MXPA01006687A - Improved cationic polymerization process and catalyst system therefor - Google Patents

Abstract

A process for producing a copolymer of an isoolefin and at least one other comonomer comprising the step of polymerizing a reaction mixture comprising an isoolefin, a catalyst and at least one of a cycloconjugated multiolefin and an unconjugated cyclic olefin in the presence of an activator comprising a carbo cation producing species, a silica cation producing species and mixtures thereof. The process can be practiced using a slurry polymerization approach. One of the main benefits achieved with the present invention is the conversion of the monomers over a shorter period of time and higher percent conversion than when the activator is not used.

Description

IMPROVED PROCEDURE OF CATIONIC POLYMERIZATION AND CATALYST SYSTEM FOR THE SAME BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to an improved cationic polymerization process and to a catalyst system therefor.

DESCRIPTION OF THE PREVIOUS TECHNIQUE Polymers and copolymers of isobutylene are well known in the art. Specifically, copolymers of isobutylene with conjugated multiolefins have found wide acceptance in the rubber field. These polymers are generally referred to in the butyl rubber art. The butyl rubber preparation is described in U.S. Patent 2,356,128 (Thomas et al.), The contents of which are incorporated herein by reference. The term "butyl rubber", as used throughout this description, is intended to include copolymers made by polymerization of a reaction mixture consisting of an isoolefin having from 4 to 7 carbon atoms (eg, isobutylene) and a conjugated multiolefin which has from 4 to 14 carbon atoms (eg, isoprene). Although said copolymers are said to contain from about 0.2 to about 15% combined multiolefin, in practice the butyl rubber polymers that exist on the market contain from about 0.6 to about 4.5% by weight of multiolefin, more specifically from approximately 0.1 to approximately 2 mol%, the remainder being constituted by the isoolefin component. Efforts to prepare olefin-multiolefin polymers of superior unsaturation have found varying degrees of success. When substantially gel-free polymers containing more than about 5% multiolefin have been prepared, the polymers have been of low numerical average molecular weight. This has been true even when these polymers had medium molecular weights of high viscosity. In general, however, the products formed by the prior art processes, whether of a high gel content or a low numerical average molecular weight, are of little use. In order to have practical commercial utility such as synthetic butyl rubber, the isobutylene-isoprene copolymers should be substantially free of gel and have a number average molecular weight of at least 120,000. The problem associated with the relatively low unsaturation content of conventional butyl rubber is the correspondingly low number of crosslinking sites that can bond with another rubber. In addition, the crosslinking behavior of conventional butyl rubber is different from that of other highly unsaturated rubbers. These properties of conventional butyl rubber give rise to a weak adhesion force, which decreases further when exposed to external shock, vibration and the like. Therefore, the isobutene-cyclopentadiene copolymer has been proposed in the prior art as an alternative to conventional butyl rubber. The isobutene-cyclopentadiene copolymer has a better adhesion strength, as well as excellent gas barrier properties, even at high degrees of unsaturation. In addition, while the unsaturation of the cyclopentadiene moiety in the copolymer is susceptible to attack by ozone and the like, since the unsaturation hangs from the polymeric backbone (ie, not part of the polymer backbone), the polymer backbone remains substantially without affecting. Therefore, the aging properties of a vulcanizate made with the copolymer are excellent and its other improved characteristics make it highly desirable for use in tires. The general problem with the isobutene-cyclopentadiene copolymers of the prior art resides in the production thereof, particularly in commercial quantities. The specific problems include one or both of the following: (i) maintaining the stability of the cyclopentadiene comonomer for a sufficient period for the copolymerization to take place (the comonomer is usually unstable against heat); (ii) as the degree of unsaturation increases, there is an increase in gel formation and a reduction in the molecular weight (Mp) of the copolymer. This latter problem can be addressed using a conventional solution polymerization approach. See, for example, one or more of: U.S. Patent 3,808,177 (Thaler et al.), U.S. Patent 3,856,763 (Thaler et al.), U.S. Patent 4,031,360 (Thaler et al.) And U.S. Patent 4,139. 695 (Thaler et al.), Whose contents are incorporated herein by reference. The use of a solution polymerization approach to produce an isobutene-cyclopentadiene copolymer has been criticized in International Publication No. WO 97/05181 (Youn et al.), Whose contents are incorporated herein by reference - see, for example, page 3, line 2, page 4, line 20, of Youn et al. Certainly, the pre-tended point of novelty shown by Youn et al. It is related to a suspension polymerization approach. In spite of the solution and suspension polymerization approaches of the prior art for the production of isobutene-cyclopentadiene copolymers, there is still room for improvement. Specifically, it would be desirable to have a polymerization process for the production of an isobutene-cyclopentadiene copolymer that could be used with a suspension approach to produce a low (or negligible) gel-content copolymer at relatively high conversion rates of the comonomer of cyclopentadiene in a shortened period of time, thus improving the efficiency of the catalyst, which is low in comparison with the butyl polymerizations of the state of the art.

