Copolymer having high multiolefin content

Patent metadata

Field	Value
Publication number	US-10077326-B2
Application number	US-201515307096-A
Country	US
Kind code	B2
Filing date	Apr 28, 2015
Priority date	Apr 30, 2014
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

A copolymer has high levels of multolefin incorporation. A process for producing the copolymer having high levels of multiolefin incorporation 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 hydrofluor-Mated 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 hydro-fluorocarbons.

First claim

The invention claimed is:

1. A copolymer comprising least one isoolefin monomer and at least one multiolefin monomer and/or β-pinene monomer, wherein the copolymer is produced by contacting at least one isoolefin monomer with at least one multiolefin monomer and/or β-pinene monomer in a diluent comprising a tetrafluorinated propane, and wherein the copolymer has a greater multiolefin monomer and/or β-pinene monomer content, and one or more of: higher molecular weight polymer chains, narrower molecular weight distribution, lower cyclic oligomer by-products, higher ratio of C21 to C13 cyclic oligomers, and lower isoprenold structure content than a polymer having the same isoolefin monomer and multiolefin monomer and/or β-pinene monomer, but produced in a butyl rubber slurry process using 1,1,1,2-tetrafluoroethane as a diluent.

2. The copolymer according to claim 1 , wherein the multiolefin and/or β-pinene monomer content is 0.5 to 15 mol % based on the weight of the copolymer.

3. The copolymer according to claim 1 , wherein the multiolefin and/or β-pinene monomer is incorporated into the copolymer in a ratio of feed monomer composition to copolymer composition (f/F) greater than 0.8.

4. The copolymer according to claim 1 , wherein the copolymer is produced in the presence of at least one Lewis acid and at least one initiator at a temperature of less than or equal to −75° C .

5. The copolymer according to claim 1 , wherein the copolymer is produced in the presence of at least one Lewis acid and at least one initiator at a temperature of less than or equal to −95° C.

6. The copolymer according to claim 4 , wherein the tetrafluorinated propene comprises 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) or mixtures thereof.

7. The copolymer according to claim 1 , wherein the tetrafluorinated propene comprises 2,3,3,3-tetrafluoro-1-propene (HFO 1234yf).

8. The copolymer according to claim 1 , wherein the at least one isoolefin monomer comprises an isoolefin having from 4 to 16 carbon atoms.

9. The copolymer according to claim 1 , wherein the at least one isoolefin monomer comprises isobutane, 2-methylol -butane, 3-methyl-1-butene, 2-methyl- -butene, 4-methyl-1-pentene or mixtures thereof.

10. The copolymer according claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises a multiolefin having from 4-14 carbon atoms.

11. The copolymer according to claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises 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, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene or mixtures thereof.

12. The copolymer according to claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene or mixtures thereof.

13. The copolymer according to claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises isoprene.

14. The copolymer according to claim 4 , further comprising contacting at least one additional monomer with the at least one isoolefin monomer and at least one multiolefin and/or β-pinene monomer.

15. The copolymer according to claim 14 , wherein the at least one additional monomer comprises indene, α-methyl styrene, p-methyl styrene, chlorostyrene or mixtures thereof.

16. The copolymer according to claim 4 , wherein:
the at least one isoolefin monomer comprises an isoolefin having from 4 to 7 carbon atoms;
the at least one multiolefin and/or β-pinene monomer comprises a multiolefin having from 4-14 carbon atoms; and
the tetrafluorinated propene comprises 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), or mixtures thereof.

17. The copolymer according to claim 4 , wherein:
the at least one isoolefin monomer comprises isobutene. 2-methyl-l-butene, 3-methyl-1-butene, 2methyl-2-butene, 4-methyl-1-pentene or mixtures thereof;
the at least one multiolefin and/or β-pinene monomer comprises 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, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, or mixtures thereof; and
the at least one Lewis acid is selected from the group consisting of ethyl aluminum dichloride (EADC), diethyl aluminum chloride (DEAC), titanium tetrachloride, stannous tetrachloride, boron trifluoride, boron trichloride, methylalumoxane, AlCl 3 , or mixtures thereof.

18. The copolymer according to claim 17 , wherein:
the Lewis acid is a mixture of EADC and DEAC;
the initiator comprises HCl as a proton source;
the contacting further comprises contacting at least one additional monomer selected from indene, α-methyl styrene, p-methyl styrene, chlorostyrene or mixtures thereof with the at least one isoolefin monomer and the at least one multiolefin and/or β-pinene monomer.

19. The copolymer according to claim 1 , wherein the multoliefin and/or β-pinene monomer is incorporated into the copolymer in a ratio of feed monomer composition to copolymer composition (f/F) 0.85 or greater.

20. The copolymer according to claim 1 , wherein the multiolefin and/or β-pinene monomer is incorporated into the copolymer in a ration of feed monomer composition to copolymer composition (f/F) 0.9 or greater.

Assignees

• Arlanxeo Singapore Pte Ltd
• Arlanxeo Canada Inc

Inventors

• Teertstra Steven John
• Nguyen Paul
• Watson Jessica
• Arsenault Gilles

Classifications

• C08F210/12 Primary

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

• C08F2/14

  Organic medium · CPC title

• C08F2500/25

  Cycloolefine · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F236/10

  with vinyl-aromatic monomers · CPC title