Butyl rubber ionomer-thermoplastic graft copolymers and methods for production thereof
View Patent ↗The present invention is directed to the functionalization of butyl rubber ionomer and optionally the grafting of polyamide to halobutyl rubber ionomers. Specifically, disclosed are methods and products resulting therefrom for creating functionalized ionomers and grafting polyamide to halobutyl ionomers via reactive extrusion. The process comprises reacting a halobutyl polymer with at least one nitrogen and/or phosphorous based nucleophile to provide a halobutyl ionomer comprising conjugated diene units; grafting of an amine-reactive dienophile to said ionomer to form a functionalized ionomer; and optionally blending the resulting functionalized ionomer with polyamide.
1. A method for preparing a butyl graft copolymer, the method comprising:
reacting a halobutyl polymer with at least one of a nitrogen based nucleophile and a phosphorous based nucleophile to provide a halobutyl ionomer; and
grafting a non-halogenated amine-reactive dienophile to the ionomer through a reactive mixing process to provide a functionalized ionomer.
2. The method according to claim 1 , wherein the halobutyl polymer comprises repeating units derived from at least one isoolefin and at least one multiolefin.
3. The method according to claim 2 , wherein the isoolefin comprises isobutylene and the multiolefin comprises isoprene.
4. The method according to claim 1 , wherein the at least one of the nitrogen based nucleophile and the phosphorus based nucleophile is a nucleophile according to the formula
wherein:
A is a nitrogen or phosphorus, and
R 1 , R 2 and R 3 are independently selected from the group consisting of linear or branched C 1 -C 18 alkyl substituents, an aryl substituent which is monocyclic or composed of fused C 4 -C 8 rings, and a hetero atom selected from a group consisting of B, N, O, Si, P, and S.
5. The method according to claim 1 , wherein the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile is triphenylphosphine.
6. The method according to claim 1 , wherein the non-halogenated amine-reactive dienophile is maleic anhydride.
7. The method according to claim 1 , further comprising pelletizing the functionalized ionomer.
8. The method according to claim 1 , wherein:
the isoolefin comprises isobutylene;
the multiolefin comprises isoprene;
the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile is triphenylphosphine;
the non-halogenated amine-reactive dienophile is maleic anhydride; and
the method further comprises conducting the reacting and grafting in an extruder.
9. The method according to claim 8 , further comprising conducting the reading and grafting in an extruder operated at a temperature of 25 to 250° C.
10. The method according to claim 9 , further comprising:
adding the at least one of the nitrogen based nucleophile and the phosphorous based nucleophile to the halobutyl polymer in the extruder; and
adding the amine-reactive dienophile to the ionomer in the extruder.
11. The method according to claim 1 , wherein the method further comprises blending the functionalized ionomer with an amino-containing thermoplastic to form a butyl rubber ionomer-thermoplastic graft copolymer.
12. The method according to claim 11 , wherein the amino containing thermoplastic is a polyamide, and the method further comprises conducting the blending in an extruder.
13. The method according to claim 11 , further comprising conducting both the grafting and the blending in an extruder, wherein the extruder has a beginning portion and a point downstream of the beginning portion, and the method comprises introducing the dienophile and ionomer at the beginning portion, and adding thermoplastic at the point downstream of the beginning portion.