초록 ▼

A process for producing polymers having at least one high vinyl end segment is provided. The process comprises: (a) forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, (b) adding a R1R2R3aluminum or R1R2R3boron compound to nullify the

A process for producing polymers having at least one high vinyl end segment is provided. The process comprises: (a) forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, (b) adding a R1R2R3aluminum or R1R2R3boron compound to nullify the effect of the vinyl modifier, and (c) initiating polymerization of diene monomers using said living prepolymer high vinyl initiator so as to form a polymer product with at least one high vinyl end segment, where R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, and alkyl-substituted phenyl, and may all be identical or may all be separately selected but cannot be H. The polymers having at least one high vinyl end segment may be coupled to produce a polymer having a high vinyl end segment on all ends.

대표청구항 ▼

The invention claimed is: 1. A process comprising: a. forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, b. adding a R1R2R3aluminum or R1R2R3boron compound, and c. initiating polymerization of diene monomers using said living prepoly

The invention claimed is: 1. A process comprising: a. forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, b. adding a R1R2R3aluminum or R1R2R3boron compound, and c. initiating polymerization of diene monomers using said living prepolymer high vinyl initiator so as to form a polymer product with at least one high vinyl end segment, wherein said polymer product has an overall vinyl content of less than 35%, and where R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, alkyl-substituted phenyl and may all be identical or may all be separately selected but cannot be H. 2. A process as claimed in claim 1 wherein the R1R2R3 aluminum or R1R2R3boron compound are trialkyl compounds. 3. A process as claimed in claim 1 wherein the R1R2R3 aluminum compound is triethylaluminum. 4. A process as claimed in claim 1 wherein step (a) comprises combining an anionic initiator, monomer and a vinyl modifier, wherein said monomer comprises at least one conjugated diene monomer. 5. A process as claimed in claim 4 wherein said anionic initiator is an organolithium compound. 6. A process as claimed in claim 4 wherein said monomer comprises 1,3-butadiene. 7. A process as claimed in claim 1 wherein the vinyl modifier comprises at least one of hexamethylphosphoric acid triamide, N,N,N',N'-tetramethylethylene diamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-diazabicyclo [2.2.2] octane, diethyl ether, triethylamine, tri-n-butylamine, tri-n-butylphosphine, p-dioxane, 1,2-dimethoxy ethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bis-oxalanyl propane, tri-n-propyl amine, trimethyl amine, triethyl amine, N,N-dimethyl aniline, N-ethylpiperidine, N-methyl-N-ethyl aniline, and N-methylmorpholine. 8. A process as claimed in claim 4 wherein said monomer further comprises at least one vinyl monomer. 9. A process as claimed in claim 1 wherein said polymerization in step (c) further comprises the use of at least one vinyl monomer. 10. A process comprising: a. forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, b. adding a R1R2R3aluminum or R1R2R3boron compound, and c. initiating polymerization of diene monomers using said living prepolymer high vinyl initiator so as to form a polymer product with a high vinyl end segment, wherein said polymer product has an overall vinyl content of less than 35%, and where R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, alkyl-substituted phenyl, and mixtures thereof and may all be identical or may all be separately selected but cannot be H where step (c) is conducted at a maximum temperature that is no more than 20�� C. higher than the maximum temperature at which steps (a) and (b) are conducted. 11. A process as claimed in claim 10 wherein the R1R2R3 aluminum or R1R2R3boron compound are trialkyl compounds. 12. A process as claimed in claim 10 wherein the R1R2R3 aluminum compound is triethylaluminum. 13. A process as claimed in claim 10 wherein step (a) comprises combining an anionic initiator, monomer and a vinyl modifier, wherein said monomer includes one or more conjugated diene monomers. 14. A process as claimed in claim 13 wherein said initiator is an organolithium compound. 15. A process as claimed in claim 13 wherein said monomer comprises 1,3-butadiene. 