Process for production of high-isoprene butyl rubber

Abstract

The present invention relates to a continuous process for producing polymers at conversions ranging from 50% to 95% having a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt. % containing repeating units derived from at least one isoolefin monomer, more than 4.1 mol % of repeating units derived from at least one multiolefin monomer and optionally further copolymerizable monomers in the presence of AlCl 3 and a suitable proton source (e.g. water) or cationogen and at least one multiolefin cross-linking agent wherein the process is conducted in the absence of transition metal compounds and organic nitro compounds.

1 . A polymer having a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt. % comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol % of repeating units derived from at least one multiolefin monomer or beta-pinene and at least one further monomer copolymerizable with the isoolefin monomer or a diene, wherein the polymer only includes catalyst residues consisting of AIC/3 or IAIC/s derivable catalyst systems. 
     
     
         2 . The polymer according to  claim 1 , wherein the isoolefin monomer has 4 to 16 carbon atoms. 
     
     
         3 . The polymer according to  claim 2 , wherein the at least one isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2methyl-2-butene, 4-methyl-1-pentene or mixtures thereof. 
     
     
         4 . The polymer according to  claim 3 , wherein the isoolefin monomer is isobutylene. 
     
     
         5 . The polymer according to  claim 1 , wherein the at least one multiolefin monomer has 4 to 14 carbon atoms. 
     
     
         6 . The polymer according to  claim 5 , wherein the at least one multiolefin monomer is selected from the group consisting of 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-vinyl-cyclohexadiene or mixtures thereof. 
     
     
         7 . The polymer according to  claim 6 , wherein the at least one multiolefin monomer is isoprene. 
     
     
         8 . The polymer according to  claim 1 , wherein the at least one further copolymerizable monomer is a styrene or indene derivative. 
     
     
         9 . The polymer according to  claim 1 , wherein the at least one further copolymerizable monomer is selected from the group consisting of α-methyl styrene, p-methyl styrene, chlorostyrene, cyclopentadiene, methylcyclopentadiene or mixtures thereof. 
     
     
         10 . The polymer according to  claim 1 , which has been either partially or completely chlorinated. 
     
     
         11 . The polymer according to  claim 1 , which has been either partially or completely brominated. 
     
     
         12 . The polymer according to  claim 10 , which has been maleated. 
     
     
         13 . The polymer according to  claim 11 , which has been maleated. 
     
     
         14 . The polymer according to  claim 10 , which has been functionalized with nucleophilic species selected from the group consisting of NR 3 ,  — OR,  — SR, PR 3 ,  — OPR 3 ,  — OSiR 3 , —CR 3 , —O 2 CR where R=H, F, Cl, Br, I, C x H 2 CH 3  (x=0 to 20), phenyl (or any aromatic derivative), or cyclohexyl group. 
     
     
         15 . The polymer according to  claim 11 , which has been functionalized with nucleophilic species selected from the group consisting of NR 3 ,  — OR,  — SR, PR 3 ,  — OPR 3 ,  — OSiR 3 , —CR 3 , —O 2 CR where R=H, F, Cl, Br, I, C x H 2 CH 3  (x=0 to 20), phenyl (or any aromatic derivative), or cyclohexyl group. 
     
     
         16 . A process for the production of a polymer(s) having a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt. % comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol % of repeating units derived from at least one multiolefin monomer comprising mixing at least isoolefin monomers, at least one multiolefin monomer and optionally further copolymerizable monomers in the presence of AlCl 3  or anAlCl 3  derivable catalyst system and at least one proton source and/or cationogen capable of initiating the polymerization process and at least one multiolefin cross-linking agent. 
     
     
         17 . The process according to  claim 16 , wherein the process is conducted in the absence of transition metal catalysts and organic nitro compound catalysts. 
     
     
         18 . The process according to  claim 16 , wherein the process is continuous. 
     
     
         19 . The process according to  claim 16 , wherein the conversion level of the polymer is between 50 and 95%. 
     
     
         20 . The process according to  claim 16 , wherein the further copolymerizable monomer is present. 
     
     
         21 . The process according to  claim 20 , wherein the at least one further copolymerizable monomer is a styrene or indene derivative. 
     
     
         22 . The process according to  claim 20 , wherein the at least one further copolymerizable monomer is selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, chlorostyrene, cyclopentadiene, methylcyclopentadiene or mixtures thereof. 
     
     
         23 . The process according to  claim 16 , wherein the AlCl 3  derivable catalyst is selected from the group consisting of diethylaluminium chloride, ethylaluminium chloride, titanium tetrachloride, stannous tetrachloride, boron trifluoride, boron trichloride, or methylalumoxane. 
     
     
         24 . The process according to  claim 16 , wherein the multiolefin content is greater than 5.0 mol %. 
     
     
         25 . The process according to  claim 24 , wherein the multiolefin content is greater than 6.0 mol %. 
     
     
         26 . The process according to  claim 25 , wherein the multiolefin content is greater than 7.0 mol %. 
     
     
         27 . The polymer according to  claim 1 , wherein the multiolefin content is greater than 5.0 mol %. 
     
     
         28 . The process according to  claim 27 , wherein the multiolefin content is greater than 6.0 mol %. 
     
     
         29 . The process according to  claim 28 , wherein the multiolefin content is greater than 7.0 mol %. 
     
     
         30 . The process according to  claim 16 , wherein the proton source comprises water. 
     
     
         31 . The process according to  claim 16 , wherein the mixing of monomers is only in the presence of AlCl 3  or an AlCl 3  derivable catalyst system. 
     
     
         32 . The polymer according to  claim 1 , wherein the polymer does not contain my transition metal catalyst residues or organic nitro compound residues.