USRE33797EExpiredUtility
Novel polyimidesiloxanes and methods for their preparation and use
Priority: Nov 14, 1988Filed: Feb 15, 1991Granted: Jan 14, 1992
Est. expiryNov 14, 2008(expired)· nominal 20-yr term from priority
H10P 14/6342H10P 14/683C08G 77/455C08G 73/106
1
PatentIndex Score
0
Cited by
28
References
57
Claims
Abstract
Substantially fully imidized polyimidesiloxanes which are based on a selected pyridine compound are soluble in diglyme which gives them particular utility in the micro-electronics industry. The polymers are prepared from the dianhydride, a difunctional siloxane monomer and an organic diamine that has the formula ##STR1## wherein X is hydrogen, halide, phenyl or combinations thereof, Z=--O--, --S--, ##STR2## >C(CX 3 ) 2 , --, or --Y--Ar--Y--. Ar= ##STR3## Y=--O--, --S--, ##STR4## >C(CH 3 ) 2 , or --. n=0 or 1. The preferred diamine has the formula ##STR5## Other diamines can be used to provide an asymmetrical structure in the polyimidesiloxane polymer chain. The polyimidesiloxane can be prepared with functional groups which render them directly curable. The polyimidesiloxanes can also be prepared with functional groups which when reacted with an unsaturated compound renders the polymers curable. The products of the invention can be used in the form of solutions in the micro-electronic industry. The polymers can also be used in wire and cable coating and to prepare films, fibers, and molded and extruded articles.
Claims
exact text as granted — not AI-modifiedI claim:
1. In a substantially fully imidized polyimidesiloxane comprising the reaction product of .[.an.]. organic dianhydride, .[.a.]. difunctional siloxane monomer, and .[.an.]. organic .[.amine.]. .Iadd.diamine.Iaddend., the improvement wherein the organic .[.amine.]. .Iadd.diamine .Iaddend.has the formula ##STR48## wherein X is hydrogen, halide, phenyl or combinations thereof, Z=--O--, --S--, ##STR49## >C(CX 3 ) 2 , --, or --Y--Ar--Y-- Ar= ##STR50## Y=--O--, --S--, ##STR51## >C(CX 3 ) 2 , or --; and n=0 or 1.
2. The polyimidesiloxane of claim 1 wherein the organic dianhydride is an oxydiphthalic anhydride.
3. The polyimidesiloxane of claim 1 wherein the organic dianhydride is 4,4'-oxydiphthalic anhydride.
4. The polyimidesiloxane of claim 1 wherein the organic dianhydride is a sulfurdiphthalic anhydride or a sulfone diphthalic anhydride.
5. The polyimidesiloxane of claim 1 wherein the organic dianhydride is 4,4'-sulfurdiphthalic anhydride or 4,4'-sulfone diphthalic anhydride.
6. The polyimidesiloxane of claim 1 wherein the organic dianhydride is benzophenone tetracarboxylic dianhydride.
7. The polyimidedesiloxane of claim 1 wherein the organic dianhydride is biphenyl tetracarboxylic dianhydride.
8. The polyimidesiloxane of claim 1 wherein the organic dianhydride is bis(dicarboxyphenyl)-hexafluoropropene dianhydride.
9. The polyimidesiloxane of claim 1 wherein the organic dianhydride is diether dianhydride.
10. The polyimidedesiloxane of claim 1 wherein the organic .[.amine.]. .Iadd.diamine .Iaddend.has the formula ##STR52##
11. The polyimidesiloxane of claim 10 which also comprises an organic diamine which provides an asymmetrical structure in the polyimidesiloxane polymer chain.
12. The polyimidesiloxane of claim 11 wherein .[.the.]. .Iadd.an .Iaddend.organic diamine .[.has.]. .Iadd.having .Iaddend.the formula ##STR53## .Iadd.is included in said reaction product .Iaddend.wherein .[.x, y and z.]. .Iadd.e, f, and g .Iaddend.are independently selected from hydrogen, halogen, alkyl or halogenated alkyl of 1 to 12 carbon atoms or aryl or halogenated aryl of 6 to 12 carbon atoms, provided that all of .[.x, y and z.]. .Iadd.e, f, and g .Iaddend.are not hydrogen.
