Copolymer having low cyclic oligomer content

Patent metadata

Field	Value
Publication number	US-11066498-B2
Application number	US-201515307111-A
Country	US
Kind code	B2
Filing date	Apr 28, 2015
Priority date	Apr 30, 2014
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

A copolymer has low levels of cyclic oligomeric compounds, which are undesirable impurities in certain applications. The cyclic oligomeric compounds are provided in an advantageously low ratio of C21/C13 oligomers. The C13 oligomers are extractable using steam to further reduce the total amount of cyclic oligomers. A process for producing the copolymer having low levels of cyclic oligomers involves contacting at least one isoolefin monomer with at least one multiolefin and/or β-pinene monomer in the presence of at least one Lewis acid and at least one initiator in a diluent. The diluent contains a hydrofluorinated olefin (HFO) comprising at least three carbon atoms and at least three fluorine atoms. Hydrofluorinated olefins used in the present invention are better diluents for butyl slurry cationic polymerization than saturated hydrofluorocarbons.

First claim

What is claimed is:

1. A copolymer composition comprising a copolymer of at least one isoolefin monomer and at least one multiolefin monomer in mixture with at least one cyclic oligomer, wherein the copolymer composition is in a slurry,
the copolymer composition produced by polymerizing the at least one isoolefin monomer with the at least one multiolefin in a slurry process at a temperature of less than or equal to −95° C. in a diluent comprising 2,3,3,3-tetrafluoro-l-propene (HFO-1234yf),
the copolymer composition has a cyclic oligomer content of less than or equal to 2000 ppm and at least 10% lower than a cyclic oligomer content of a polymer composition produced from the same isoolefin monomer and the same multiolefin monomer, made with the same amounts and molar ratios of isoolefin and multiolefin monomers, in the same slurry process except using 1,1,1,2-tetrafluoroethane as a diluent,
wherein the at least one cyclic oligomer has a C 13 cyclic oligomer content and a C 21 cyclic oligomer content, and a ratio of the C 21 cyclic oligomer content to the C 13 cyclic oligomer content is less than or equal to 1.5.

2. A copolymer composition comprising a copolymer of at least one isoolefin monomer and at least one multiolefin monomer in mixture with at least one cyclic oligomer, wherein the copolymer composition is in a slurry,
the copolymer composition produced by polymerizing the at least one isoolefin monomer with the at least one multiolefin in a slurry process at a temperature of less than or equal to −95° C. in a diluent comprising 2,3,3,3-tetrafluoro-l-propene (HFO-1234yf),
the copolymer composition has a total cyclic oligomer content of less than 1000 ppm, wherein the cyclic oligomers include C 13 cyclic oligomers and C 21 cyclic oligomers, wherein a ratio of the C 21 cyclic oligomers to the C 13 cyclic oligomers is less than 1.5.

3. A purified copolymer composition prepared by stripping the copolymer composition according to claim 2 ,
wherein the purified copolymer composition has a total cyclic oligomer content of less than or equal to 600 ppm following the stripping.

4. The copolymer composition according to claim 2 , wherein the at least one isoolefin monomer comprises an isoolefin having from 4 to 16 carbon atoms and the at least one multiolefin comprises a conjugated diene having from 4-14 carbon atoms.

5. The copolymer composition according to claim 4 , wherein:
the at least one isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof, and
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-methyl-1,5-hexadiene, 2,5-dimethyl- 2 , 4 -hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof.

6. The copolymer composition according to claim 5 , wherein:
the at least one isoolefin monomer comprises isobutene; and
the at least one multiolefin monomer comprises isoprene.

7. The copolymer composition according to claim 6 , wherein the process further comprises contacting at least one additional monomer with the at least one isoolefin monomer and the at least one multiolefin.

8. The copolymer composition according to claim 1 , wherein:
the copolymer composition has a cyclic oligomer content at least 75% lower than a cyclic oligomer content of a polymer composition produced from the same isoolefin monomer and the same multiolefin monomer in the same slurry process except using 1,1,1,2-tetrafluoroethane as a diluent;
the at least one isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof; and
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-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, and mixtures thereof.

9. The copolymer composition according to claim 2 , wherein:
the total cyclic oligomer content is less than or equal to 650 ppm;
the at least one isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof; and
the at least one multiolefin monomer comprises one or more compounds selected form the group consisting of isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, and mixtures thereof.

Assignees

• Arlanxeo Singapore Pte Ltd

Inventors

• Nguyen Paul
• Watson Jessica
• Arsenault Gilles

Classifications

• C08F236/04

  conjugated · CPC title

• C08F236/08

  Isoprene · CPC title

• C08F210/12 Primary

  with conjugated diolefins, e.g. butyl rubber · CPC title

• C08F2/14

  Organic medium · CPC title

• C08F6/10

  Removal of volatile materials, e.g. solvents {(C08F6/001, C08F6/003, C08F6/005, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)} · CPC title