Title of Invention | "POLYMERIZATION PROCESS USING ZINC HALIDE INITIATORS" |
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Abstract | A cationic polymerization process for isoolefins using a zinc halide initiator. The zinc halide initiator is added to a solution of the isoolefin in a suitable solvent, preferably a halocarbon solvent. Polymerization reactions are normally conducted at temperatures high enough to allow the zinc halide initiator to dissolve in the solution. An alkyl halide activator may optionally be used and is preferably added to the solution prior to the zinc halide initiator. A multiolefin may optionally be present in the solution. The process is particularly useful in the formation of isoolefin homopolymers and co-polymers of isoolefins and multiolefins, such as butyl rubber. |
Full Text | POLYMERIZATION PROCESS USING ZINC HALIDE INITIATORS Field of the Invention The invention relates to the cationic polymerization of isoolefins and optionally multiolefins using zinc halide initiators. More particularly, the invention relates to the cationic polymerization of isobutene and isoprene to form butyl rubber polymers using zinc halide initiators and optionally alkyl halide co-initiators. Background Poly(isobutylene-co-isoprene), or MR, is a synthetic elastomer commonly known as butyl rubber which has been prepared since the 1940's through the random cationic copolymerization of isobutylene with small amounts of isoprene 2 mole %) . As a result of its molecular structure, IIR possesses superior air impermeability, a high loss modulus, oxidative stability and extended fatigue resistance. Butyl rubber is a copolymer of an isoolefin and one or more, preferably conjugated, multiolefins as comonomers. Commercial butyl comprises a major portion of isoolefin and a minor amount, not more than 2.5 mol %, of a conjugated multiolefin. Butyl rubber or butyl polymer is generally prepared in a slurry process using a suitable polymerization solvent, such as methyl chloride, and a Friedel-Crafts catalyst, such as AICI3, as the polymerization initiator. The methyl chloride offers the advantage that Aids, a relatively inexpensive Friedel-Crafts catalyst, is soluble in it, as are the isobutylene and isoprene comonomers. Additionally, the butyl rubber polymer is insoluble in the methyl chloride and precipitates out of solution as fine particles. The polymerization is generally carried out at temperatures of about - 90° C to -100° C. See U.S. Patent No. 2,356,128 and Ullmanns Encyclopedia of Industrial Chemistry, volume A 23, 1993, pages 288-295. The low polymerization temperatures are used to achieve molecular weights which are sufficiently high for rubber applications. Other compounds that have been found to be active as catalysts for polymerizing isoolefins include organometallic compounds in combination with a cation-generating agent, for example CsMesTiMes/B^eFsh (WO-00/04061-A1), Cp2AIMe/B(C6F5)3 (US-5,703,182), and combinations of zirconocenes and related complexes with either B(C6F5)3 or CPh3[B(C6F5)4] (WO-95/29940-A1 , DE-A1-198 36 663), Song, X.; Thornton-Pett, M.; Bochmann, M. Organometallics 1998, 17, 1004, Carr, A. G.; Dawson, D. M.; Bochmann, M. Macromol. Rapid Commun. 1998, 205. Nuyken, in collaboration with M. Bohnenpoll (Chem. Eur. J. 2004, 10, 6323), published a system based on [Mn(NCMe)6]2+ salts of non-coordinating borate anions which was active at room temperature: YX- B(C6F5)4, B{C6H3(CF3)2}4 This system operated at +30°C in IB/CH2CI2 but showed no activity 0°C. Polymerizations were generally slow (55 - 110 h for IB homopolymerizations), and there was some doubt about the mechanism. IB homopolymers and copolymers had Mn = 8,000 - 10,000. Conversion was rapidly depressed at higher IP feed. Zinc compounds have not commonly been used as catalysts for isoalkene polymerizations. Indeed, ZnCI2 in the presence or absence of alkyl halide activators (such as MeaCCI or MeCOCI) and used either in neat isobutene or in isobutene/methyl chloride mixtures, proves to be inactive, and no polymer is obtained. Recently however, Bochmann and coworkers filed a patent on the use of Zn(C6P5)2 / Bu'CI system for IB homo- and IB/IP copolymerizations (Canadian patent application 2,441,079, filed September 16, 2003). Zinc had never been used as an initiator for cationic polymerizations