13. The polyimidesiloxane of claim 12 wherein .[.x, y and z.]. .Iadd.e, f, and g .Iaddend.are independently selected from hydrogen, halogen, alkyl of 1 to 12 carbon atoms or aryl of 6 to 12 carbon atoms, provided that all of .[.x, y and z.]. .Iadd.e, f, and g .Iaddend.are not hydrogen.
14. The polyimidesiloxane of claim 13 wherein the organic diamine is 2,4-tolyldiamine, 2,6-tolyldiamine or a mixture thereof.
15. The polyimidesiloxane of claim 1 wherein .[.at least a portion of the.]. .Iadd.an .Iaddend.organic diamine .[.has.]. .Iadd.having .Iaddend.the formula ##STR54## .Iadd.is included in said reaction product, .Iaddend.wherein .[.Ar.]. .Iadd.Ar 2 .Iaddend.is an aromatic radical, and R" is at least one of a hydroxyl, carboxyl, or hydrothiol.
16. The polyimidesiloxane of claim 15 wherein R" is a carboxyl group or the metal salt of said carboxyl group.
17. The polyimidesiloxane of claim 1 wherein .[.at least a portion of the.]. .Iadd.an .Iaddend.organic diamine .[.component has.]. .Iadd.having .Iaddend.the formula ##STR55## .Iadd.is included in said reaction product .Iaddend.wherein .[.Ar.]. .Iadd.Ar 2 .Iaddend.is an aromatic radical, and .[.R'".]. .Iadd.R 2 .Iaddend.is at least one of an arcylic-, an ethylenic- or an acetylenic-bearing radical.
18. The polyimidesiloxane of claim 17 wherein the siloxane monomer is a siloxane diamine.
19. The polyimidesiloxane of claim 18 wherein the siloxane diamine has the formula ##STR56## wherein .Iadd.each .Iaddend.R' is independently selected from .Iadd.the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic difunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms, .[.or.]. substituted .[.or.]. .Iadd.aromatic difunctional radicals of 6 to 10 carbon atoms, and .Iaddend.unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein .[.one or more of R 1 , R 2 , R 3 and R 4 can be vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ' and R 4 ' .Iaddend.are .Iadd.each .Iaddend.independently selected from .[.a.]. .Iadd.the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic monofunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic monofunctional .[.radical.]. .Iadd.radicals .Iaddend.of 1 to 12 carbon atoms, .[.or.]. substituted .[.or.]. .Iadd.aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iaddend.unsubstituted aromatic monofunctional .[.radical.]. .Iadd.radicals .Iaddend.of 6 to 10 carbon atoms, .Iadd.and hydroxyl, where at least one of R 1 ', R 2 ', R 3 ' and R 4 ' is vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radical, .Iaddend.and m is .[.a number from about 5.]. .Iadd.1 .Iaddend.to about 200.
20. The polyimidesiloxane according to claim 19 wherein .[.R 1 , R 2 , R 3 and R 4 are.]. .Iadd.at least one of R 1 ', R 2 ', R 3 ', and R 4 ' is a .Iaddend.methyl .[.groups.]. .Iadd.group.Iaddend..
21. The polyimidesiloxane according to claim 20 wherein R' is .[.--CH 2-3 .]. .Iadd.--CH 2 ) 3 .Iaddend..
22. The polyimidesiloxane of claim 19 wherein at least a portion of the siloxane diamine of the formula comprises a diamine wherein at least one of .[.R 1 , R 2 , R 3 and R 4 is a radical selected from.]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' is .Iaddend.hydroxyl or vinyl.
23. The polyimidesiloxane according to claim 22 wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is vinyl and the remainder are methyl groups.
