Copolymer having low isoprenoid content

Patent metadata

Field	Value
Publication number	US-9850331-B2
Application number	US-201515307128-A
Country	US
Kind code	B2
Filing date	Apr 28, 2015
Priority date	Apr 30, 2014
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

A copolymer has low levels of isoprenoid (short chain branching) structures. A process for producing the copolymer having low isoprenoid content 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 may contain 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. Blends of saturated hydrofluorocarbons (e.g. 1,1,1,2-tetrafluoroethane) with an inert solvent (e.g. methyl chloride) may also be used as diluents.

First claim

The invention claimed is:

1. A copolymer of at least one isoolefin monomer and at least one multiolefin monomer and/or β-pinene monomer, the copolymer being produced by contacting the at least one isoolefin monomer with the at least one multiolefin and/or the β-pinene monomer in a diluent comprising 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) or mixtures thereof, and the copolymer having an isoprenoid content lower than an isoprenoid content of a comparable polymer 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 isoprenoid content is less than 15% based on total unsaturations in the copolymer.

3. The copolymer according to claim 1 , wherein the contacting is done 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.

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

5. The copolymer according to claim 1 , wherein the at least one isoolefin monomer comprises an isoolefin having from 4 to 16 carbon atoms or preferably 4 to 7 carbon atoms.

6. The copolymer 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.

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

8. 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-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.

9. The copolymer 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;
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;
the isoprenoid content is less than 6% based on total unsaturations in the copolymer;
the copolymer is produced by contacting the at least one isoolefin monomer with the at least one multiolefin and/or the β-pinene monomer in the presence of at least one Lewis acid and at least one initiator in the diluent at a temperature of less than or equal to −95° C., wherein:
the diluent comprises 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
the at least one Lewis acid is selected from a group consisting of ethyl aluminum dichloride (EADC), diethyl aluminum chloride (DEAC), titanium tetrachloride, stannous tetrachloride, boron trifluoride, boron trichloride, methylalumoxane, and mixtures thereof; and
the at least one initiator comprises a cationogen and/or a proton source selected from a group consisting of water, hydrochloric acid (HCl), alcohol, phenol, thiols, carboxylic acids and mixtures thereof.

10. The copolymer according to claim 1 , wherein the isoprenoid content is less than 12% based on total unsaturations in the copolymer.

11. The copolymer according to claim 1 , wherein the isoprenoid content is less than 11% based on total unsaturations in the copolymer.

12. The copolymer according to claim 1 , wherein the isoprenoid content is less than 6% based on total unsaturations in the copolymer.

Assignees

• Arlanxeo Singapore Pte Ltd
• Lanxess Inc

Inventors

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

Classifications

• C08F210/12 Primary

  with conjugated diolefins, e.g. butyl rubber · 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

• C08F2500/04

  Broad molecular weight distribution, i.e. Mw/Mn > 6 · CPC title

• C08F210/14

  Monomers containing five or more carbon atoms · CPC title

• C08F210/10

  Isobutene · CPC title