before. This patent teaches that this system possessed particularly good copolymerization characteristics and allowed the formation of IB/IP copolymers in neat IB solutions (no solvent). The polymers had up to 15 mol-% IP, with little gel content. However, monitoring the reaction of Zn(C6F5)2 with tert-butyl chloride fBuCI) always found substantial amounts of C6F5H together with insoluble precipitates. In addition, the Zn(CeF5)2 is expensive to use in a commercial scale process and lower cost alternatives are therefore being sought. The need therefore remains for improved polymerization processes using zinc-based initiators. Summary of the Invention According to the present invention, there is provided a process for the cationic polymerization of an isoolefin monomer using a zinc-based initiator, the process comprising: providing a solution of the isoolefin monomer in a halocarbon solvent; adding a zinc-based initiator comprising an alkyl or aryl zinc halide to the solution; and, reacting the solution containing the zinc-based initiator to form a polymer comprising the isoolefin. Polymerization reactions may be conducted at temperatures high enough to allow the zinc halide initiator to dissolve in the solution. An alkyl halide activator may optionally be used and is preferably added to the solution prior to the zinc halide initiator. Multiolefins may optionally be present with the isoolefin in the solvent and may participate in the reaction to form co-polymers with the isoolefin. The isoolefin may comprise isobutene, the multiolefin may comprise isoprene and the polymer may comprise butyl rubber. The zinc halide initiators used in the process of the present invention advantageously exhibit high solubility in the solvent and are low in cost. Further features of the invention and preferred embodiments thereof will now be more thoroughly described. Detailed Description The present invention relates to isoolefin homopolymers and co-polymers of isoolefins, multiolefins and optionally other co-polymerizable monomers. In a preferred embodiment, the co-polymer is a butyl rubber polymer. The terms "butyl polymer", "butyl rubber" and "butyl rubber polymer" are used interchangeably throughout this specification and are intended to mean a polymer prepared by reacting a major portion of an isoolefin monomer with a minor portion of a multiolefin monomer. The process is not limited to a specific isoolefin. However, isoolefins within the range of from 4 to 16 carbon atoms, in particular 4-8 carbon atoms, such as isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1- pentene and mixtures thereof are preferred. Most preferred is isobutene. When multiolefins are present in the reaction mixture, the process is not limited to a specific multiolefin. Every multiolefin copolymerizable with the isoolefins 3 known by the skilled in the art can be used. Multiolefins with in the range of from 4- 14 carbon atoms are preferred. A preferred C4 to Cu multiolefin comprises a C4 to Cio conjugated diolefin. Some specific non-limiting examples of suitable multiolefins include isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methly-1,5- hexadiene, 2,5-dimethly-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6- heptadiene, cyclopenta-diene, methylcyclopentadiene, cyclohexadiene, 1-vinylcyclohexadiene and mixtures thereof. Isoprene is particularly preferably used. The polymer may be derived from a mixture comprising only the isoolefin monomer. The polymer may also be derived from a mixture from about 70 to 99.5 parts by weight of the C4 to CQ isoolefin monomer and from about 30 to about 0.5 parts by weight of the C4 to Ci4 multiolefin monomer. More preferably, the polymer is derived from a mixture comprising from about 80 to about 99.5 parts by weight of the C4 to Ca isoolefin monomer and from about 20 to about 0.5 parts by weight of the C4 to Ci4 multiolefin monomer. A most preferred polymer according to the present invention is derived from a mixture comprising from about 97 to about 99.5 parts by weight of isobutylene and from about 3 to about 0.5 parts by weight of isoprene. Those of skill in the art will recognize that it is possible to include an optional third monomer to produce a butyl terpolymer. For example, it is possible to include a styrenic monomer in the monomer mixture, preferably in