Process for continuous production of halogen-free thermoplastic elastomer compositions
A continuous process for the production of a dynamically vulcanized thermoplastic elastomer comprising a thermoplastic resin and a non-halogenated elastomer with a multiolefin content of greater than 3.5 mol % that has been modified in situ with a carboxylic anhydride. The process provides materials with improved elongation at break and ultimate tensile strength that can be produced economically and with reduced environmental impact.
1. A continuous process for the preparation of a thermoplastic elastomer composition, the process comprising:
a) admixing in a first stage of a continuous mixer:
a thermoplastic resin;
a non-halogenated elastomer comprising repeating units derived from at least one C 4 to C 7 isomonoolefin monomer and at least 3.5 mol % of a C 4 to C 16 multiolefin monomer;
a curing agent for curing the non-halogenated elastomer; and
an unsaturated carboxylic compound having 4 to 16 carbon atoms, and selected from the group consisting of carboxylic a, carboxylic amide, carboxylic ester and carboxylic anhydride;
to graft the carboxylic compound to the non-halogenated elastomer and form a thermoplastic elastomer composition;
b) introducing, in a second stage of the continuous mixer subsequent to the first stage, an additional curing agent suitable for curing the non-halogenated elastomer to dynamically vulcanize the thermoplastic elastomer composition, and admixing the thermoplastic elastomer composition and the additional curing agent,
wherein the admixing in each of the first and second stages is done at a temperature sufficient for melting the thermoplastic resin and curing the non-halogenated elastomer.
2. The process of claim 1 , wherein the admixing in the second stage further comprises admixing at a temperature of 100 to 260° C. to cure the non-halogenated elastomer and dynamically vulcanize the thermoplastic elastomer composition.
3. The process of claim 2 , wherein the additional curing agent comprises a first peroxide curing agent, and wherein the curing agent for the non-halogenated elastomer in the first stage comprises a second peroxide curing agent, the second peroxide curing agent being the same as or different from the first peroxide curing agent, and the admixing in the first stage further comprises admixing the second peroxide curing agent with the thermoplastic resin, the non-halogenated elastomer and the carboxylic compound in the first stage at a temperature of 100 to 260° C.
4. The process of claim 3 , wherein the second peroxide curing agent is provided in an amount of 0.05 to 0.3 phr.
5. The process of claim 3 , wherein the first peroxide curing agent is provided in an amount of 0.1 to 3 phr.
6. The process of claim 3 , wherein the first peroxide curing agent is provided in an amount of 0.1 to 3 phr and the second peroxide curing agent is provided in a non-zero amount of less than 0.1 phr.
7. The process of claim 6 , wherein the second peroxide curing agent is provided in an amount of greater than 0.01 phr.
8. The process of claim 3 , wherein the first peroxide curing agent and/or the second peroxide curing agent are each independently 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, di-(2-tert-butylperoxy isopropyl)benzene, dicumyl peroxide, butyl 4,4-di-(tert-butylperoxy)valerate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, dibenzyl peroxide, di(4-methylbenzoyl) peroxide, di-2,4-dichlorobenzoyl peroxide or mixtures thereof.
9. The process of claim 1 , wherein the continuous mixer comprises an extruder.
10. The process of claim 1 , wherein the thermoplastic resin is a polyamide.
11. The process of claim 1 , wherein the isomonoolefin monomer is isobutene and the multiolefin monomer isisoprene.
12. The process of claim 11 , wherein the isoprene is present in an amount of at least 5 mol %.
13. The process of claim 12 , wherein the isoprene is present in an amount of at least 7 mol %.
14. The process of claim 1 , wherein the carboxylic compound is maleic anhydride, chloromaleic anhydride, itaconic anhydride, or hemic anhydride.
15. The process of claim 1 , wherein the non-halogenated elastomer is provided in a pelletized form.
16. The process of claim 1 , wherein:
the additional curing agent in the second stage comprises a first peroxide curing agent, and the curing agent in the first stage comprises a second peroxide curing agent the same as or different from the first peroxide curing agent; and
the first peroxide curing agent is provided in an amount of 0.1 to 3 phr and the second peroxide curing agent is provided in an amount of 0.01 to 0.1 phr.
17. The process of claim 16 , wherein:
the continuous mixer comprises an extruder;
the first peroxide curing agent and the second peroxide curing agent are each independently selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, di(2-tert-butylperoxy isopropyl)benzene, dicumyl peroxide, butyl 4,4-di(tert-butylperoxy)valerate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, dibenzyl peroxide, di(4-methylbenzoyl) peroxide, di-2,4-dichlorobenzoyl peroxide and mixtures thereof; and
the admixing in the first stage and in the second stage further comprises admixing at a temperature of 100° C. to 260° C.
18. The process of claim 17 , wherein:
the thermoplastic resin is a polyamide;
the isomonoolefin monomer is isobutene and the multiolefin monomer is isoprene in an amount of at least 7 mol %; and
the carboxylic compound is maleic anhydride, chloromaleic anhydride, itaconic anhydride, or hemic anhydride.
19. A continuous process for the preparation of a thermoplastic elastomer, the process comprising:
a) in a first stage of a continuous mixer:
admixing:
a thermoplastic resin;
a non-halogenated elastomer comprising repeating units derived from at least one C 4 to C 7 isomonoolefin monomer and a C 4 to C 16 multiolefin monomer;
a curing agent for curing the non-halogenated elastomer; and
a C 4 to C 16 unsaturated cyclic anhydride;
to graft the carboxylic anhydride to the non-halogenated elastomer and form a thermoplastic elastomer composition; and
curing at least a portion of the non-halogenated elastomer;
b) in a second stage of the continuous mixer subsequent to the first stage:
admixing the thermoplastic elastomer composition and an additional curing agent suitable for curing the non-halogenated elastomer; and
curing an additional portion of the thermoplastic elastomer composition to produce a dynamically vulcanized thermoplastic elastomer.
20. The process of claim 19 , wherein:
the thermoplastic resin is a polyamide;
the isomonoolefin monomer is isobutene and the multiolefin monomer is isoprene;
the carboxylic compound is maleic anhydride; and
the curing agent and the additional curing agent are each independently selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl cumyl peroxide, di(2-tert-butylperoxy isopropyl)benzene, dicumyl peroxide, butyl 4,4-di(tert-butylperoxy)valerate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxybenzoate, tert-butyl peroxy 3,5,5-trimethylhexanoate, dibenzyl peroxide, di(4-methylbenzoyl) peroxide, di-2,4-dichlorobenzoyl peroxide, and mixtures thereof.