24. The polyimidesiloxane according to claim 23 wherein the R' is --CH 2 ) 3 .
25. The polyimidedesiloxane of claim 19 wherein .[.at least a portion of the siloxane diamine of the formula comprises a siloxane diamine component wherein.]. at least one of .[.R 1 , R 2 , R 3 and R 4 is a radical selected from.]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' is an .Iaddend.acrylic-, ethylenic- or acetylenic-bearing .[.radicals.]. .Iadd.radical.Iaddend..
26. The polyimidesiloxane of claim 25 comprising an .[.acrylicbearing.]. .Iadd.acrylic-bearing .Iaddend.radical.
27. The polyimidesiloxane of claim 1 wherein the siloxane monomer is a siloxane dianhydride.
28. The polyimidesiloxane of claim 27 wherein the siloxane dianhydride .[.as.]. .Iadd.has .Iaddend.the formula ##STR57## wherein .Iadd.each .Iaddend.R is .Iadd.independently selected from the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic trifunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic trifunctional radicals of 1 to 12 carbon atoms, .[.or.]. substituted .[.or.]. .Iadd.aromatic trifunctional radicals of 6 to 10 carbon atoms, and .Iaddend.unsubstituted aromatic trifunctional radicals of 6 to 10 carbon atoms, and wherein .[.one or more of R 1 , R 2 , R 3 and R 4 can be halogen, hydride (H), vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 , .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are .Iadd.each .Iaddend.independently selected from .[.a.]. .Iadd.the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic monofunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic monofunctional .[.radical.]. .Iadd.radicals .Iaddend.of 1 to 12 carbon atoms, .[.or.]. substituted .[.or.]. .Iadd.aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iaddend.unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iadd.halogen, hydride (H), and hydroxyl, where at least one of R 1 ', R 2 ', R 3 ' and R 4 ' is halogen, hydride (H), vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radical, .Iaddend.and wherein m is .[.about 5.]. .Iadd.1 .Iaddend.to about .[.50.]. .Iadd.200.
29. The polyimidesiloxane of claim 28 wherein .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are methyl groups.
30. The polyimidesiloxane of claim 29 wherein R is ##STR58##
31. The polyimidesiloxane of claim 28 wherein at least a portion of the siloxane dianhydride of the formula comprises a dianhydride wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is a radical selected from hydride (H), halogen, hydroxyl or vinyl.
32. The polyimidesiloxane according to claim 31 wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is vinyl and the remainder are methyl groups.
33. The polyimidesiloxane according to claim 32 wherein R is ##STR59##
34. The polyimidesiloxane of claim 28 wherein at least a portion of the siloxane dianhydride component of the formula comprises a siloxane dianhydride component wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is a radical selected from acrylic, ethylenic or acetylenic radicals.
35. The polyimidesiloxane of claim 34 comprising an acrylic-bearing radical.
36. A process for producing a polyimidesiloxane that is soluble in diglyme, which comprises reacting a difunctional siloxane monomer, an organic dianhydride and .[.an amine.]. .Iadd.a diamine .Iaddend.of the formula of claim 1.
37. The process of claim 36 wherein the reaction is conducted in a solvent for the polyimidesiloxane.
38. The process of claim 37 wherein the .[.amine.]. .Iadd.diamine .Iaddend.has the formula ##STR60## and the solvent is selected from diglyme, triglyme, γ-butyrolactone, N,N-dimethylacetamide, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
39. The process of claim 36 wherein the siloxane monomer is a siloxane diamine.
40. The process of claim 36 wherein the siloxane monomer is a siloxane diamine having the formula ##STR61## wherein .Iadd.each .Iaddend.R' is independently selected from .Iadd.the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic difunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms .[.or.]. substituted .[.or.]. .Iadd.aromatic difunctional radicals of 6 to 10 carbon atoms, and .Iaddend.unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein .[.one or more of R 1 , R 2 , R 3 and R 4 can be vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are .Iadd.each .Iaddend.independently selected from .[.a.]. .Iadd.the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic monofunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic monofunctional .[.radical.]. .Iadd.radicals .Iaddend.of 1 to 12 carbon atoms .[.or.]. substituted .[.or.]. .Iadd.aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iaddend.unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iadd.and hydroxyl, where at least one of R 1 ', R 2 ', R 3 ' and R 4 ' is vinyl, hydroxyl, arcrylic-, ethylenic-, or acetylenic-bearing radical, .Iaddend.and m is an integer from about .[.5.]. .Iadd.1 .Iaddend.to about .[.50.]. .Iadd.200.Iaddend..
