Hydrofluorinated olefins (HFO's) as diluents for butyl rubber production

Patent metadata

Field	Value
Publication number	US-9714304-B2
Application number	US-201515307114-A
Country	US
Kind code	B2
Filing date	Apr 28, 2015
Priority date	Apr 30, 2014
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

A process for producing a copolymer 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 a tetrafluorinated propene. Copolymers produced by a process of the present invention have a cyclic oligomer content lower than comparable polymers produced in a butyl rubber slurry process using 1,1,1,2-tetrafluoroethane and/or methyl chloride as a diluent as well as a more favorable ratio of C21/C13. 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 process for producing a copolymer, the process comprising 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, and in a diluent comprising a tetrafluorinated propene.

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

3. The process according to claim 1 , 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.

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

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

6. The process according to claim 1 , wherein the at least one isoolefin monomer comprises an isoolefin having from 4 to 7 carbon atoms.

7. The process according to claim 1 , wherein the at least one isoolefin monomer comprises isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, or mixtures thereof.

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

9. The process 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-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 or mixtures thereof.

10. The process according to claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises indene, α-Methyl styrene, p-methyl styrene, chlorostyrene or mixtures thereof.

11. The process according to claim 1 , wherein the at least one multiolefin and/or β-pinene monomer comprises p-methyl styrene.

12. The process according to claim 1 , further comprising contacting at least one additional monomer with the at least one isoolefin monomer and the at least one multiolefin and/or β-pinene monomer.

13. The process according to claim 12 , wherein the at least one additional monomer comprises indene, α-Methyl styrene, p-methyl styrene, chlorostyrene or mixtures thereof.

14. The process according to claim 1 , wherein the Lewis acid comprises ethyl aluminum dichloride (EADC), diethyl aluminum chloride (DEAC) and/or mixtures thereof.

15. The process according to claim 1 , wherein the initiator comprises a proton source and/or cationogen.

16. The process according to claim 1 , wherein the monomers are polymerized at a temperature in a range of about −120° C. to about −50° C., preferably, in a range of about −100° C. to about −75° C., preferably in a range of about −98° C. to about −90° C. or preferably about −95° C. or about −75° C.

17. The process according to claim 1 , wherein the diluent further comprises methyl chloride.

18. The process according to claim 17 , wherein a ratio of methyl chloride to tetrafluorinated propene in the diluent is about 50:50.

19. The process according to claim 1 , wherein:
the tetrafluorinated propene comprises 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
the at least one isoolefin monomer comprises isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-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-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, indene, α-Methyl styrene, p-methyl styrene, chlorostyrene, or mixtures thereof;
the Lewis acid comprises ethyl aluminum dichloride (EADC), diethyl aluminum chloride (DEAC) and/or mixtures thereof;
the initiator comprises a proton source and/or a cationogen;
the monomers are polymerized at a temperature of about −98° C. to about −75° C.; and
the diluent further comprises methyl chloride, wherein a ratio of methyl chloride to 2,3,3,3-tetrafluoro-1-propene in the diluent is about 50.50.

20. A copolymer produced by the process as defined in claim 1 .

Assignees

• Arlanxeo Singapore Pte Ltd
• Lanxess Inc

Inventors

• Nguyen Paul
• Watson Jessica
• Arsenault Gilles

Classifications

• C08F210/12 Primary

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

• C08F236/08

  Isoprene · CPC title

• C08F212/08

  Styrene · CPC title

• C08F212/12

  Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical · CPC title

• C08F236/04

  conjugated · CPC title