US4853452A
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Novel soluble polyimidesiloxanes and methods for their preparation using a flourine containing anhydride
Assignee: Sumitomo Bakelite Co Ltd
•
Filing: 1988-02-09
•
Granted: 1989-08-01
•
Expires: 2008-02-09
Abstract
Abstract Substantially fully imidized polyimidesiloxanes which are based on 6FDA and optionally also a mixture of a biphenyl tetracarboxylic dianhydride and a benzophenone tetracarboxylic dianhydride, are soluble in diglyme which gives them particular utility in the micro-electronics industry. The polymers are prepared from the mixture of dianhydrides, a difunctional siloxane monomer and an organic diamine. 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 product 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.
Inventors
- 👤 Chung J. Lee
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 20:14
CPC Classifications
C; C08; C08G; C08G77/00; C08G77/42; C08G77/452; C08G77/455; C08G73/00; C08G73/06; C08G73/10; C08G73/1057; C08G73/106; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31652; Y10T428/31663; Y10T428/31678; Y10T428/31681; Y10T428/31721
Claims Analysis
Total Claims: 73
Claim 1
Independent Claim
55 words
In a substantially fully imidized polyimidesiloxane comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the polyimidesiloxane is soluble in diglyme and the organic dianhydride comprises a bis(dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) as the sole essential organic dianhydride, and the organic dianhydride is free of polyether linkage.
Claim 2
Dependent Claim
55 words
In a substantially fully imidized polyimidesiloxane comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the polyimidesiloxane is soluble in diglyme and the organic dianhydride comprises a bis(dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) as the sole essential organic dianhydride, and the organic dianhydride is free of polyether linkage.
Claim 3
Dependent Claim
12 words
The polyimidesiloxane of claim 1 wherein the organic dianhydride is 2,2-bis(3',4'-dicarboxylphenyl)hexafluoropropane dianhydride.
Claim 4
Dependent Claim
45 words
The polyimidesiloxane of claim 1 which also comprises an oxydiphthalic anhydride (ODPA) wherein the molar ratio of 6FDA to ODPA is in the range of about 9 parts of 6FDA to 1 part ODPA to about 0.1 part of 6FDA to 1 part of ODPA.
Claim 5
Dependent Claim
11 words
The polyimidesiloxane of claim 3 wherein the ODPA is 4,4'-oxydiphthalic anhydride.
Claim 6
Dependent Claim
47 words
The polyimidesiloxane of claim 1 which also comprises a biphenyl tetracarboxylic dianhydride (BPDA) wherein the molar ratio of 6FDA to BPDA is in the range of about 9 parts of 6FDA to 1 part of BPDA to about 0.5 part of 6FDA to 1 part of BPDA.
Claim 7
Dependent Claim
12 words
The polyimidesiloxane of claim 5 wherein the BPDA is 3,3',4,4'-biphenyl tetracarboxylic dianhydride.
Claim 8
Dependent Claim
18 words
The polyimidesiloxane of claim 1 wherein the organic diamine provides an asymmetrical structure in the polyimidesiloxane polymer chain.
Claim 9
Dependent Claim
56 words
The polyimidesiloxane of claim 1 wherein the organic diamine has the formula ##STR31## wherein x, y and z 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 are not hydrogen.
Claim 10
Dependent Claim
42 words
The polyimidesiloxane of claim 8 wherein x, y and z 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 are not hydrogen.
Claim 11
Dependent Claim
16 words
The polyimidesiloxane of claim 1 wherein the organic diamine is 2,4-tolyldiamine, 2,6-tolyldiamine or a mixture thereof.
Claim 12
Dependent Claim
24 words
The polyimidesiloxane of claim 1 wherein the organic diamine is a mixture of about 80 weight percent 2,4-tolyldiamine and about 20 weight percent 2,6-tolyldiamine.
Claim 13
Dependent Claim
20 words
The polyimidesiloxane of claim 1 wherein the organic diamine has the formula ##STR32## wherein x is --CH 2 --, ##STR33##
Claim 14
Dependent Claim
14 words
The polyimidesiloxane of claim 1 wherein the organic diamine is p,p-oxydianiline, or m,m-methylene dianiline.
Claim 15
Dependent Claim
13 words
The polyimidesiloxane of claim 12 wherein the organic diamine is a 3,3'-sulfone dianiline.
Claim 16
Dependent Claim
13 words
The polyimidesiloxane of claim 12 wherein the organic diamine has the formula ##STR34##
Claim 17
Dependent Claim
35 words
The polyimidesiloxane in claim 1 wherein at least a portion of the organic diamine has the formula ##STR35## wherein Ar is an aromatic radical, and R" is at least one of hydroxyl, carboxyl, or hydrothiol.
Claim 18
Dependent Claim
9 words
The polyimidesiloxane of claim 16 wherein R" is carboxyl.