SUMMARY OF THE INVENTION It is an object of the present invention to obviate or mitigate at least one of the previously identified drawbacks of the prior art. It is another object of the present invention to provide an improved catalyst system for the copolymerization and terpolymerization of isoolefins. It is another object of the present invention to provide an improved process for the copolymerization and terpolymerization of isoolefins. Accordingly, in one of its aspects, the present invention provides a suspension process for producing a copolymer of an isoolefin and at least one other comonomer, consisting of the step of polymerizing a reaction mixture consisting of an isoolefin, a catalyst and less one of a cycloconjugated mutri-olefin and a non-conjugated cyclic olefin, in the presence of an activator containing a cation-producing species carbo, a species producing cations of silica and their mixtures. Thus, the present inventors have discovered, surprisingly and unexpectedly, that the use of a specific activator in this cationic polymerization process surprisingly and unexpectedly improves the process by exhibiting a better conversion in less time while maintaining a desirable Mp. This is certainly surprising, given the teachings of Kennedy et al. (J. Macromol, Sci. Chem. Al (16), pp. 977-993 (1967), whose contents are incorporated herein by reference), where tert-butyl chloride was used as a chain transfer agent and a Mp reduction The present process is characterized by the lack of a significant reduction of Mp, especially when the procedure is carried out in a semi-batch mode. One of the main benefits achieved with the present invention is the conversion of the monomers over a shorter period of time and the higher percentage of conversion than when the activator is not used. In addition, one or more of the following advantages are also added: 1. High conversion of a second comonomer in a shorter period of time, 2. a low or negligible gel content, 3. ability to achieve useful results at temperatures in the range from about - 110 ° C to about -80 ° C. Other advantages will be apparent to those skilled in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention relates to a method of preparing a copolymer of an isoolefin and at least one of a cycloconjugated multiolefin and a non-conjugated cyclic olefin. Of course, those skilled in the art will recognize that the products of the present process can be at least any of: a copolymer of an isoolefin and a cycloconjugated multiolefin, a copolymer of an isoolefin and a non-conjugated cyclic olefin, a terpolymer of a isoolefin, a cycloconjugated multiolefin and a non-conjugated cyclic olefin, a terpolymer of one isoolefin and two (or more) different cycloconjugated multiolefins and a terpolymer of one isoolefin and two (or more) different non-conjugated cyclic olefins. Preferably, the copolymer has a number average molecular weight of from about 30,000 to about 600,000, more preferably from about 50,000 to about 400,000, still more preferably from about 70,000 to about 350,000, and a molar% unsaturation of at least about 1 to about 45 mole%, more preferably at least about 1 to about 40 mole% and, more preferably, the unsaturation is about 2-25%. Preferably, the isoolefin suitable for use in the present process is a C4-C? 0 hydrocarbon monomer. Non-limiting examples of suitable isoolefins can be selected from the group consisting of isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and mixtures thereof. The preferred isoolefin is isobutylene. Preferably, the cycloconjugated multiolefin suitable for use in the present process is a C5-C20 hydrocarbon monomer having at least one pair of conjugated double bonds. The monomer may consist of a 5-membered ring structure. Non-limiting examples of suitable monomers including said ring structure can be selected from the group consisting of cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 1,3-dimethylcyclopentadiene and mixtures thereof. In addition, the monomer may include a 6-membered ring structure containing a conjugated diene. Non-limiting examples of suitable monomers including said ring structure can be selected from the group consisting of 1,3-cyclohexadiene, 1-methyl-1,3-cyclohexadiene, 1-methylene-2-cyclohexene, 2-methyl- 1, 3-cyclohexadiene, 1,3-dimethyl-1,3-cyclohexadiene and mixtures thereof. You can also use indene and its derivatives.

