Process for producing chlorinated butyl rubber

Patent metadata

Field	Value
Publication number	US-11919977-B2
Application number	US-201917311297-A
Country	US
Kind code	B2
Filing date	Dec 12, 2019
Priority date	Dec 27, 2018
Publication date	Mar 5, 2024
Grant date	Mar 5, 2024

Abstract

The invention relates to an energy efficient, fast and environmentally favourable process for the preparation of chlorinated butyl rubbers, that uses hypochlorous acid (HOCl) and/or dichlorine monoxide (Cl 2 O) as halogenating agent. The process comprises reacting a copolymer with hypochlorous acid and/or dichlorine oxide. The copolymer comprises units derived from an isoolefin monomer and units derived from a multiolefin monomer. A preferred isoolefin is isobutene and a preferred multiolefin is isoprene.

First claim

What is claimed is:

1. A process for the preparation of a chlorinated copolymer comprising at least the steps of:
polymerizing a copolymer from a reaction medium comprising:
an aliphatic medium including at least 50 weight percent of one or more aliphatic hydrocarbons, and
a monomer mixture comprising at least one isoolefin monomer and at least one multiolefin monomer,
in the presence of an initiator to form a product comprising the copolymer, the aliphatic medium, and residual monomers of the monomer mixture;

removing the residual monomer to obtain an organic phase comprising the copolymer and the aliphatic medium;
contacting the organic phase with hypochloric acid, dichlorine oxide, or an aqueous phase containing hypochloric acid or dichlorine oxide; and
reacting the copolymer in the organic phase
with hypochloric acid and or dichlorine oxide.

2. The process according to claim 1 , wherein the isoolefin monomer is selected from those having from 4 to 16 carbon atoms.

3. The process according to claim 1 , wherein the isoolefin monomer is isobutene.

4. The process according to claim 1 , wherein the multiolefin 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, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene and 1-vinyl-cyclohexadiene.

5. The process according to claim 1 , wherein the multiolefin is isoprene.

6. The process according to claim 4 , wherein the copolymers further comprise further structural units derived from olefins selected from the group consisting of β-pinene, styrene, divinylbenzene, diisopropenylbenzene, and o-, m- and p-alkylstyrenes.

7. The process according to claim 1 , wherein the reacting includes a chlorination reaction and is carried out by contacting the aqueous phase with the organic.

8. The process according to claim 1 , wherein hypochloric acid and/or dichlorine oxide are prepared by reacting one or more hypochlorites with acidic compounds having a pKa of 0.00 to 7.60, as measured at standard conditions.

9. The process according claim 8 , wherein the acidic compounds are carboxylic acids.

10. The process according claim 8 , wherein the one or more hypochlorites is sodium hypochlorite.

11. The process according to claim 7 , wherein the aqueous phase comprising hypochloric acid and/or dichlorine oxide exhibits a pH value of from 2.0 to 7.4 under reaction conditions.

12. The process of claim 1 ,
wherein the reaction is carried out in the presence of an antioxidant.

13. The process of claim 1 , wherein the isoolefin monomer is selected from those having 4 to 7 carbon atoms.

14. The process of claim 1 , wherein the isoolefin monomer is selected from the group consisting of isobutene, 2-methyl-1-butene, 3-methyl-1-butene, and 2-methyl-2-butene.

15. A process for the preparation of a chlorinated copolymer comprising at least the step of reacting a copolymer comprising
i) structural units derived from at least one isoolefin monomer and
ii) structural units derived from at least one multiolefin monomer with hypochloric acid and or dichlorine oxide;
wherein the chlorinated copolymer has a chlorine content from 0.1 to 4 wt.-%,
wherein the structural units derived from isoprene are at least partially chlorinated to form exo-methylene and endo-Cl and cis-endo and trans-endo and microstructure units such that the microstructure Index X being the ratio of mol-% (exo-methylene+endo-Cl)/mol-% (cis-endo and trans-endo) as measured by 1H-NMR is from 1.50 to 3.30.