an amount up to about 15 percent by weight of the monomer mixture. The preferred styrenic monomer may be selected from the group comprising p-methylstyrene, styrene, amethylstyrene, p-chlorostyrene, p-methoxystyrene, cyclopentadiene, methylcyclopentadieneindene, indene derivatives and mixtures thereof. The most preferred styrenic monomer may be selected from the group comprising styrene, pmethylstyrene and mixtures thereof. Other suitable copolymerizable termonomers will be apparent to those of skill in the art. Suitable polymerization processes for producing isoolefin-containing polymers, particularly butyl rubber polymers, are known to persons skilled in the art and are further described in US 2,356,128. Generally, the processes involve providing the monomer mixture dissolved in a suitable solvent. The solvents are generally organic fluids. Organic fluids suitable for use in commercial butyl rubber polymerization include inert Ci to C4 halogenated hydrocarbons and mixtures thereof, Cs to Ca aliphatic hydrocarbons, Cs to Cs cyclic hydrocarbons, mixtures of one or more of the halogenated hydrocarbons and one or more of the aliphatic hydrocarbons, and mixtures of one or more of the halogenated hydrocarbons and one or more of the cyclic hydrocarbons. Examples of preferred inert organic fluids or solvents include pentane, hexane, heptane and mixtures thereof with one another or with halogenated hydrocarbons such as methyl chloride and/or dichloromethane . Most preferably the organic fluid is a halogenated hydrocarbon selected from the group consisting of methyl chloride, dichloromethane and mixtures thereof. A zinc based initiator according to the present invention comprises a divalent zinc halide Lewis acid that is preferably soluble in either neat IB or in mixtures of IB and a suitable organic solvent. Although zinc chloride (ZnCI2) is a simple zinc halide that would be suitable for use as an initiator, it is not soluble in either neat IB or IB/solvent mixtures. The preferred zinc halides therefore comprise soluble organic zinc halides, more preferably alkyl or aryl zinc halides, yet more preferably shortchain alkyl zinc halides. Since the zinc is divalent, there is only one alkyl or aryl group present in addition to the halide group. The zinc halide preferably does not comprise an alkoxide. The preferred halogen is chlorine, although bromine may also be used. Examples of preferred zinc halides include compounds of the formula: R-Zn-X (1) wherein, R is methyl, ethyl, propyl or butyl; and, X isCI, Br, or I. It might be advantageous to further add an activator or co-initiator to the monomer mixture. The invention is not limited to any special co-initiator/activator as long as the co-initiator compound does not adversely affect the polymerisation reaction. Preferred are activators of the general formula HX, RX, R3CX or RCOX with each R independently being a Ci to C5o hydrocarbon radical which may be linear, branched or cyclic and may contain one or more non-carbon atoms in the carbon-chain, such as methyl, ethyl, n-propyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, cumyl, 3-methylpentyl, 2,4,4-trimethylpentyl and 3,5,5- trimethylhexyl and each X being a halogen, preferably chlorine, bromine or iodine. Preferred co-initiators are Me3CCI, 'BuCI, cumyl chloride, TMP-2-chloride, MeCOCI, and Me3CBr. Most preferred are teuCI and cumyl chloride. The preferred ratio of zinc compound to co-initiator(s) is in the range of from 1:0.1 to 1:10 by mol, and the most preferred ratio is in the range of from 1:1 to Ethyl zinc chloride (EtZnCI) is a particularly preferred zinc-based initiator that exhibits good solubility in mixtures of IB with the halocarbon solvent dichloromethane (CH2CI2), but limited solubility in neat IB. EtZnCI is a Cl-bridged tetramer. The solid is soluble in organic solvents at room temperature. The system EtZnCI / Bu'CI shows good activity for IB polymerization and IB/IP copolymerizations. Because even in this system the in-situ generated ZnCI2 is insoluble in IB/CHzCfe mixtures at -78°C, the system shows best activities at temperatures > -35°C. However, the system EtZnCI / cumyl chloride has improved low temperature solubility and exhibits good polymerization activity at temperatures of -78°C down to -90 °C or lower. The monomers are therefore preferably polymerized