Preferably, the non-conjugated cyclic olefin suitable for use in the present process is a bicyclo containing an unsaturated bond. Non-limiting examples of such suitable monomers can be selected from terpene-for example, β-pinene. In a preferred embodiment, terpolymers of an isobutylene, a cycloconjugated diolefin, and a third monomer (e.g., unconjugated terpenes) can be prepared according to the method embodied by the present process, wherein these terpolymers have a number average molecular weight (Mn). ) from about 30,000 to about 600,000, more preferably from about 50,000 to about 400,000 and, even more preferably, from about 70,000 to about 350,000, and a molar percent of cyclopentadiene unsaturation of at least 1 to about 45 mole%, more preferably at least 1 to about 25 mol%. The total unsaturation of all the comonomers and cyclopentadiene is preferably between 1 and 45 mol%, more preferably between 1 and 40 mol% and, more preferably, between 1 and 30 mol%. It is possible and preferred to practice the present process using a suspension polymerization approach. As is known in the art, the use of a suspension polymerization allows higher conversions than for solution polymerization (eg, 80% to 95% or more) without a concomitant increase in viscosity in the reaction mixture. The suspension polymerization approach uses a diluent that is a non-solvent for the polymer product. The choice of diluent is within the reach of those skilled in the art. Preferably, the diluent is a polar diluent. The term polar diluent, as used in the description and claims, means liquids having a dielectric constant at 25 ° C of less than about 20, more preferably less than about 17, more preferably less than about 10. These liquids, however, preferably do not contain sulfur, oxygen or phosphorus in the molecule, since the compounds containing these elements will react with the catalyst or deactivate it in some other way. Preferred polar diluents are inert halogenated aliphatic hydrocarbons, more preferably halogenated paraffinic hydrocarbons and vinyl or vinylidene halides, more preferably primary or secondary chlorinated paraffinic hydrocarbons. The term "inert" means that the cosolvent will not react with the catalyst or enter the polymerization reaction in any other way. The halogenated hydrocarbon is preferably a Ci-C5 paraffinic hydrocarbon, more preferably, a C? -C2 paraffin. The ratio of carbon atoms to halogen atoms in the polar diluent is preferably 5 or less. Preferably, the halogen is chloro. Illustrative examples of these polar diluents are methyl chloride, ethyl chloride, propyl chloride, methyl bromide, ethyl bromide, chloroform, methylene chloride, vinyl chloride, vinylidine chloride, dichloroethylene, etc. Preferably, the polar diluent is methyl chloride or ethyl chloride. When the suspension polymerization approach is used, any of the catalysts discussed above with respect to the solution polymerization approach can be used. In the practice of this invention, a catalyst is used. Preferably, in the suspension polymerization approach the catalyst has the formulas AlY3, where Y is a halogen. The most preferred catalyst for use in the suspension approach is AlCl3. However, the use of aluminum catalysts in Ziegler-Natta polymerization processes is well known and alternative choices of aluminum catalysts for use in the present process are within the scope of one skilled in the art. For example, the aluminum catalyst can include at least one compound having the formula: (R) pAlYq where R is selected from the group consisting of a C2-C?? alkyl group, a C2-C? 0 alkoxy group and a cycloalkyl group C3-C20, Y is a halogen, and p + q is 3. More preferably, q is different from 0. Possibly, the aluminum catalyst consists of a mixture of at least two of said compounds. Preferably, p is a number in the range of about 1 to about 2 and q is a number in the range of about 1 to about 2. In a most preferred embodiment, p is 2 and q is 1. In another more preferred embodiment, p and q are 1,5. In yet another more preferred embodiment, p is 1 and q is 2. Preferably, R is ethyl. Of course, the halogen Y in the preferred formula for the aluminum catalyst can be selected from the group consisting of bromide, chloride, iodide and astatus. The preferred halogen moiety is chloride. If two or more halogen moieties are present in the aluminum catalyst, it is preferred that they be the same. Non-limiting examples of aluminum catalysts useful in the present invention may be selected from the group consisting of diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyldiethoxyalu-minium, methylaluminum dichloride, isobutylalu-minium dichloride, methylaluminum dibromide, ethylaluminum dibromide, benzylaluminum dichloride, phenylaluminum dichloride, xylylaluminum dichloride, toluylaluminum dichloride, butyl aluminum dichloride, hexylaluminum dichloride, octyl aluminum dichloride, cyclohexylaluminum dichloride and mixtures thereof. Preferred catalysts are methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminium dichloride, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride and mixtures thereof. As is known to those skilled in the art, if it is desired to use ethylaluminum sesquichloride as the aluminum catalyst, it is possible to produce the cocatalyst by mixing equimolar amounts of diethylaluminum chloride and ethylaluminum dichloride. When an aluminum halide is used, it is preferably in the form of a homogeneous solution or a submicron dispersion of catalyst particles, for example a colloidal dispersion. Therefore, the catalyst is preferably dispersed or dissolved in a suitable solvent or mixture of catalyst solvents. The catalyst solvent is preferably a polar solvent. It is preferred that the aluminum halide catalyst be in solution in the polar organic solvent prior to the introduction of the catalyst into the reaction medium. The use of the term solution in relation to polar organic solvent / aluminum halide systems is intended to include both true solutions and colloidal dispersions, since they can exist at the same time in the same system. The aluminum halide / polar solvent catalyst contains about 0.01 to about 2% by weight of aluminum halide, more preferably about 0.01 to about 1, more preferably 0.04 to about 0, 8 The hydrocarbylaluminum dihalide catalyst can be added net or in solution. Preferably, when a catalyst solvent is used, it is a liquid paraffin solvent or a cycloparaffin solvent. It