Claim 19
Dependent Claim
40 words
The polyimidesiloxane of claim 1 wherein at least a portion of the organic diamine component has the formula ##STR36## wherein Ar is an aromatic radical, and R'" is at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 20
Dependent Claim
13 words
The polyimidesiloxane of claim 1 wherein the siloxane monomer is a siloxane diamine.
Claim 21
Dependent Claim
126 words
The polyimidesiloxane of claim 19 wherein the siloxane diamine has the formula ##STR37## wherein R' is independently selected from substituted or unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein none or one or more of R 1 , R 2 , R 3 and R 4 are vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 are independently selected from substituted or unsubstituted aliphatic monofunctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and m is a number from about 5 to about 200.
Claim 22
Dependent Claim
22 words
The polyimidesiloxane according to claim 20 wherein R 1 , R 2 , R 3 , and R 4 are methyl groups.
Claim 23
Dependent Claim
14 words
The polyimidesiloxane according to claim 21 wherein R' is (CH 2 ) 3 .
Claim 24
Dependent Claim
41 words
The polyimidesiloxane of claim 20 wherein at least a portion of a siloxane diamine comprises a diamine wherein at least one of R 1 , R 2 , R 3 and R 4 is a radical selected from hydroxyl or vinyl.
Claim 25
Dependent Claim
30 words
The polyimidesiloxane according to claim 23 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 26
Dependent Claim
15 words
The polyimidesiloxane according to claim 24 wherein the R' is (CH 2 ) 3 .
Claim 27
Dependent Claim
45 words
The polyimidesiloxane of claim 20 wheren at least a portion of the siloxane diamine comprises a siloxane diamine component wherein at least one of R 1 , R 2 , R 3 and R 4 is a radical selected from acrylic-, ethylenic- or acetylenic-bearing radicals.
Claim 28
Dependent Claim
9 words
The polyimidesiloxane of claim 26 having an acrylic-bearing radical.
Claim 29
Dependent Claim
13 words
The polyimidesiloxane of claim 1 wherein the siloxane monomer is a siloxane dianhydride.
Claim 30
Dependent Claim
126 words
The polyimidesiloxane of claim 28 wherein the siloxane dianhydride has the formula ##STR38## wherein R is a substituted or unsubstituted aliphatic trifunctional radical of 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic trifunctional radical of 6 to 10 carbon atoms, and wherein none or one or more of R 1 , R 2 , R 3 and R 4 are halogen, hydride (H), vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 , are independently selected from substituted or unsubstituted aliphatic monofunctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and wherein m is about 5 to 50.
Claim 31
Dependent Claim
20 words
The polyimidesiloxane of claim 29 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 32
Dependent Claim
9 words
The polyimidesiloxane of claim 30 wherein R is ##STR39##
Claim 33
Dependent Claim
44 words
The polyimidesiloxane of claim 29 wherein at least a portion of the siloxane dianhydride comprises a dianhydride wherein at least one of R 1 , R 2 , R 3 and R 4 is a radical selected from hydride (H), halogen, hydroxyl or vinyl.
Claim 34
Dependent Claim
30 words
The polyimidesiloxane according to claim 32 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 35
Dependent Claim
10 words
The polyimidesiloxane according to claim 33 wherein R is ##STR40##
Claim 36
Dependent Claim
45 words
The polyimidesiloxane of claim 29 wherein at least a portion of the siloxane dianhydride component comprises a siloxane dianhydride wherein at least one of R 1 , R 2 , R 3 and R 4 is a radical selected from acrylic, ethylenic or acetylenic radicals.
Claim 37
Dependent Claim
9 words
The polyimidesiloxane of claim 35 having an acrylic-bearing radical.
Claim 38
Dependent Claim
48 words
A process for producing a polyimidesiloxane that is soluble in diglyme, which comprises reacting an organic diamine, a difunctional siloxane monomer, and an organic dianhydride that consists essentially of a bis(dicarboxylphenyl)hexafluoropropane dianhydride as the sole essential organic dianhydride and wherein the organic dianhydride is free of polyether linkage.
Claim 39
Dependent Claim
48 words
A process for producing a polyimidesiloxane that is soluble in diglyme, which comprises reacting an organic diamine, a difunctional siloxane monomer, and an organic dianhydride that consists essentially of a bis(dicarboxylphenyl)hexafluoropropane dianhydride as the sole essential organic dianhydride and wherein the organic dianhydride is free of polyether linkage.
Claim 40
Dependent Claim
14 words
The process of claim 37 wherein the reaction mixture also comprises an oxydiphthalic anhydride.
Claim 41
Dependent Claim
15 words
The process of claim 37 wherein the reaction mixture also comprises a biphenyl tetracarboxylic dianhydride.
Claim 42
Dependent Claim
16 words
The process of claim 37 wherein the reaction is conducted in a solvent for the polyimidesiloxane.