at temperatures in the range of from -100°C to 40°C, more preferably in the range of from -90°C to 35°C, yet more preferably in the range of from -80°C to 35°C, even more preferably in the range of from -70°C to 35°C, still more preferably in the range of from -60°C to 35°C, yet even more preferably in the range of from -50°C to 35°C, yet still more preferably in the range of from -35°C to 20 35°C and at pressures in the range from 0.1 to 4 bar. The use of a continuous reactor as opposed to a batch reactor may have a positive effect on the process. Preferably, the process is conducted in at least one continues reactor having a volume of between 0.1 m3 and 100 m3, more preferable between 1 m3 and 10 m3. If polymerization is performed continuously, the process is preferably performed with at least the following feed streams: I) solvent/diluent (preferably dichloromethane) + isoolefin (preferably isobutene) + multiolefin (if present, preferably a diene, such as isoprene); and, II) zinc halide compound (preferably ethyl zinc chloride) The alkyl halide activator (if present) can be either pre-dissolved in the solvent or added to the solvent in conjunction with or following addition of the monomers. The alkyl halide activator is preferrably provided prior to addition of the zinc halide initiator. The zinc halide initiator system may be used to produce either IB homopolymers of co-polymers of IB and a diene monomer. When the diene monomer is isoprene, the co-polymer of IB and IP is butyl rubber. The IB homopolymer has a molecular weight (Mn) in the range of from 25,000 to 500,000 and the IB/IP co-polymer has a molecular weight in the range of from 15,000 to 500,000. Polymers comprising residual double bonds resulting from the inventive process may be the starting material for a halogenation process in order to produce halo-butyl polymers. Bromination or chlorination can be performed according to the procedures described in Rubber Technology, 3rd Ed., Edited by Maurice Morton, Kluwer Academic Publishers, pp. 297 - 300 and references cited within this reference. The copolymers presented in this invention are ideally suitable for the production of moldings of all kinds, in particular tire components and industrial rubber articles, such as bungs, damping elements, profiles, films, coatings. The polymers are used to this end in pure form or as a mixture with other rubbers, such as NR, BR, HNBR, NBR, SBR, EPDM or fluororubbers. The preparation of these compounds is known to those skilled in the art. In most cases carbon black is added as filler and a sulfur based curing system is used. Peroxide based curing systems may also be used, particularly when the polymer contains at least 4 mol% of repeating units derived from at least one multiolefin monomer. For compounding and vulcanization, reference is made to Encyclopedia of Polymer Science and Engineering, Vol. 4, S. 66 et seq. (Compounding) and Vol. 17, S. 666 et seq. (Vulcanization). The vulcanization of the compounds is usually effected at temperatures in the range of 100 to 200°C, preferred 130 to 180°C (optionally under pressure in the range of 10 to 200 bar). The following Examples are provided to illustrate the present invention. Examples Example 1: EtZnCI system for IB homopolvmerizations IB (9 ml) was condensed into a graduated vessel at -78 °C. Pre-chilled dichloromethane was injected to complete a 22 ml total reaction volume. A 'BuCI stock solution in dichloromethane (100 ^mol/ ml_ CH2CI2) was prepared at -78 °C. An aliquot with the appropriate amount of 'BuCI was added to the reactor, followed by the addition of solid EtZnCI. At this temperature the white solid did not change. However, when the mixture was allowed to warm to -35°C (checked with internal thermocouple) the solid dissolved completely. EtZnCI was used in an excess, and 'BuCI was used to control the polymerization rate as the limiting reagent. Reactions were quenched in methanol, dried at 60 °C until constant weight. Results are reported in Tables 1-4. The system was sealed and was warmed to the set temperature indicated in the tables. For reactions at 20°C the internal pressure has been calculated to be 2 bar. The solution became very cloudy after one minute (the time required for the mixture to reach the critical temperature of -35 °C where reaction starts). Cooling