Polysiloxane-polyorgano block copolymers
View Patent ↗Disclosed herein is a process for the production of a polysiloxane-polyorgano block copolymer. The process includes reacting a reaction mixture containing (a) an ester-functional polydiorganosiloxane and (b) a bisphenolic compound or a bisphenolic compound oligomer. This process has the advantage of yielding block copolymers with controlled block structures and avoiding the impurities that may be carried over from the conventional hydroxyaryloxy-terminated-polydiorganosiloxanes.
1. A process for the production of a polysiloxane-polyorgano block copolymer comprising reacting a reaction mixture containing (a) an ester-functional polydiorganosiloxane and (b) a bisphenolic compound or a bisphenolic compound oligomer,
wherein the ester-functional polydiorganosiloxane is a compound of the general formula (XI)
wherein Y 1 and Y 2 are independently a divalent C6-C30 aryl, alkyl, alkylaryl or aryloxy group, R5 and R6 are independently C1-C20 alkyl, alkylaryl, or aryl groups, n has a value of from 10 to 400, and m has a value of from 0 to 10.
2. The process of claim 1 wherein the ester-functional polydiorganosiloxane is of the general formula (XVI)
wherein R 5 is a C1-C20 alkyl, alkylaryl, or aryl group, and n has a value between 10 and 100.
3. The process of claim 1 wherein the bisphenolic compound is of the general formula (XIII)
wherein R 7 and R 8 are independently selected from the group consisting of hydrogen, halogen, C1 to C8 alkyl, C5 or C6 cycloalkyl, C6 to C10 aryl, and C7 to C12 aralkyl, and X is a single bond, —CH 2 —,
O, S, SO 2 ,
wherein a is an integer of from 4 to 7, R 9 and R 10 are independently hydrogen, or C1-C6 alkyl, P is carbon, provided on at least one ring carbon atom, R 9 and R 10 both represent C1-C6 alkyl.
4. The process of claim 3 wherein the bisphenolic compound is selected from the group consisting of
5. The process of claim 1 wherein the bisphenolic compound oligomer is a polycarbonate, polysulfone or polyester oligomer of a bisphenolic compound of the general formula (XIII)
wherein R 7 and R 8 are independently selected from the group consisting of hydrogen, halogen, C1 to C8 alkyl, C5 or C6 cycloalkyl, C6 to C10 aryl, and C7 to C12 aralkyl, and X is a single bond, —CH 2 —,
O, S, SO 2 ,
wherein a is an integer of from 4 to 7, R 9 and R 10 are independently hydrogen, or C1-C6 alkyl, P is carbon, provided on at least one ring carbon atom, R 9 and R 10 both represent C1-C6 alkyl.
6. The process of claim 5 wherein the bisphenolic compound oligomer is a polycarbonate, polysulfone or polyester oligomer of a bisphenolic compound selected from the group consisting of
7. The process of claim 1 wherein the bisphenolic compound oligomer is of the general formula (XVI)
wherein z is a divalent C6-C30 aryl, bisarylalkyl or bisaryloxy group, p is a number between 2 and 150, Q 1 and Q 2 are each independently hydrogen or a —C(═O)—OX group, and X is a C1-C20 alkyl, alkylaryl, or aryl group.
8. The process of claim 1 wherein the bisphenolic compound oligomer is a polysulfone oligomer of the bisphenolic compound (XIII) having the general formula (XXIII) or formula (XXIV)
wherein Y 1 is a divalent C6-C30 aryl, alkyl, alkylaryl or aryloxy group, p and q are independently between 1 and 150, Q 1 and Q 2 are each independently hydrogen or a —C(═O)—OX grou, and X is a C1-C20 alkyl, alkylaryl, or aryl group.
9. The process of claim 1 wherein the bisphenolic compound oligomer is a polyester oligomer of the bisphenolic compound (XIII) having the general formula (XXV):
Wherein Y 1 and Y 3 are each independently a divalent C6-C30 aryl, alkyl, alkylaryl or aryloxy group, q is between 2 and 150, Q 1 and Q 2 are each independently hydrogen, a C1 to C20 alkyl, alkylaryl, aryl group, or a —C(═O)—OX group, and X is a C1-C20 alkyl, alkylaryl, or aryl group.
10. The process of claim 1 wherein (a) the ester-functional polydiorganosiloxane and (b) the bisphenolic compound of the bisphenolic compound oligomer are co-condensed with phosgene under the reaction conditions of a two-phase boundary process.
11. The process of claim 1 wherein (a) the ester-functional polydiorganosiloxane and (b) the bisphenolic compound of the bisphenolic compound oligomer are co-condensed under the reaction conditions of a solvent-free melt process.
12. The process of claim 1 wherein the reaction mixture additionally comprises at least one of a chain stopper or a catalyst.
13. A polyorganosiloxane-polyorgano block copolymer prepared by the process of claim 1 .
14. An article of manufacture comprising the polysiloxane-polyorgano copolymer of claim 13 .
15. An ester-functional polysiloxane of the general formula (XI):
wherein Y 1 and Y 2 are independently a divalent C6-C30 aryl, alkyl, alkylaryl or aryloxy group, R5 and R6 are independently C1-C20 alkyl, alkylaryl, or aryl groups, n has a value of from 10 to 400, and m has a value of from 0 to 10.
16. The ester-functional polysiloxane of claim 15 wherein the polydiorganosiloxane is of the general formula (XVI)
wherein R 5 is a C1-C20 alkyl, alkylaryl, or aryl group, and n has a value between 10 and 100.