Claim 43
Dependent Claim
22 words
The process of claim 40 wherein the solvent is selected from diglyme, triglyme, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
Claim 44
Dependent Claim
13 words
The process of claim 37 wherein the siloxane monomer is a siloxane diamine.
Claim 45
Dependent Claim
130 words
The process of claim 37 wherein the siloxane monomer is a siloxane diamine having the formula ##STR41## wherein R' is independently selected from substituted or unsubstituted aliphatic difunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic difunctional radicals of 6 to 10 carbon atoms, and wherein none or one or more of R 1 , R 2 , R 3 and R 4 are vinyl, hydroxyl, acrylic-, ethylenic-, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 are independently selected from substituted or unsubstituted aliphatic monofunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and m is an integer from about 5 to about 50.
Claim 46
Dependent Claim
20 words
The process of claim 43 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 47
Dependent Claim
13 words
The process of claim 44 wherein R' is (CH 2 ) 3 .
Claim 48
Dependent Claim
13 words
The process of claim 37 wherein the siloxane monomer is a siloxane dianhydride.
Claim 49
Dependent Claim
130 words
The process of claim 46 wherein the siloxane monomer is a siloxane dianhydride having the formula ##STR42## wherein R is a substituted or unsubstituted aliphatic trifunctional radical of 1 to 12 carbon atoms or a substituted or unsubstituted aromatic trifunctional radical of 6 to 10 carbon atoms, and wherein none or one or more R 1 , R 2 , R 3 and R 4 are halogen, hydride (H), vinyl, hydroxyl, acrylic-, ethylenic, or acetylenic-bearing radicals, and the remainder of R 1 , R 2 , R 3 and R 4 , are independently selected from substituted or unsubstituted aliphatic monofunctional radicals of 1 to 12 carbon atoms or substituted or unsubstituted aromatic monofunctional radicals of 6 to 10 carbon atoms, and wherein m is about 5 to about 50.
Claim 50
Dependent Claim
20 words
The process of claim 47 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 51
Dependent Claim
9 words
The process of claim 48 wherein R is ##STR43##
Claim 52
Dependent Claim
35 words
The process of claim 37 wherein at least a portion of the organic diamine has the formula ##STR44## wherein Ar is an aromatic radical, and R" is at least one of hydroxyl, carboxyl, or hydrothiol.
Claim 53
Dependent Claim
9 words
The process of claim 50 wherein R" is carboxy.
Claim 54
Dependent Claim
41 words
The process of claim 43 wherein at least a portion of the siloxane diamine comprises a diamine wherein at least one of R 1 , R 2 , R 3 and R 4 is a radical selected from hydroxyl or vinyl.
Claim 55
Dependent Claim
32 words
The process according to claim 52 wherein at least one of R 1 , R 2 , R 3 and R 4 is a vinyl radical, and the remainder are methyl groups.
Claim 56
Dependent Claim
15 words
The process according to claim 53 where the R' is (CH 2 ) 3 .
Claim 57
Dependent Claim
48 words
The process according to claim 47 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 is a radical selected from hydride (H), halogen, hydroxyl, or vinyl.
Claim 58
Dependent Claim
30 words
The process according to claim 55 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 59
Dependent Claim
10 words
The process according to claim 56 wherein R is ##STR45##
Claim 60
Dependent Claim
30 words
The process according to claim 50 wherein the product of the process is reacted with a compound having at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 61
Dependent Claim
29 words
The process of claim 52 wherein the product of the process is reacted with a compound having at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 62
Dependent Claim
29 words
The process of claim 55 wherein the product of the process is reacted with a compound having at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 63
Dependent Claim
15 words
A solution comprising the polyimidesiloxane of claim 1 dissolved in a solvent for the polyimidesiloxane.
Claim 64
Dependent Claim
22 words
The solution of claim 61 wherein the solvent is selected from diglyme, triglyme, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or chlorinated solvents.
Claim 65
Dependent Claim
13 words
An article comprising a substrate coated with the polyimidesiloxane according to claim 1.
Claim 66
Dependent Claim
13 words
An article of claim 63 wherein the substrate is a wire or cable.
Claim 67
Dependent Claim
10 words
A film prepared from the polyimidesiloxane according to claim 1.
Claim 68
Dependent Claim
10 words
A fiber prepared from the polyimidesiloxane according to claim 1.
Claim 69
Dependent Claim
11 words
A molded article prepared from the polyimidesiloxane according to claim 1.
Claim 70
Dependent Claim
11 words
An extruded article prepared from the polyimidesiloxane according to claim 1.
Claim 71
Dependent Claim
6 words
A cured composition of claim 1.
Claim 72
Dependent Claim
6 words
A cured composition of claim 26.
Claim 73
Dependent Claim
6 words
A cured composition of claim 35.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1992-07-31 | 1993-01-30 | 1993-08-01 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-07-31 | 1997-01-30 | 1997-08-01 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-07-31 | 2001-01-30 | 2001-08-01 | $7700.00 | Window Closed / Lapsed |