is advantageous, although not necessary, to use low freezing point paraffins. Methylcyclohexane is particularly useful, since the catalyst solutions of about 1% concentration do not freeze at -120 ° C. The concentration of catalyst is not critical. However, very dilute catalyst solutions are not desirable, since substantial fractions of the catalyst can be deactivated due to impurities. Highly concentrated solutions are not desirable, since, at polymerization temperatures, the catalyst can be lost by separating from the solution by freezing. By carrying out the present procedure, those skilled in the art will be aware that only catalytic amounts of catalyst solution are required. Preferably, the ratio of monomer volume plus diluent to catalyst solution is from about 100/1 to about 9/1, preferably from about 80/1 to about 10/1, more preferably from about 50/1 to about 20/1. /1. It is desirable to conduct the reaction below about -80 C, more preferably from about 90 C to 110 C. In the Examples given here below, specifically preferred embodiments of this suspension approach will be illustrated. For more general information, see, for example, Youn et al., Cited and incorporated herein by reference. In the present process, use is made of an activator consisting of a species producing cations carbo, a species producing cations of silica and their mixtures. Preferably, the activator is used in an amount in the range of about 0.0005 to about 0.2, more preferably from about 0.001 to about 0.1, more preferably from about 0.002 to about 0. , 06% by weight, based on the total weight of the monomers. In a preferred embodiment, the activator is a carbocation-producing species having the formula: R x -X where R 1 is a cyclohydrocarbon optionally substituted with one or more heteroatoms and X is selected from the group consisting of a halogen, - OH and -OR2, where R2 is the same or different from R1 and is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms. In a preferred embodiment, each of R 1 and R 2 is a straight or branched chain C 1 -C 0 alkyl group optionally having one or more unsaturation. In another preferred embodiment, each of R1 and R2 is a substituted or unsubstituted C5-C40 aryl group. In yet another embodiment, each of R1 and R2 is a substituted or unsubstituted C3-C40 cycloalkyl group. Preferably, X is selected from the group consisting of Cl, Br and I. The most preferred embodiments of X can be selected from the group consisting of Cl, OH and OCH3. In another preferred embodiment, the activator has the formula: X ^ R-X2 where R is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms and X1 and X2 are the same or different and are each a halogen, -OH and -OR3, where R3 is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms. In a preferred embodiment, R is a straight or branched chain Ci-C40 alkyl group optionally having one or more unsaturations. In another preferred embodiment, R is a substituted or unsubstituted C5-C0 aryl group. In yet another embodiment, R is a substituted or unsubstituted C3-C0 cycloalkyl group. In a preferred embodiment, R 3 is a straight or branched chain C 1 -C 4 alkyl group optionally having one or more unsaturations. In another preferred embodiment, R3 is a substituted or unsubstituted C5-C40 aryl group. In yet another embodiment, R3 is a substituted or unsubstituted C3-C40 cycloalkyl group. Preferably, X1 and X2 are selected from the group consisting of Cl, Br and I; more preferably, X1 and X2 are both Cl. Non-limiting examples of activators useful in the present process as a suitable carbo-cation producing species include: CH 3 CH 3 Cl-C-R-C-Cl I I CH 3 CH 3 where R is a C 1 -C 40 hydrocarbon optionally substituted with one or more heteroatoms, and cis and trans isomers of: C1H2C-CH = CH-CH2C1. In another preferred embodiment, the activator can be selected from the group consisting of allyl chloride, tere-butyl chloride, benzyl chloride, 4-methylbenzyl chloride and mixtures thereof. In another preferred embodiment, the activator is a silica cation producing species having the formula: R4R5R6SiX where R4, R5 and R6 are the same or different and each is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms and X It is a halogen. In a preferred embodiment, each of R 4, R 5 and R 6 is a linear or branched C 1 -C 4 alkyl group optionally having one or more substitutions. In another preferred embodiment, each of R4, R5 and R6 is a substituted or unsubstituted C5-C40 aryl group. In yet another preferred embodiment, each of R4, R5 and R6 is a substituted or unsubstituted C3-C40 cycloalkyl group. Preferably, X is selected from the group consisting of Cl, Br and I; more preferably X is Cl. A non-limiting example of a species producing silica cations is trimethylsilyl halide. Embodiments of the present invention will now be described with reference to the following Examples, which are not to be considered as limiting the scope of the invention. Example 1 At -30 ° C, 0.0267 g of AlCl 3 (purity 99.99% - <100 ppm H20) was dissolved in 55.4 ml of methyl chloride H 20 ppm H20) to form a catalyst solution. This solution was stirred for 30 minutes at -30 ° C and then cooled to -95 ° C. In a 500 ml, 3-necked reaction flask with a stirrer in the upper position, a reaction mixture was stirred, consisting of 0.66 g of cyclopentadiene, 38.5 ml of isobutene and 161 ml of methyl chloride a- 95 ° C. The temperature of the mixture was brought to -93 ° C and the catalyst solution was added immediately to start the polymerization. All temperature changes during the reaction were followed by a thermocouple. After 20 minutes, the reaction was stopped by adding 3 ml of a solution of NaOH in ethanol (1.0% by weight) to the reaction mixture. The polymerization was carried out in a Braun dry box under an atmosphere of dry nitrogen H 5 ppm H20, - < 20 ppm 02). The solvent, the unreacted monomers and the ethanol were removed in vacuo and the yield of the polymer was determined by gravimetry to be 16.3% by weight. Dissolving in hexane and reprecipitating with ethanol, the polymer was cleaned. After 3 days of drying in a vacuum oven at room temperature, the molecular weight, determined by CPG (UV detection) was Mn = 130,000, Mp = 195,000; it was determined that the cyclopentadiene content in the polymer was 7.2 mol% per 1 H-NMR. This Example represents a control reaction without the addition of an accelerator and is therefore facilitated for comparative purposes only.