16. A process as claimed in claim 10 wherein the vinyl modifier comprises at least one of hexamethylphosphoric acid triamide, N,N,N',N'-tetramethylethylene diamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-diazabicyclo [2.2.2] octane, diethyl ether, triethylamine, tri-n-butylamine, tri-n-butylphosphine, p-dioxane, 1,2-dimethoxy ethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bis-oxalanyl propane, tri-n-propyl amine, trimethyl amine, triethyl amine, N,N-dimethyl aniline, N-ethylpiperidine, N-methyl-N-ethyl aniline, and N-methylmorpholine. 17. A process as claimed in claim 13 wherein said monomer further comprises at least one of vinyl monomer. 18. A process as claimed in claim 10 wherein said polymerization in step (c) further comprises the use of at least one vinyl monomer. 19. A process comprising: a. forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, b. adding a R1R2R3aluminum or R1R2R3boron compound, and c. initiating polymerization of diene monomers using said living prepolymer high vinyl initiator so as to form a polymer product with at least one high vinyl end segment, wherein said polymer product has an overall vinyl content of less than 35%, and said polymer product with a high vinyl end segment from step (c) is coupled to produce a further product with at least two high vinyl end segments, and R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, alkyl-substituted phenyl and may all be identical or may all be separately selected but cannot be H. 20. A process as claimed in claim 19, wherein a di-coupling, tri-coupling, tetra-coupling, quatra-coupling, penta-coupling or hexa-coupling agent is used for the coupling. 21. A process as claimed in claim 19 wherein said polymerization in step (c) further comprises the use of at least one vinyl monomer. 22. A method comprising the steps of: (a) adding the polymer produced in any of claims 1-8, 9, or 19-21 to a solvent comprising at least one vinyl monomer; (b) optionally adding at least one additional inert solvent; (c) optionally adding additives selected from the group consisting of extender oils, modifiers, and antioxidants, (d) initiating polymerization of the vinyl monomer by the use of an initiator and/or heat, wherein steps a, b and c can be performed in any order; whereby the result of steps (a)-(d) is production of an engineered plastic; and wherein the engineered plastic is selected from the group consisting of high impact polystyrene, styrene-maleic anhydride copolymer, methylmethacrylate-butadiene-styrene copolymer, transparent impact polystyrene, and acrylonitrile butadiene styrene copolymer. 23. A process comprising: a. forming a living prepolymer high vinyl initiator with a vinyl content greater than about 45% using a vinyl modifier, b. adding a R1R2R3aluminum or R1R2R3boron compound, and c. initiating polymerization of diene monomers using said living prepolymer high vinyl initiator so as to form a polymer product with a high vinyl end segment wherein said polymer product has an overall vinyl content of less than 35%, and said polymer product with a high vinyl end segment from step (c) is coupled to produce a further product with at least two high vinyl end segments, and R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, alkyl-substituted phenyl, and mixtures thereof and may all be identical or may all be separately selected but cannot be H where step (c) is conducted at a maximum temperature that is no more than 20�� C. higher than the maximum temperature at which steps (a) and (b) are conducted. 24. A process as claimed in claim 23, wherein a di-coupling, tri-coupling, tetra-coupling, quatra-coupling, penta-coupling or hexa-coupling agent is used for the coupling. 25. A process as claimed in claim 23 wherein said polymerization in step (c) further comprises the use of at least one vinyl monomer. 26. A process comprising: a. adding an anionic initiator to a mixture of monomers in the presence of a vinyl modifier to form a living polymer with a vinyl content greater than about 45%; b. adding a R1R2R3aluminum or R1R2R3boron compound to the mixture in step (a) when said living polymer has a number average molecular weight in the range of about 100 to about 20,000; c. allowing said living polymer to obtain a number average molecular weight in the range of about 20,000 to about 500,000; and d. optionally, coupling said living polymer; wherein said living polymer produced in step (c) has an overall vinyl content of less than 35%, and where R1, R2, and R3 are selected from the group consisting of C1-C12 alkyl, C2-C12 alkene, C2-C12 alkyne, phenyl, alkyl-substituted phenyl and may all be identical or may all be separately selected but cannot be H.