Butyl rubber with new sequence distribution
View Patent ↗The invention relates to an efficient polymerization process and its use to produce novel copolymers with a specific microstructure. In particular, the invention relates to butyl rubbers with novel microstructure, preferably those obtainable by copolymerization of monomer mixtures comprising isobutylene and isoprene. In a further aspect the invention relates to halogenated copolymers obtainable from such novel copolymers by halogenation.
1. Copolymers of isobutylene and isoprene having a copolymer sequence distribution defined by equation (I)
F=mA /(1+ mA ) 2 (eq. I)
wherein
A is the molar ratio of isoprene to isobutylene in the copolymer as determined by 1 H NMR; and
F is the isobutylene-isoprene-isoprene triad fraction in the copolymer as determined by 13 C NMR; and
m is in the range of
[1.27−(0.025×MOC)]≥ m ≥[1.17−(0.025×MOC)]
whereby MOC is the content of isoprene in the copolymer in mol-% as determined by 1 H NMR, and m is 1.12 or less.
2. The copolymers according to claim 1 , wherein the isobutylene content is 85.0 to 99.5 mol.-% and the isoprene content is 0.5 to 15.0 mol.-%.
3. The copolymers according to claim 1 , wherein the isobutylene content is 96.2 to 99.5 mol.-% and the isoprene content is 0.5 to 3.8 mol.-%.
4. The copolymers according to claim 1 wherein the copolymers are halogenated copolymers.
5. The copolymers according to claim 4 , wherein the copolymers have an amount of halogen of 0.1 to 8.0 wt.-% by weight of the halogenated copolymer.
6. A process for the preparation of the copolymers according to claim 1 , the process comprising:
a) contacting a diluent and a monomer mixture comprising isobutylene and isoprene in a mass ratio of monomer mixture to diluent of 5:95 to 95:5 to form a reaction medium;
b) polymerizing the monomer mixture within the reaction medium in the presence of an initiator system to form a copolymer solution comprising the copolymer which is at least substantially dissolved in the reaction medium comprising the diluent and residual monomers of the monomer mixture; and
c) separating residual monomers of the monomer mixture and additionally diluent from the reaction medium to obtain the copolymer
whereby step b) is carried out
at a temperature of −95° C. to −60° C.,
and whereby the diluent
comprises at least 95.0 wt.-% of one or more aliphatic hydrocarbons having a boiling point of 5° C. to 95° C. at a pressure of 1013 hPa and
comprises at maximum 1.0 wt.-% of halogenated hydrocarbons or is free of such halogenated hydrocarbons.
7. The process according to claim 6 , wherein, for the diluent, the aliphatic hydrocarbons having a boiling point in the range of 5° C. to 95° C. at a pressure of 1013 hPa comprise linear (n-alkanes) and the content of the linear (n-alkanes) does not exceed 85 wt.-%.
8. The process according to claim 6 , wherein, for the diluent, the aliphatic hydrocarbons include cyclic hydrocarbons having a boiling point in the range of 5° C. to 95° C. at a pressure of 1013 hPa, and the content of cyclic hydrocarbons does not exceed 25 wt.-%.
9. Process according to claim 6 , wherein the initiator system comprises ethyl aluminum sesquichloride generated by mixing equimolar amounts of diethyl aluminum chloride and ethyl aluminum dichloride in a diluent.
10. The process according to claim 6 , wherein, for the initiator system, water and/or alcohols are used as a proton source.
11. A process for the preparation of the halogenated copolymers according to claim 4 , the process comprising:
a) contacting a diluent and a monomer mixture comprising isobutylene and isoprene in a mass ratio of monomer mixture to diluent of 5:95 to 95:5 to form a reaction medium;
(b) polymerizing the monomer mixture within the reaction medium in the presence of an initiator system to form a copolymer solution comprising the copolymer which is at least substantially dissolved in the reaction medium comprising the diluent and residual monomers of the monomer mixture;
c) separating residual monomers of the monomer mixture to separate copolymer from the monomers; and
d) halogenating the copolymer.
12. The process according to claim 11 , wherein the halogenation is carried out using elemental chlorine (Cl 2 ) or bromine (Br 2 ) as halogenation agent.
13. A polymer product comprising cured or uncured copolymers according to claim 1 .
14. The copolymers according to claim 1 , wherein the isobutylene content is 96.3 to 99.0 mol.-% and the isoprene content is 1.0 to 3.7 mol.-%.
15. The copolymers according to claim 1 , wherein the copolymers are halogenated copolymers and have an amount of halogen of 0.8 wt.-% to 3 wt.-% by weight of the halogenated copolymer.
16. The copolymers according to claim 1 , wherein the copolymers are halogenated copolymers and have an amount of halogen of 1.8 to 2.3 wt.-% by weight of the halogenated copolymer.
17. The copolymers according to claim 1 , wherein:
the copolymers are halogenated and have an amount of halogen of 0.1 to 8.0 wt.-% by weight of the halogenated copolymer; and
the isobutylene content is 85.0 to 99.5 mol.-% and the isoprene content is 0.5 to 15.0 mol.-%.
18. The copolymers according to claim 1 , wherein:
the copolymers are halogenated and have an amount of halogen of 1.8 to 2.3 wt.-% by weight of the halogenated copolymer; and
the isobutylene content is 96.3 to 99.0 mol.-% and the isoprene content is 1.0 to 3.7 mol.-%.
19. The copolymers according to claim 1 , wherein m is 0.95 to 1.12.