Polysiloxane/polyimide copolymers and blends thereof
View Patent ↗Disclosed herein is a polysiloxane/polyimide block copolymer having a siloxane content of 5 to 30 weight percent, based on the total weight of the block copolymer and comprising repeating units of Formula (I) wherein R 1-6 are independently at each occurrence selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms and substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers, g equals 1 to 30, and d is greater than or equal to 1. Also disclosed are blends of the disclosed block copolymers, methods of making the blends and articles comprising the block copolymer and block copolymer blends.
1. A polysiloxane/polyimide block copolymer having a siloxane content of 5 to 30 weight percent, based on the total weight of the block copolymer and a single Tg, comprising a polysiloxane block and a non-siloxane polyimide block wherein the polysiloxane block comprises repeating units of Formula (I)
wherein
R 2-5 are methyl groups and R 1 and R 6 are substituted or unsubstituted alkylene groups having 3 to 20 carbon atoms,
V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers,
g equals 1 to 30, and
d+1 equals 4 to 10.
2. The block copolymer of claim 1 wherein the block copolymer has a notched Izod greater than or equal to 374 joules per meter at 23° C. as determined by ASTM method D256.
3. The block copolymer of claim 1 , wherein d+1 has a value from 4 to 6.
4. The block copolymer of claim 1 , wherein the block copolymer has a residual solvent content less than or equal to 500 parts by weight of solvent per million parts by weight of block copolymer.
5. The block copolymer of claim 1 wherein the block copolymer is halogen free.
6. The block copolymer of claim 1 wherein the polyimide block comprises repeating units of Formula (X)
wherein each R 10 is independently derived from p-phenylene, m-phenylene, diamino aryl sulfone or a mixture thereof and T is a divalent radical of the Formula (XI):
7. The block copolymer of claim 1 wherein the siloxane content is 10 to 25 weight percent based on the total weight of the block copolymer.
8. The block copolymer of claim 1 wherein the amount of alkali and alkaline earth metal ions is less than or equal to 1000 parts by weight per million parts by weight of block copolymer.
9. An article of manufacture comprising the block copolymer of claim 1 .
10. A thermoplastic composition comprising a first polysiloxane/polyimide block copolymer having a first siloxane content, based on the total weight of the first block copolymer, and comprising a polysiloxane block and a non-siloxane polyimide block wherein the polysiloxane block comprises repeating units of Formula (I)
a second polysiloxane/polyimide block copolymer having a second siloxane content, based on the total weight of the second block copolymer, and comprising a polysiloxane block and a non-siloxane polyimide block wherein the polysiloxane block comprises repeating units of Formula (I)
wherein in the first and second polysiloxane/polyimide block copolymers
R 2-5 are methyl groups and R 1 and R 6 are substituted or unsubstituted alkylene groups having 3 to 20 carbon atoms,
V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers,
g equals 1 to 30, and
d+1 equals 4 to 10,
the weight percent of siloxane of the first block copolymer based on the total weight of the first block copolymer does not equal the weight percent of siloxane of the second block copolymer based on the total weight of the second block copolymer, and
the first polysiloxane/polyimide block copolymer has a value for d equal the value for d of the second polysiloxane/polyimide block copolymer, and
the copolymer composition has a single Tg.
11. The thermoplastic composition of claim 10 wherein the composition has a residual solvent content less than or equal to 500 parts by weight of solvent per million parts by weight of block copolymer.
12. The thermoplastic composition of claim 10 wherein the siloxane content of the first block copolymer is 10 to 25 weight percent based on the total weight of the first block copolymer and the siloxane content of the second block copolymer is 10 to 25 weight percent based on the total weight of the second block copolymer.
13. The thermoplastic composition of claim 10 wherein the composition is halogen free.
14. The thermoplastic composition of claim 10 wherein d+1 has a value of 4 to 6 in the first and second block copolymers.
15. The thermoplastic composition of claim 10 wherein the amount of alkali and alkaline earth metal ions in the first block copolymer and in the second block copolymer is less than or equal to 1000 parts by weight per million parts by weight of block copolymer.
16. An article of manufacture comprising the thermoplastic composition of claim 10 .
17. A thermoplastic composition comprising
a first polysiloxane/polyimide block copolymer having a first siloxane content, based on the total weight of the first block copolymer, and comprising a polysiloxane block and a non-siloxane polyimide block wherein the polysiloxane block comprises repeating units of Formula (I)
a second polysiloxane/polyimide block copolymer having a second siloxane content, based on the total weight of the second block copolymer, and comprising a polysiloxane block and a non-siloxane polyimide block wherein the polysiloxane block comprises repeating units of Formula (I)
wherein in the first and second polysiloxane/polyimide block copolymers,
R 2-5 are methyl groups and R 1 and R 6 are substituted or unsubstituted alkylene groups having 3 to 20 carbon atoms,
V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers,
g equals 1 to 30, and
d+1 equals 4 to 10,
the weight percent of siloxane of the first polysiloxane/polyimide block copolymer based on the total weight of the first polysiloxane/polyimide block copolymer does not equal the weight percent of siloxane of the second polysiloxane/polyimide block copolymer based on the total weight of the second polysiloxane/polyimide block copolymer, and
the value of d for the first polysiloxane/polyimide block copolymer does not equal the value of d for the second polysiloxane/polyimide block copolymer, and
the copolymer composition has a single Tg.
18. The thermoplastic composition of claim 17 wherein the composition has a residual solvent content less than or equal to 500 parts by weight of solvent per million parts by weight of block copolymer.
19. The thermoplastic composition of claim 17 wherein the siloxane content of the first block copolymer is 10 to 25 weight percent based on the total weight of the first block copolymer and the siloxane content of the second block copolymer is 10 to 25 weight percent based on the total weight of the second block copolymer.
20. The thermoplastic composition of claim 17 wherein the composition is halogen free.
21. The thermoplastic composition of claim 17 wherein d+1 has a value of 4 to 6 in the first and second block copolymers.
22. The thermoplastic composition of claim 17 wherein the amount of alkali and alkaline earth metal ions in the first block copolymer and in the second block copolymer is less than or equal to 1000 parts by weight per million parts by weight of block copolymer.
23. An article of manufacture comprising the thermoplastic composition of claim 17 .
24. A polysiloxane/polyimide block copolymer having a siloxane content of 5 to 30 weight percent, based on the total weight of the block copolymer and a single Tg comprising a polysiloxane block and a non-siloxane polyimide block,
wherein the polysiloxane block comprises repeating units of Formula (I)
wherein
R 2-5 are methyl groups and R 1 and R 6 are substituted or unsubstituted alkylene groups having 3 to 20 carbon atoms,
V is a tetravalent linker selected from the group consisting of substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups having 5 to 50 carbon atoms, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms and combinations comprising at least one of the foregoing linkers,
g equals 1 to 30, and
d+1 equals 4 to 10;
wherein the polyimide block comprises repeating units of Formula (X)
wherein each R 10 is independently derived from p-phenylene, m-phenylene, diamino aryl sulfone or a mixture thereof and T is a divalent radical of the Formula (XI):
and wherein the block copolymer is halogen free and has a residual solvent content less than or equal to 500 parts by weight of solvent per million parts by weight of block copolymer.
25. The composition of claim 24 , wherein d+1 has a value of 4 to 6.
26. The article of manufacture of claim 23 , wherein the article is a conductive wire comprising a conductor and the thermoplastic composition as a covering disposed over the conductor.