Process for producing brominated butyl rubber

Patent metadata

Field	Value
Publication number	US-9657158-B2
Application number	US-201514810703-A
Country	US
Kind code	B2
Filing date	Jul 28, 2015
Priority date	Jul 20, 2011
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

The invention relates to an energy efficient, environmentally favorable process for the preparation of brominated butyl rubbers, that uses a bromination agent and a oxidizing agent in order to enhance the utilization of bromine contained in the bromination agent. In a preferred embodiment a common medium for both solution polymerization and subsequent bromination of the rubber is employed.

First claim

What is claimed is:

1. A process for the preparation of cements comprising aliphatic medium and at least one brominated butyl rubber, the process comprising:
a) contacting butyl rubber cement comprising aliphatic medium with elemental bromine in the presence of hydrogen peroxide in a continuous process to brominate butyl rubber contained in the butyl rubber cement and produce a heterophasic mixture comprising:
a cement comprising aliphatic medium and brominated butyl rubber, and
an aqueous phase; and

b) separating the cement comprising aliphatic medium and brominated butyl rubber from the aqueous phase.

2. The process according to claim 1 , wherein separating the cement from the aqueous phase comprises at least one of:
b1) adjusting the pH-valve of the heterophasic mixture to 6 to 13, and separating the cement comprising aliphatic medium and brominated butyl rubber from the aqueous phase; or
b2) separating the cement comprising aliphatic medium and brominated butyl rubber from the aqueous phase, and washing the cement comprising aliphatic medium and brominated butyl rubber with an aqueous mixture.

3. The process according to claim 1 , wherein the butyl rubber cement comprising aliphatic medium comprises:
A) 5 to 30 wt-% of at least one butyl rubber,
B) 0 to 6 wt-% of water,
C) and an amount of an aliphatic medium comprising at least 50 wt-% of one or more aliphatic hydrocarbons having a boiling point of 45.0° C. to 80° C. at a pressure of 1013 hPa,
wherein the sum of A), B) and C) adds up to 96 to 100 wt-% of the total content of the butyl rubber cement.

4. The process according to claim 1 , wherein the butyl rubber cement is prepared in a process comprising:
mixing an aliphatic medium comprising at least 50 wt-% of one or more aliphatic hydrocarbons having a boiling point in the range of 45° C. to 80° C. at a pressure of 1013 hPa, and a monomer mixture comprising at least one C 4 to C 7 isoolefin, at least one C 4 to C 14 conjugated diene, and either no, one, or more than one further co-polymerizable monomers, in a mass ratio of monomer mixture to aliphatic medium of 35:65 to 99:1 to form a reaction mixture;
polymerizing the monomer mixture within the reaction medium to form a butyl rubber solution comprising a butyl rubber which is at least substantially dissolved in the medium comprising the aliphatic medium and residual monomers of the monomer mixture; and
separating residual monomers of the monomer mixture from the butyl rubber solution to form the butyl rubber cement.

5. The process according to claim 3 , wherein the butyl rubber comprises;
repeating units derived from 92.0 to 9.5 mol-% of at least one C 4 to C 7 isoolefin and 0.5 to 8.0 mol-% of at least one C 4 to C 14 conjugated diene, or repeating units derived from
i) at least one, C 4 to C 7 isoolefin,
ii) 0.5 to 8.0 mol-% of at least one C 4 to C 14 conjugated diene, and
iii) 0.1 to 20 wt-% of further co-polymerizable monomers,

whereby the repeating units derived from i), ii) and iii) add up to 100 mol-% of the repeating units contained in the butyl rubber.

6. The process according to claim 5 , wherein;
the butyl rubber is a copolymer of isobutene and isoprene comprising 1.5 to 2.5 mol-% repeating units derived from isoprene;
the aliphatic medium has a content of cyclic aliphatic hydrocarbons of less than 25 wt-%; and
the hydrogen peroxide used is 25 to 60 wt-% aqueous solution.

7. The process according to claim 6 , wherein the aliphatic medium has a content of cyclohexane of less than 5 wt-%.

8. The process according to claim 6 , wherein the weight ratio of hydrogen peroxide to water within the reaction mixture formed by adding the hydrogen peroxide to the butyl rubber cement is initially greater than 0.05.

9. The process according to claim 1 , wherein no surfactants are added.

10. The process according to claim 3 , wherein:
the elemental bromine is either added to the butyl rubber cement either in substance or as solution of elemental bromine in the aliphatic medium, or the elemental bromine is additionally or alternatively formed by reaction of hydrogen bromide or metal bromides or mixtures of hydrogen bromide or metal bromides as bromine precursors with the hydrogen peroxide in situ; and
the hydrogen peroxide is added to the butyl rubber cement prior to, concurrently with, or subsequent to the addition of elemental bromine.

11. The process according to claim 9 , wherein a quantity of bromine atoms as elemental bromine or bromine precursor or bromine and bromine precursor is 0.2 to 1.2 times the molar quantity of double bonds contained in the butyl rubber.

12. The process according to claim 9 , wherein 0.6 to 5 mol of hydrogen peroxide per mol of elemental bromine is used, or if hydrogen bromide or metal bromides as bromine precursors are used, 1 to 5 mol of hydrogen peroxide per mol of bromide contained in the bromine precursors is used.

13. The process according to claim 1 , wherein contacting the butyl rubber with bromine is done at a temperature of 0° C. to 90° C. for 1 minute to 1 hour.

14. The process according to claim 1 , wherein during contacting of the butyl rubber cement with the bromine, the butyl rubber cement, the added hydrogen peroxide, and the bromine are agitated with a mechanical power input of 0.5 W/l or more.

15. The process according to claim 2 , wherein the pH value is adjusted with a base that is an aqueous solution or slurry of alkaline or earth alkaline metal hydroxides or carbonates.

16. The process according to claim 2 , wherein separating the cement comprising aliphatic medium and brominated butyl rubber from the aqueous phase is effected continuously in a separating apparatus comprising a settling section whereby the separation is supported by means of a coalesces.

17. The process according to claim 1 , further comprising removing volatile components having a boiling point below 250° C. at 1013 hPa from the brominated butyl rubber to obtain the brominated butyl rubber in solid form.

18. The process according to claim 17 , wherein removing volatile components is effected by a process using an extruder.

19. The process according to claim 1 , further comprising curing the brominated butyl rubber.

20. The process according to claim 1 wherein in the brominated butyl rubber greater than 40% of the bromine atoms are in allylic position to exo-double bonds as measured by 1H-NMR with respect to the total bromine content of the brominated butyl rubber as measured by XRF.

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Leiberich Ricarda
• Ritter Joachim
• Paul Hanns-Ingolf
• Wiesner Udo
• Luesgen Holger

Classifications

• C08F8/22 Primary

  by reaction with free halogens · CPC title

• C08C19/14

  by reaction with halogens · CPC title

• C09J115/02

  Rubber derivatives containing halogen · CPC title

• C09D115/02

  Rubber derivatives containing halogen · CPC title

• C08K5/01 Primary

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title