pouring the reaction mixture into the methanol by stirring. The polymer product was isolated and dried. 2.13 g of PIB
was collected (100% yield) having a Mn of 40,600 and a ~094/19380 PCT~S94/01711 21~6503 MWD of l.47. This procedure was repeated except that - time or temperature or monomer amount was varied. The data are presented in Table l.

.
TABLE l No Isobutylene (g) Temp, C Time (min) Conver,%
10 l 3.55 -75 2 16 2 3.55 -75 lO lO0 3 3.55 -75 20 lO0 4 0.71 -75 lO lO0 l.42 -75 lO lO0 15 6 2.13 -75 lO lO0 7 2.84 -75 lO 96 8 3.55 -75 lO lO0 9 3.55 -40 30 75 3.55 -30 30 20 20 ll 3.55 -15 30 6 The co-initiator to initiator site molar concentration ratio was 7 for all the experiments, and the proton scavenger (DTBP) was present at a concentration of 3.0 x lO-2 mol/liter. The active co-initiator to initiator sites ratio was 2Ø

ExamPle 2: "All Monomer In" ExPeriments These reactions were carried out as in Example l except that the initial monomer concentration was varied when added to the polymerization vessel. After lO minutes chilled methanol is added to the polymerization to stop the reaction. Isolated yield of polymers is near 100%. The data are presented in Figures 3 and 4 as triangles or squares. Wp is the weight of the polymer prepared, NI = number of initiator sites, Np = number of polymer chains in the product. Since the reactions went to 100% or substantially 100% conversion the weight of the monomer introduced into the reactor is the same as the weight of the polymer product.

WO94/19380 PCT~S94/01711 ~S6~3 - 14 -Table 2 Exp Wp Mn Np /NI
12 1.79g 34,800 0.820 13 2.13g 40,630 0.835 14 2.84g 51,260 0.833 15 3.55 60,000 0.942 These data support the conclusion that isobutylene polymerizations with this catalyst are living systems but the chains have a shorter lifetime than other living carbocationic polymerization catalysts.

The data can be used in two ways to assess the livingness of a polymerization. First a plot of Mn vs Wp (Figure 4) creates a comparison of experimental Mn with that expected for a truly living system based on starting tM] and [I]. Plotting Np/NI (Np: number of polymer molecules prepared; NI: number of initiator molecules) v. Wp (Figure 5) addressed the total number of polymer ch~ inc created in the system compared with that intended from the amount of initiator added to the system. Both Figures show that actual data follows closely the theoretical line calculated for a living system. Both Figures indicate the system is living.

ExamPle 3:

The procedure used in Example 1 was followed, except that the solvent ratio was 40/60, to conduct a diethyl aluminum chloride polymerization of isobutylene at -75 degrees C.

~094/19380 PCT~S94/01711 21~ili51)3 Proton ACI/IS Yield %
S Scavenger 16 no 8 0 17 yes 2 96 18 yes 1.5 82 19 yes 1 93 yes 0.5 84 21 yes 0 o Proton scavenger = DTBP, [DTBP] = 3.0 x 10-2 mol/liter ACI/IS: ratio of moles active co-initiator to number lS of initiator sites, assuming [water] = 2.3 x 10-3 mol/l.
The data show that the proton scavenger has a beneficial effect on the yield. The data for Example 21 show 0% yield because the proton trap is present at a concentration equal to or greater than the co-initiator, thus there was no "active" co-initiator to polymerize the monomer.

EXAMPLE 4:
The polymerization conducted in Example 2 was repeated however, the solvent ratios were varied. The results are presented in Table 4 and Figure 1.

Exp MeCl~/MCH MWD

24 20/80 1.58 - 25 40/60 2.1 26 60/40 2.5 27 70/30 4.41 - 40 28 80/20 15.14 29 90/lo 9.40 100/0 4.46 wo 94,lg380 S6~ ~ - 16 - ~CT~S94/01711 These data show that when the composition of the solvent was changed from 100% methylene chloride to 20/80 methylene chloride/methyl cyclohexane improved molecular weight distribution was obtained. The narrowing effect of the non-polar methyl cyclohexane is evident at 60/40 methyl dichloride and methyl cyclyhexane mixtures and at 20/80 methylene chloride and methyl cyclohexane mixtures. No polymerization occurred at 10/90 methylene chloride and methyl cyclohexane ratios or in 100% methyl cyclohexane.