16. The process of claim 15 , wherein the chlorine content of the copolymer is from 1.1 to 2.2 wt.-%, and the microstructure Index X is from 2.20 to 2.80.

17. A process for the preparation of a chlorinated copolymer comprising at least the step of reacting a copolymer comprising
i) structural units derived from at least one isoolefin monomer and
ii) structural units derived from at least one multiolefin monomer
with hypochloric acid and or dichlorine oxide;
wherein the multi-olefin includes isoprene;
wherein the chlorinated copolymer comprises 1-(1-chloromethylethenyl)-2,2,4,4-tetramethylcyclohexane (C1-C13) and 1,1,5,5-tetramethyl-2-(1-chloromethylethenyl)-3-(2,2,4-trimethylpentyl)-cyclohexane (C1-C21) in a ratio (C1-C13)/(C1-C21) of 0.60 or more.

18. A process for the preparation of a chlorinated copolymer comprising at least the steps of:
polymerizing a copolymer from a reaction medium comprising:
an aliphatic medium including at least 50 weight percent of one or more aliphatic hydrocarbons, and
a monomer mixture comprising at least one isoolefin monomer and at least one multiolefin monomer,
in the presence of an initiator to form a product comprising the copolymer, the aliphatic medium, and residual monomers of the monomer mixture;

removing the residual monomer to obtain an organic phase;
contacting the organic phase with hypochloric acid, dichlorine oxide, or an aqueous phase containing hypochloric acid or dichlorine oxide; and
reacting the copolymer in the organic phase with hypochloric acid and or dichlorine oxide;
wherein the chlorinated copolymer comprises 1-(1-chloromethylethenyl)-2,2,4,4-tetramethylcyclohexane (C1-C13) and 1,1,5,5-tetramethyl-2-(1-chloromethylethenyl)-3-(2,2,4-trimethylpentyl)-cyclohexane (C1-C21) in a ratio (C1-C13)/(C1-C21) of 1.50 to 5.00.

19. A process for the preparation of a chlorinated copolymer comprising at least the step of reacting a copolymer comprising
i) structural units derived from at least one isoolefin monomer and
ii) structural units derived from at least one multiolefin monomer
with dichlorine oxide;
wherein the chlorinated copolymer comprises 1-(1-chloromethylethenyl)-2,2,4,4-tetramethylcyclohexane (C1-C13) and 1,1,5,5-tetramethyl-2-(1-chloromethylethenyl)-3-(2,2,4-trimethylpentyl)-cyclohexane (C1-C21) in a ratio (C1-C13)/(C1-C21) of 0.60 or more.

20. The process of claim 15 , wherein the reaction is carried out by contacting an aqueous phase comprising hypochloric acid and/or dichlorine oxide with an organic phase comprising the copolymer and an organic diluent wherein the organic diluent is hexane.

21. The process of claim 15 , wherein the isoolefin monomer is selected from those having from 4 to 16 carbon atoms, optionally wherein the isoolefin monomer is isobutene.

22. The process of claim 15 , wherein the 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, 4-butyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene and 1-vinyl-cyclohexadiene.

23. The process of claim 15 ,
wherein the method includes preparing the hypochloric acid and/or dichlorine oxide by reacting hypochlorites with acidic compounds having a pKa of 0.00 to 7.60 as measured at standard conditions;
optionally, wherein the acidic compounds are carboxylic acids;
optionally, wherein the hypochlorite is sodium

Assignees

• Arlanxeo Singapore Pte Ltd

Inventors

• Davidson Gregory J E
• Jayatissa Kuruppu

Classifications

• C08C19/12 Primary

  Incorporating halogen atoms into the molecule · CPC title

• C08F8/20 Primary

  Halogenation · CPC title

• C08F210/12

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

• C08F2800/10

  as molar percentages · CPC title

• C08F2810/50

  wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority · CPC title