Example 2 The methodology of Example 1 was repeated, except for the fact that the reaction mixture consisted of 1.65 g of cyclopentadiene, 37 ml of isobutene and 161 ml of methyl chloride. The yield of the polymer was 13.9% by weight, the molecular weight was Mn = 53,000, Mp = 130,000 and the cyclopentadiene content in the polymer was 17.9 mol%. This Example represents a control reaction without the addition of an accelerator and is therefore facilitated for comparative purposes only. Example 3 The methodology of Example 1 was repeated, except for the fact that the reaction mixture consisted of 0.81 g of methylcyclopentadiene, 38.5 ml of isobutene and 161 ml of methyl chloride. The yield of the polymer was 49.0% by weight, the molecular weight was Mn = 57,000, Mp = 327,000 and the content of methylcyclopentadiene in the polymer was 4.0 mol%. This Example represents a control reaction without the addition of an accelerator and is therefore facilitated for comparative purposes only. Example 4 The methodology of Example 1 was repeated, except for the fact that the reaction mixture consisted of 0, 33 g of cyclopentadiene, 0.40 g of methylcyclopentadiene, 38.5 ml of isobutene and 161 ml of methyl chloride. The yield of the polymer was 25.8% by weight, the molecular weight was Mn = 52,000, Mp = 182,000 and the content of cyclopentadiene in the polymer was 2.8 mol% and the content of methylcyclopentadiene in the polymer It was 3.5% molar. This Example represents a control reaction without the addition of an accelerator and is therefore facilitated for comparative purposes only. Example 5 The methodology of Example 1 was repeated, except for the addition of 9.3 mg tere-butyl chloride to the reaction mixture before starting the reaction. The polymer yield was 77.4% by weight, the molecular weight was Mn = 47,000, Mp = 109,000 and the cyclopentadiene content in the polymer was 2.9 mol%. Example 6 The methodology of Example 5 was repeated, except for the addition of 18.6 mg tere-butyl chloride to the reaction mixture before starting the reaction. The polymer yield was 98.5% by weight, the molecular weight was Mn = 37,000, Mp = 75,000 and the cyclopentadiene content in the polymer was 1.9 mol%. Example 7 The methodology of Example 5 was repeated, except for the addition of 4.6 mg tere-butyl chloride to the reaction mixture before starting the reaction. The polymer yield was 50.3% by weight, the molecular weight was Mn = 69,000, Mp = 134,000 and the cyclopentadiene content in the polymer was 3.7 mol%.