41. The process of claim 40 wherein .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are methyl groups.
42. The process of claim 41 wherein R' is --CH 2 ) 3 .
43. The process of claim 36 wherein the siloxane monomer is a siloxane dianhydride.
44. The process of claim 43 wherein the siloxane monomer is a siloxane dianhydride having the formula ##STR62## wherein .Iadd.each .Iaddend.R is .Iadd.independently selected from the group consisting of .Iaddend.substituted .[.or.]. .Iadd.aliphatic trifunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic trifunctional radicals of 1 to 12 carbon atoms.Iadd., .Iaddend..[.or.]. substituted .[.or.]. .Iadd.aromatic trifunctional radicals of 6 to 10 carbon atoms, and .Iaddend.unsubstituted aromatic trifunctional radicals of 6 to 10 carbon atoms, and wherein .[.one or more of R 1 , R 2 , R 3 and R 4 can be halogen, hydride (H), vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 ,.]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are .Iadd.each .Iaddend.independently selected from .[.a.]. .Iadd.the group consisting of .Iaddend.substituted .[. or.]. .Iadd.aliphatic monofunctional radicals of 1 to 12 carbon atoms, .Iaddend.unsubstituted aliphatic monofunctional .[.radical.]. .Iadd.radicals .Iaddend.of 1 to 12 carbon atoms .[.or.]. substituted .[.or.]. .Iadd.aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iaddend.unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, .Iadd.halogen, hydride (H), and hydroxyl, where at least one of R 1 ', R 2 ', R 3 ' and R 4 ' is halogen, hydride (H), vinyl, hydroxyl, arcrylic-, ethylenic-, or acetylenic-bearing radical, .Iaddend.and wherein m is .[.about 5.]. .Iadd.1 .Iaddend.to about .[.54.]. .Iadd.200.Iaddend..
45. The process of claim 44 wherein .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.are methyl groups.
46. The process of claim 45 wherein R is ##STR63##
47. The process of claim 36 wherein .[.at least a portion of the.]. .Iadd.an .Iaddend.organic diamine .[.has.]. .Iadd.having .Iaddend.the formula ##STR64## .Iadd.is included in said reaction product, .Iaddend.wherein .[.Ar.]. .Iadd.Ar 2 .Iaddend.is an aromatic radical, and R" is at least one of a hydroxyl, carboxyl, or hydrothiol.
48. The process of claim 47 wherein R" is .[.carboxy.]. .Iadd.carboxyl.Iaddend..
49. The process of claim 40 wherein at least a portion of the siloxane diamine of the formula comprises a diamine wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is a radical selected from hydroxyl or vinyl.
50. The process according to claim 49 wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is a vinyl radical, and the remainder are methyl groups.
51. The process according to claim 50 where the R' is --CH 2 ) 3 .
52. The process of claim 44 wherein at least a portion of the siloxane dianhydride of the formula comprises a dianhydride wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is a radical selected from hydride (H), halogen, hydroxyl, or vinyl.
53. The process according to claim 52 wherein at least one of .[.R 1 , R 2 , R 3 and R 4 .]. .Iadd.R 1 ', R 2 ', R 3 ', and R 4 ' .Iaddend.is vinyl and the remainder are methyl groups.
54. The process according to claim 53 wherein R is ##STR65##
55. The process of claim 47 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
56. The process of claim 49 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
57. The process of claim 52 wherein the product of the process is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.Join the waitlist — get patent alerts
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