again to -78°C gave only traces of polymer (run 637). This shows that the zinc species involved in the polymerization are insoluble at -78 °C. However, if the system is sealed in order to avoid IB evaporation, very high conversions are reached at room temperature (run 639). Polymers thus prepared showed Mn values of 25 - 47 x 103. High concentrations of 'BuCI (Run 654-655) were used to give nearly quantitative conversions after a 30 minute reaction. A decrease of temperature increases the molecular weights of the polymers. A molecular weight of(Table Removed) Claims: 1) A process for the cationic polymerization of an isoolefin monomer using a zincbased initiator, the process comprising: a) providing a solution of the isoolefin monomer in a halocarbon solvent; b) adding a zinc-based initiator comprising an alkyl or aryl divalent zinc halide to the solution; and, c) reacting the solution containing the zinc-based initiator to form a polymer comprising the isoolefin. 2) The process according to claim 1, wherein the isoolefin is isobutene. 3) The process according to claim 1, wherein the halocarbon solvent is dichloromethane. 4) The process according to claim 1, wherein the ratio of isoolefin to halocarbon solvent is in the range of from 1:1 to 1:3 by volume. 5) The process according to claim 1, wherein the process further comprises adding an alkyl halide activator to the solution prior to addition of the zinc-based initiator. 6) The process according to claim 5, wherein the alkyl halide activator is tert-butyl chloride ('BuCI) or cumyl chloride. 7) The process according to claim 5, wherein the alkyl halide activator is present in a molar amount less than or equal to the molar amount of the zinc-based initiator. 8) The process according to claim 1, wherein the zinc-based initiator is added to the solution as a solid. 9) The process according to claim 1, wherein the zinc-based initiator is added at a temperature of from -90 °C to -35 °C. 10)The process according to claim 1, wherein the reaction is conducted at a temperature of from -90 °C to 35 °C. 11 )The process according to claim 1, wherein the polymer is an isoolefin homopolymer. 12)The process according to claim 1, wherein the solution further comprises a multiolefin monomer in an amount of from 1 to 15 mol % of total monomers in the solution. 13)The process according to claim 12, wherein the polymer is a co-polymer of the isoolefin and the multiolefin monomers. 14)The process according to claim 12, wherein the isoolefin monomer is isobutene, the multiolefin monomer is isoprene and the polymer is butyl rubber. 15)A polymer prepared by the process according to claim 1. 16)The polymer of claim 15, wherein the isoolefin is isobutene and wherein the polymer is a homopolymer of isobutene. 17)The polymer according to claim 16, wherein the polymer has a molecular weight (Mn) of from 25,000 to 500,000. 18)A polymer prepared by the process according to claim 12. 19)The polymer of claim 18, wherein the isoolefin monomer is isobutene, the multiolefin monomer is isoprene and the polymer is butyl rubber. 20)The polymer according to claim 19, wherein the polymer has a molecular weight |
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440-del-2007-Abstract-(19-10-2012).pdf
440-del-2007-Claims-(19-10-2012).pdf
440-del-2007-correspondence others-(09-05-2008).pdf
440-del-2007-Correspondence-Others-(19-10-2012).pdf
440-DEL-2007-Correspondence-Others.pdf
440-del-2007-description (complete).pdf
440-del-2007-form-18-(09-05-2008).pdf
440-del-2007-Form-3-(19-10-2012).pdf
440-del-2007-GPA-(19-10-2012).pdf
440-del-2007-Petition-137-(19-10-2012).pdf
Patent Number | 255506 | ||||||||||||
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Indian Patent Application Number | 440/DEL/2007 | ||||||||||||
PG Journal Number | 09/2013 | ||||||||||||
Publication Date | 01-Mar-2013 | ||||||||||||
Grant Date | 27-Feb-2013 | ||||||||||||
Date of Filing | 28-Feb-2007 | ||||||||||||
Name of Patentee | LANXESS INC. | ||||||||||||
Applicant Address | CITY OF SARNIA,IN THE PROVINCE OF ONTARIO,CANADA N7T 7M2 | ||||||||||||
Inventors:
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PCT International Classification Number | C08F210/00 | ||||||||||||
PCT International Application Number | N/A | ||||||||||||
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