Example 8 The methodology of Example 3 was repeated, except for the addition of 9.3 mg of tert-butyl chloride to the reaction mixture before starting the reaction. The polyurethane yield was 70.5% by weight, the molecular weight was Mn = 65,000, Mp = 310,000 and the methylcyclopentadiene content in the polymer was 2.6 mol%. Example 9 The methodology of Example 4 was repeated, except for the addition of 9.3 mg of tert-butyl chloride to the reaction mixture before starting the reaction. The polymer yield was 53.1% by weight and the molecular weight was Mn = 32,000, Mp = 120,000. The content of cyclopentadiene in the polymer was 1.8 mol% and the content of methylcyclopentadiene in the polymer was 2.1 mol%. Example 10 The methodology of Example 5 was repeated, except for the addition of 12.7 mg of benzyl chloride to the reaction mixture before starting the reaction. The polymer yield was 27.0% by weight, the molecular weight was Mn = 91,000, Mp = 176,000 and the cyclopentadiene content in the polymer was 5.6 mol%. Example 11 The methodology of Example 5 was repeated, except for the addition of 14.1 mg of 4-methylbenzyl chloride to the reaction mixture before starting the reaction. The polymer yield was 20.2% by weight, the molecular weight was Mn = 115,000, Mp = 185,000 and the cyclopentadiene content in the polymer was 6.2 mol%. Example 12 The methodology of Example 5 was repeated, except for the addition of 6.2 mg of cis-1,4-dichloro-2-butene to the reaction mixture before starting the reaction. The polymer yield was 52.9% by weight, the molecular weight was Mn = 72,000, Mp = 263,000 and the cyclopentadiene content in the polymer was 2.8 mol%. Example 13 The methodology of Example 5 was repeated, except for the addition of 6.2 mg of trans-1,4-dichloro-2-butene to the reaction mixture before starting the reaction. The polymer yield was 100% by weight, the molecular weight was Mn = 193,000, Mp = 1,429,000 and the cyclopentadiene content in the polymer was 2.0 mol%. Example 14 The methodology of Example 5 was repeated, except for the addition of 15.1 mg of 4-vinylbenzyl chloride to the reaction mixture before starting the reaction. The polymer yield was 86.7% by weight, the molecular weight was Mn = 62,000, Mp = 140,000 and the cyclopentadiene content in the polymer was 2.3 mol%. Example 15 The methodology of Example 5 was repeated, except for the addition of 15.1 mg of α, α'-dichloro-p-xylene to the reaction mixture before starting the reaction. The yield of the polymer was 99.5% by weight, the molecular weight was Mn = 84,000, Mp = 202,000 and the cyclopentane content in the polymer was 2.1 mol%. Example 16 The methodology of Example 5 was repeated, except for the addition of 9.7 mg of a, a, a ', a'-tetramethyl-1,4-benzenedimethanol to the reaction mixture before starting the reaction. The yield of the polymer was 25.4% by weight, the molecular weight was Mn = 87,000, Mp = 215,000 and the cyclopentane content in the polymer was 6.0 mol%. Example 17 At -30 ° C, 0.0267 g of AlCl3 (purity 99.99%, <100 ppm H20) was dissolved in 55.4 ml of methyl chloride (<20 ppm H20) to form the solution of catalyst. The solution was stirred for 30 minutes at -30 ° C and then cooled to -95 ° C. In a 500 ml, 4-neck reaction flask equipped with an overhead stirrer and two coated addition funnels, 150 ml of methyl chloride was stirred at -93 ° C. After cooling the addition funnels to -93 ° C, one was filled with 50 ml of the catalyst solution and the other was filled with 50 ml of a reaction solution consisting of 0.66 g of cyclopentadiene, 38.5 ml of isobutene and 11 ml of methyl chloride. The catalyst and reaction solutions were added to the reaction flask at a constant rate of 1.4 ml / min. All temperature changes during the reaction were followed with a thermocouple. One minute after the addition of the catalyst and reaction solutions was complete, the reaction was stopped by adding 3 ml of a solution of NaOH in ethanol (1.0% by weight) to the reaction mixture. Polymerization was carried out in a Braun ™ dry box under a dry nitrogen atmosphere (<; 5 ppm H20, < 20 ppm 02). The solvent, unreacted monomers and ethanol were removed in vacuo and the yield of the polymer was determined by gravimetry at 12.3% by