Block copolymers having amine or phosphine functionalized end blocks
Disclosed herein is a functionalized block copolymer comprising (a) at least one end block D comprising on average at least one amino- or phosphino-functionalized polymer unit of formula (I) and one or more additional blocks selected from the group consisting of (b) one or more A blocks substantially free of amino- or phosphino- functional groups and having a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature, and (c) one or more B blocks, wherein each block B is essentially non-functionalized, has a number average molecular weight of from about 1,000 to about 1,000,000, and has a glass transition temperature of at most about 20° C., and (d) mixtures of one or more A blocks and one or more B blocks; wherein Z is nitrogen or phosphorus; R 1 is hydrogen or alkyl; R 2 is hydrogen or is tertiary alkyl; R each independently, is alkyl or phenyl optionally substituted by a moiety -(A 1 -NR a ) x R b or -(A 1 -OR a ) x R b ; or two R groups, together with the Z to which they are bonded, form an optionally substituted ring; x is 1, 2 or 3; A 1 is straight chain alkylene optionally substituted by one or more methyl and/or ethyl groups; and R a and R b , each independently, is hydrogen or alkyl; or a corresponding onium salt.
1. A functionalized block copolymer comprising:
(a) at least one end block D comprising on average at least one amino-functionalized polymer unit of formula (I)
and
one or more additional blocks selected from the group consisting of:
(b) one or more A blocks substantially free of amino- functional groups and having a number average molecular weight of from about 1,000 to about 60,000, and has a high service temperature of at least about 20° C., and
(c) one or more B blocks, wherein each block B is essentially non-functionalized, has a number average molecular weight of from about 1,000 to about 1,000,000, and has a glass transition temperature of at most about 20° C.,
and
(d) mixtures of one or more A blocks and one or more B blocks;
wherein
Z is nitrogen;
R 1 is hydrogen or alkyl;
R 2 is hydrogen or tertiary alkyl;
the two R groups, together with the Z to which they are bonded, form an optionally substituted ring;
or a corresponding onium salt.
2. The functionalized block copolymer of claim 1 , wherein the D block is formed on each of the external ends of the block copolymer.
3. The functionalized block copolymer of claim 1 , wherein the at least one end block D is at least 25 wt % of the block copolymer.
4. The functionalized block copolymer of claim 1 , wherein the at least one end block D is 15 wt % or less of the total molecular weight of the block copolymer.
5. The functionalized block copolymer of claim 1 , wherein the at least one end block D is 3 wt % or the less of total molecular weight of the block copolymer.
6. The functionalized block copolymer of claim 1 , wherein the B block comprises segments of conjugated dienes.
7. The functionalized block copolymer of claim 6 , wherein at least 50% of the conjugated dienes units are hydrogenated.
8. The functionalized block copolymer of claim 7 , wherein the D block comprises 15 wt % or less of the total molecular weight of the block copolymer.
9. The functionalized block copolymer of claim 6 , wherein at least 70% of the conjugated dienes units are hydrogenated.
10. The functionalized block copolymer of claim 1 , comprising at least one B block, wherein the at least one B blocks together are at least 50 wt % of the molecular weight of the block copolymer, and wherein 10 to 100% of the functional groups of the block(s) D are in the form of the onium salt.
11. A membrane or film comprising the functionalized block copolymer of claim 10 .
12. The functionalized block copolymer of claim 1 comprising at least one B block, wherein the at least one B blocks together are at least 75 wt % of the molecular weight of the block copolymer, and wherein the block copolymer is star-branched.
13. The functionalized block copolymer of claim 1 comprising at least one block B, wherein each block B is essentially non-functionalized.
14. The functionalized block copolymer according to claim 12 , wherein each block B is independently selected from the group consisting of polymerized (i) ethylene monomers, (ii) C 3 -C 8 alpha-olefin monomers, (iii) isobutylene monomers, (iv) conjugated diene monomers, (v) (meth)acrylate ester monomers, (vi) a silicon polymer, and (vii) mixtures of monomers selected from (i) to (v), wherein segments containing polymerized conjugated diene monomers are optionally hydrogenated.
15. The functionalized block copolymer according to claim 1 , having a general configuration of A-B-D, D-B-D, or B-D.
16. The functionalized block copolymer according to claim 15 , wherein the D block(s) taken together comprises less than 15 wt % of the total molecular weight of the block copolymer.
17. The functionalized block copolymer according to claim 1 , having a general configuration D-A, D-A-D, D-A-D-A-D, (D-A-D) n X, (D-A) n X, D-B-A-B-D, D-A-B-A-D, (D-B-A) n X, (D-A-B) n X, D-B, D-B-D, D-B-D-B-D, (D-B-D) n X, or (D-B) n X, or mixtures thereof, wherein n is an integer from 2 to about 30, and X is a coupling agent residue, and wherein the plurality of A blocks, B blocks, or D blocks are the same or different.
18. The functionalized block copolymer according to claim 1 , wherein each block D is independently selected from the group consisting of (i) segments derived from homo- and copolymers of styrene, (ii) segments derived from homo- and copolymers of styrene having a phenyl ring which is substituted by a primary alkyl group, (iii) segments derived from homo- and copolymer of alpha-alkyl styrene, (iv) segments derived from homo- and copolymers of alpha-alkyl styrene having a phenyl ring which is substituted by a primary alkyl group, and (v) combinations of (i) to (iv).
19. The functionalized block copolymer according to claim 1 , wherein the D block is a mixed block comprising additional polymer units selected from one of (i) conjugated diene, or (ii) styrene or alpha-alkyl styrene monomers having a phenyl ring which is optionally substituted by one or more alkyl groups.
20. A process for preparing an amino-functionalized block copolymer comprising:
in an inert hydrocarbon solvent and in the presence of an initiator,
(a) polymerizing an end block D from a plurality of p-vinylbenzylamine monomers, the p-vinylbenzylamine monomers capable of being polymerized at a temperature range of from 20° C. to 60° C.;
(b) polymerizing at least one or more additional blocks, wherein the one or more additional blocks are selected from the group comprising:
an amorphous block B, the B block having a T g of at most 20° C., wherein the block B is essentially non-functionalized, and has a number average molecular weight of from about 1,000 to about 1,000,000,
a crystalline or semi-crystalline block A, the block A having a high service temperature of at least about 20° C., wherein the block A is substantially free of amino- functional groups, and has a number average molecular weight of from about 1,000 to about 60,000,
and mixtures thereof; and
(c) optionally coupling the block copolymer formed from steps (a)-(b), or polymerizing a second end block D;
wherein:
the end block D comprises on average at least one amino functionalized polymer unit of formula (I)
wherein
Z is nitrogen;
R 1 is hydrogen or alkyl;
R 2 is hydrogen or tertiary alkyl;
the two R groups, together with the Z to which they are bonded, form an optionally substituted ring;
or a corresponding onium salt.
21. The process of claim 20 , wherein the D block is formed on each of the external ends of the block copolymer.
22. The process of claim 20 , wherein block D is polymerized from a plurality of p-vinylbenzylamine monomers.
23. The process of claim 22 , wherein each end block D comprises 10 wt % or less of the total molecular weight of the block copolymer.
24. The process of claim 22 , wherein the functionalized block copolymer comprises at least one B block, wherein the at least one B blocks together are at least 50 wt % of the molecular weight of the block copolymer, and wherein 10 to 100% of the functional groups of the block(s) D are in the form of the onium salt.
25. The process of claim 22 , further comprising casting the functionalized block copolymer into a membrane or film.