Process for production of halobutyl ionomers
View Patent ↗The invention relates to an energy efficient, environmentally favorable process for the preparation of butyl ionomers that uses a common medium for both solution polymerization and subsequent bromination of butyl rubber. More particularly, the invention relates to a process that employs a common aliphatic medium for both solution polymerization and bromination of butyl rubber in the presence of a brominating agent and optionally for subsequent reaction with at least one nitrogen and/or phosphorus based nucleophile.
1. A process for the preparation of ionomers comprising at least the steps of:
a) providing a reaction medium comprising
a common aliphatic medium comprising at least 50 wt-% of one or more aliphatic hydrocarbons having a boiling point of 45° C. to 80° C. at a pressure of 1013 hPa, and
a monomer mixture comprising at least one monoolefin monomer, at least one multiolefin monomer and either no or at least one other co-polymerizable monomer in a mass ratio of monomer mixture to common aliphatic medium of 40:60 to 99:1;
b) polymerizing the monomer mixture within the reaction medium to form a rubber solution comprising a rubber polymer which is at least substantially dissolved in the medium comprising the common aliphatic medium and residual monomers of the monomer mixture;
c) separating residual monomers of the monomer mixture from the rubber solution to form a separated rubber solution comprising the rubber polymer and the common aliphatic medium,
d) brominating the rubber polymer in the separated rubber solution to obtain a solution comprising the brominated rubber polymer and the common aliphatic medium,
e) reacting the brominated rubber polymer obtained in step d) with at least one nitrogen and/or phosphorous containing nucleophile.
2. The process according to claim 1 , wherein the rubber is a butyl rubber.
3. The process according to claim 2 , wherein the weight average molecular weight of butyl rubber as measured prior to bromination is 200 to 1000 kg/mol.
4. The process according to claim 1 , wherein the monomer mixture comprises 80.0% to 99.9% by weight of the at least one monoolefin monomer and 0.1% to 20.0% by weight of the at least one multiolefin monomer.
5. The process according to claim 1 , wherein the monoolefin monomer is isobutene and the multiolefin monomer is isoprene.
6. The process according to claim 1 , wherein the common aliphatic medium comprises at least 80 wt.-% of one or more aliphatic hydrocarbons having a boiling point of 45° C. to 80° C. at a pressure of 1013 hPa.
7. The process according to claim 1 , wherein the process temperature of step b) is −100° C. to −40° C.
8. The process according to claim 1 , wherein the reaction is performed in a polymerization reactor, and wherein the viscosity of the solution at the discharge of the polymerization reactor is less than 2000 cP.
9. The process according to claim 1 , wherein the solids content of the rubber solution obtained following in step b) is 3 to 25%.
10. The process according to claim 1 , wherein molecular bromine is used as brominating agent.
11. The process according to claim 1 , wherein the amount of brominating agent used is 0.1 to 20% by weight of the rubber.
12. The process according to claim 1 , wherein the brominating agent is used in combination with an oxidizing agent.
13. The process according to claim 1 , wherein the nitrogen and/or phosphorous containing nucleophiles are those of formula I
AR 1 R 2 R 3 (I),
wherein:
A denotes nitrogen or phosphorus, and
R 1 , R 2 and R 3 are independently of each other selected from the group consisting of C 1 -C 18 -alkyl, C 6 -C 15 -arylalkyl, and C 5 -C 14 -aryl.
14. The process according to claim 1 , wherein step a) is accomplished by reactive kneading or carried out in solution.
15. The process according to claim 1 , wherein in a further step f) the ionomer is cured.