weight. Dissolving in hexane and reprecipitating with ethanol, the polymer was cleaned. After 3 days of drying in a vacuum oven at room temperature, the molecular weight, determined by CPG (IR detection), was Mn = 101,000, Mp = 184,000, and the cyclopentadiene content, determined by 1 H-NMR spectrometry , in the polymer it was 7.3 mol%. This Example represents the semicontinuous control reaction without addition of an accelerator and, therefore, is provided for comparative purposes only. Example 18 The methodology of Example 17 was repeated, except for the fact that the reaction mixture consisted of 0.66 g of cyclopentadiene, 38.5 ml of isobutene, 9.3 mg of tert-butyl chloride and 11 ml of Methyl chloride. The yield of the polymer was 73.6% by weight, the molecular weight was Mn = 75,000, Mp = 210,000, and the cyclopentadiene content in the polymer was 2.5 mol%. Example 19 The methodology of Example 17 was repeated, except for the fact that the reaction mixture consisted of 0.33 g of cyclopentadiene, 0.40 g of methylcyclopentadiene, 38.5 ml of isobutene and 11 ml of sodium chloride. methyl. The yield of the polymer was 26.5% by weight; the molecular weight was Mn = 94,000, Mp = 198,000; the content of cyclopentadiene in the polymer was 2.6 mol% and the content of methylcyclopentadiene was 5.8 mol%. This Example represents the semicontinuous control reaction without addition of an accelerator and, therefore, is provided for comparative purposes only. EXAMPLE 20 The methodology of Example 17 was repeated, except for the fact that the reaction mixture consisted of 0.33 g of cyclopentadiene, 0.40 g of methylcyclopentadiene, 38.5 ml of isobutene, 9.3 mg of sodium chloride. tert-butyl and 11 ml of methyl chloride. The yield of the polymer was 61.1% by weight; the molecular weight was Mn = 98,000, Mp = 205,000; the content of cyclopentadiene in the polymer was 1.3 mol% and the content of methylcyclopentadiene was 2.8 mol%. Example 21 The methodology of Example 17 was repeated, except for the fact that the reaction mixture consisted of 0.81 g of methylcyclopentadiene, 38.5 ml of isobutene and 11 ml of methyl chloride. The yield of the polymer was 26.7% by weight; the molecular weight was Mn = 151,000, Mp = 397,000, and the methylcyclopentadiene content was 5.7 mol%. This Example represents the semicontinuous control reaction without addition of an accelerator and, therefore, is provided for comparative purposes only. Example 22 The methodology of Example 17 was repeated, except for the fact that the reaction mixture consisted of 0.81 g of methylcyclopentadiene, 38.5 ml of isobutene, 9.3 mg of tert-butyl chloride and 11 ml of Methyl chloride. The yield of the polymer was 56.3% by weight; the molecular weight was Mn = 135,000, Mp = 365,000, and the content of methylcyclopentadiene was 2.8 mol%. In each of the above Examples, the weight ratio of solvent to monomers was 8.4, the wt% of the catalyst solution was 0.047, the weight ratio of catalyst solution to monomers was 1. , 96, the reaction temperature was -93 ° c and the reaction time was 20 minutes in Examples 1-16 and 36 minutes in Examples 17-22. Other various process parameters of the previous Examples and various properties of the polymers produced in the examples are given in the attached tables (Note: IPD = polydispersity index). The results given in the attached tables illustrate the advantages of the present procedure. In particular, higher polymer yields and catalyst efficiencies are achieved by using the accelerator (i.e., the activator) of the present process as compared to its non-use. This can be seen especially in Examples 17-22, where there is a lack of significant reduction of Mp for Examples 18, 20 and 22 compared to Examples 17, 19 and 21, respectively. While the invention has been described hereinbefore in relation to various preferred embodiments and specific examples, those skilled in the art will clearly understand that modifications and variations of preferred embodiments and specific examples are possible which do not deviate from spirit and scope. of the present invention. Accordingly, it is contemplated that said modifications and variations of the preferred embodiments and the specific Examples will be protected by the invention.