As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, 1~ various modifications can be made without departing from the spirit and scope of the invention.
Accordingly, it is not intended that the invention be limited thereby.

Claims (16)

CLAIMS:
I claim:

1. A catalyst composition comprising:
an initiator or one of a tertiary alkyl halide, a tertiary arly halide, or a tertiary aralkyl halide;
a co-initiator or an alkyl aluminum compound or an alkyl boron compound;
a proton scavenger; and a solvent medium having a dielectric constant between 2.5 and 3.25.

2. The catalyst composition of claim 1 wherein the co-initiator is a di-alkyl aluminum halide wherein each alkyl is independently a straight or branched chain alkyl containing 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms.

3. The catalyst composition of claim 1 or 2 wherein the co-initiator is diethyl aluminum chloride.

4. The catalyst composition of claim 1 wherein the initiator is represented by the formula:

wherein R1, R2 and R3 are independently a C1 to C15, preferably C1 to C8, straight or branched chain alkyl, aryl or aralkyl group, X is a halogen and n is a number greater than or equal to 1, preferably between 1 and 6.

5. The catalyst composition of any of the above claims wherein the proton scavenger is 2,6-di-tert-butylpyridiene, 4-methyl-2,6-di-tert-butyl-pyridine, 1,8-bis(dimethylamino)-naphthalene, diisopropylethylamine or mixtures thereof.

. - 18 -

6. The use of the catalyst composition of any of the above claims at a temperature less than -30 degrees C, preferably less than -70 degrees C.

7. The catalyst composition of any of the above claims wherein the ratio of number of moles of co-initiator to the number of active initiator sites is 0.001:1 to 8:1, preferably 0.5:1 to 6:1.

8. The composition of any of the above claims present in a solvent of 60 to 20 parts by volume methylene chloride and 40 to 80 parts by volume methyl cyclohexane.

9. A process for producing a polymer comprising contacting under polymerization conditions one or more olefinic, alpha olefinic, di-substituted olefinic or styrenic monomers with the catalyst composition of any of the above claims.

10. The process of claim 9 wherein the polymerization is conducted at a temperature at or below -30 degrees C, preferably -70 degrees C.

11. The process of claim 9 wherein the initiator is present in a concentration greater than the concentration of the proton scavenger.

12. The process of any of the above claims wherein the co-initiator is diethyl aluminum chloride, the initiator is a tertiary alkyl halide, a tertiary aryl halide or tertiary aralkyl halide wherein each alkyl or aralkyl independently has 1 to 8 carbon atoms and the proton scavenger is 2,6-di-tert-butyl pyridine.

13. The process of claim 9, 10, 11 or 12 wherein the monomer is isobutylene.

14. A process for producing block copolymers comprising sequentially contacting monomers selected from the group consisting of alpha-olefins, olefins, di-substituted olefins, styrenics and mixtures thereof under polymerization conditions with:
an initiator of a tertiary polymeric halide;
a co-initiator of an alkyl aluminum halide or an alkyl boron halide;
a proton scavenger; and a solvent medium having a dielectric constant of 2.5 to 3.25.

15. A process for producing comb copolymers comprising contacting monomers selected from the group consisting or olefins, alpha-olefins, styrenes, di-substituted olefins and mixtures thereof under polymerization conditions with:
an initiator of a multiply-halogenated tertiary polymeric halide;
a co-initiator of an alkyl aluminum halide or an alkyl boron halide;
a proton scavenger; and a solvent medium having a dielectric constant between 2.5 and 3.25.

16. A process for producing polymers with long chain branching comprising contacting monomers selected from the group consisting of olefins, alpha-olefins, styrenes, di-substituted olefins and mixtures thereof under polymerization conditions with:
an initiator of a multiply-halogenated tertiary polymeric halide;
a co-initiator of an alkyl aluminum halide or an alkyl boron halide;

a proton scavenger; and a solvent medium havinga dielectric constant between 2.5 and 3.25;
provided that the initiator has at least one tertiary halide in or along the polymer backbone.