Claims (35)

Claims

1. A suspension process for producing a co-limero of an isoolefin and at least one other comonomer, consisting of the step of polymerizing a reaction mixture consisting of an isoolefin, a catalyst having the formula AlY3, wherein Y is a halogen, and except one of a cycloconjugated multiolefin and a non-conjugated cyclic olefin in the presence of an activator, which consists of a species producing cations carbo, a species producing cations of silica and their mixtures.

2. The process defined in claim 1, wherein the activator is a carbocation-producing species having the formula: R1-X where R1 is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms and X is selected from the group consisting of in a halogen, -OH and -OR2, where R2 is the same or different from R1 and is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms.

3. The process defined in claim 2, wherein each of R 1 and R 2 is a straight or branched chain C 1 -C 40 alkyl group optionally having one or more insatu-rations.

4. The process defined in claim 2, wherein each of R1 and R2 is a substituted or unsubstituted C5-C40 aryl group.

5. The process defined in claim 2, wherein each of R1 and R2 is a substituted or unsubstituted C3-C40 cycloalkyl group.

6. The method defined in claims 1-5, wherein X is selected from the group consisting of Cl, Br and I.

7. The method defined in any of claims 1-5, wherein X is Cl.

8. The method defined in any of claims 1-5, wherein X is OH.

9. The method defined in any of claims 1-5, wherein X is 0CH3.

10. The process defined in claim 1, wherein the activator has the formula: Xx-R-X2 where R is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms and X1 and X2 are the same or different and each is a halogen? , -OH and -OR3, where R3 is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms.

11. The process defined in claim 10, wherein R is a straight or branched chain C? -C40 alkyl group which optionally has one or more unsaturations.

12. The process defined in claim 10, wherein R is a substituted or unsubstituted C5-C40 aryl group.

13. The process defined in claim 10, wherein R is a substituted or unsubstituted C3-C40 cycloalkyl group.

14. The process defined in any of claims 10-13, wherein R3 is a straight or branched chain C? -C40 alkyl group optionally having one or more unsaturations.

15. The process defined in any of claims 10-13, wherein R3 is a substituted or unsubstituted C5-C40 aryl group.

16. The process defined in any of the re-vindi.ccaaeciiooness 1100--1133, ddoonnddee R3 is a C3-Co substituted or unsubstituted cycloalkyl group.

17. The process defined in any of claims 10-16, wherein X1 and X2 are selected from the group consisting of Cl, Br and I.

18. The method defined in any of claims 10-16, wherein both X1 and X2 are Cl.

19. The process defined in claim 1, wherein the activator consists of allyl chloride.

20. The process defined in claim 1, wherein the activator consists of tert-butyl chloride.

21. The method defined in claim 1, wherein the activator consists of: CH 3 CH 3 I I Cl-C-R-C-Cl I I CH3 CH3 where R is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms.

22. The method defined in claim 1, wherein the activator is selected from the group consisting of:

23. The method defined in claim 1, wherein the activator is:

24. The process defined in claim 1, wherein the activator is selected from the group consisting of the cis and trans isomers of: C1H2C-CH = CH-CH2C1.

25. The method defined in claim 1, wherein the activator has the formula:

26. The process defined in claim 1, wherein the activator is a silica cation producing species having the formula: R4R5R6SiX wherein R4, R5 and R6 are the same or different and each is a C? -C40 hydrocarbon optionally substituted with one or more heteroatoms and X is a halogen.

27. The process defined in claim 26, wherein each of R 4, R 5 and R 6 is a straight or branched chain C 1 -C 40 alkyl group optionally having one or more unsaturations.

28. The process defined in claim 26, wherein each of R4, R5 and R6 is a substituted or unsubstituted C5-C40 aryl group.

29. The process defined in claim 26, wherein each of R4, R5 and R6 is a substituted or unsubstituted C3-C40 cycloalkyl group.

30. The process defined in any of claims 26-29, wherein X is selected from the group consisting of Cl, Br and I.

31. The process defined in claim 1, wherein the activator consists of trimethylsilyl chloride.

32. The process defined in any of claims 1-31, wherein the isoolefin is selected from the group consisting of isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-pentene and mixtures thereof .

33. The process defined in any of claims 1-32, wherein the cycloconjugated multiolefin is selected from the group consisting of cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,3-cyclohexadiene, -methyl-1,3-cyclohexadiene, l-methylene-2-cyclohexene, 2-methyl-1,3-cyclohexadiene, 1,3-dimethyl-1,3-cyclohexadiene and mixtures thereof.

34. The process defined in any of claims 1-33, wherein the non-conjugated cyclic olefin consists of β-pinene.

35. The process defined in any one of claims 1-34, wherein the catalyst consists of AlCl 3.