US4829131A
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Novel soluble polymidesiloxanes and methods for their preparation and use
Assignee: Sumitomo Bakelite Co Ltd
•
Filing: 1988-02-09
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Granted: 1989-05-09
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Expires: 2008-02-09
Abstract
Abstract Substantilly fully imidized polyimidesiloxanes which are based on a mixture consisting essentially 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 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.
Inventors
- 👤 Chung J. Lee
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 06:22
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
Claims Analysis
Total Claims: 60
Claim 1
Independent Claim
80 words
In a substantially fully imidized polyimidesiloxane which is soluble in diglyme, comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the organic dianhydride consists essentially of a mixture of a biphenyl tetracarboxylic dianhydride and a benzophenone tetracarboxylic dianhydride, the organic diamine is a mixture of 2,4-tolyldiamine and 2,6-tolyldiamine, and the siloxane monomer is present in a proportion and has a sufficient block size to render the polyimidesiloxane soluble in diglyme.
Claim 2
Dependent Claim
80 words
In a substantially fully imidized polyimidesiloxane which is soluble in diglyme, comprising the reaction product of an organic dianhydride, a difunctional siloxane monomer, and an organic diamine, the improvement wherein the organic dianhydride consists essentially of a mixture of a biphenyl tetracarboxylic dianhydride and a benzophenone tetracarboxylic dianhydride, the organic diamine is a mixture of 2,4-tolyldiamine and 2,6-tolyldiamine, and the siloxane monomer is present in a proportion and has a sufficient block size to render the polyimidesiloxane soluble in diglyme.
Claim 3
Dependent Claim
55 words
The polyimidesiloxane of claim 1 wherein the organic dianhydride consists essentially of a mixture of 3,3',4,4' biphenyl tetracarboxylic dianhydride (BPDA) and 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) in a molar ratio in the range of about 5 parts of BPDA to 1 part of BTDA to about 0.2 part of BPDA to 1 part of BTDA.
Claim 4
Dependent Claim
45 words
The polyimidesiloxane of claim 2 wherein the organic diamine is a mixture of 2,4-tolyldiamine and 2,6-tolyldiamine, in a molar ratio in the range of about 9 moles of 2,4-tolyldiamine to 1 mole of 2,6-tolyldiamine to about 0.1 mole of 2,4-tolyldiamine to 1 mole of 2,6-tolyldiamine.
Claim 5
Dependent Claim
36 words
The polyimidesiloxane of claim 1 wherein at least a portion of the organic diamine has the formula ##STR27## wherein Ar is an aromatic radical, and R" is at least one of a hydroxyl, carboxyl, or hydrothiol.
Claim 6
Dependent Claim
9 words
The polyimidesiloxane of claim 4 wherein R" is carboxyl.
Claim 7
Dependent Claim
40 words
The polyimidesiloxane of claim 1 wherein at least a portion of the organic diamine component has the formula ##STR28## wherein Ar is an aromatic radical, and R'" is at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 8
Dependent Claim
13 words
The polyimidesiloxane of claim 1 wherein the siloxane monomer is a siloxane diamine.
Claim 9
Dependent Claim
126 words
The polyimidesiloxane of claim 7 wherein the siloxane diamine has the formula ##STR29## 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 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 are independently selected from a substituted or unsubstituted aliphatic monofunctional radical of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic monofunctional radical of 6 to 10 carbon atoms, and m is a number from about 5 to about 200.
Claim 10
Dependent Claim
22 words
The polyimidesiloxane according to claim 8 wherein R 1 , R 2 , R 3 , and R 4 are methyl groups.
Claim 11
Dependent Claim
14 words
The polyimidesiloxane according to claim 9 wherein R' is --CH 2 -- 3 .
Claim 12
Dependent Claim
44 words
The polyimidesiloxane of claim 8 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 hydroxyl or vinyl.
Claim 13
Dependent Claim
30 words
The polyimidesiloxane according to claim 11 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 14
Dependent Claim
15 words
The polyimidesiloxane according to claim 12 wherein the R' is --CH 2 -- 3 .
Claim 15
Dependent Claim
48 words
The polyimidesiloxane of claim 8 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 acrylic-, ethylenic- or acetylenic-bearing radicals.
Claim 16
Dependent Claim
9 words
The polyimidesiloxane of claim 14 comprising an acrylic-bearing radical.
Claim 17
Dependent Claim
13 words
The polyimidesiloxane of claim 1 wherein the siloxane monomer is a siloxane dianhydride.
Claim 18
Dependent Claim
124 words
The polyimidesiloxane of claim 16 wherein the siloxane dianhydride as the formula ##STR30## wherein R is substituted or unsubstituted aliphatic trifuctional radicals of 1 to 12 carbon atoms, or substituted or unsubstituted aromatic trifuctional 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 , are independently selected from a substituted or unsubstituted aliphatic monofunctional radical 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 19
Dependent Claim
20 words
The polyimidesiloxane of claim 17 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 20
Dependent Claim
9 words
The polyimidesiloxane of claim 18 wherein R is ##STR31##
Claim 21
Dependent Claim
47 words
The polyimidesiloxane of claim 17 wh-erein 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 22
Dependent Claim
30 words
The polyimidesiloxane according to claim 20 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 23
Dependent Claim
10 words
The polyimidesiloxane according to claim 21 wherein R is ##STR32##
Claim 24
Dependent Claim
49 words
The polyimidesiloxane of claim 17 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 is a radical selected from acrylic, ethylenic or acetylenic radicals.
Claim 25
Dependent Claim
9 words
The polyimidesiloxane of claim 23 comprising an acrylic-bearing radical.
Claim 26
Dependent Claim
71 words
A process for producing a polyimidesiloxane which comprises reacting an organic diamine, a difunctional siloxane monomer, and an organic dianhydride, wherein the organic dianhydride consists essentially of a mixture of a biphenyl tetracarboxylic dianhydride and a benzophenone tetracarboxylic dianhydride, the organic diamine is a mixture of 2,4-tolyldiamine and 2,6-tolyldiamine, and the siloxane monomer is present in a proportion and has a sufficient block size to render the polyimidesiloxane soluble in diglyme.
Claim 27
Dependent Claim
71 words
A process for producing a polyimidesiloxane which comprises reacting an organic diamine, a difunctional siloxane monomer, and an organic dianhydride, wherein the organic dianhydride consists essentially of a mixture of a biphenyl tetracarboxylic dianhydride and a benzophenone tetracarboxylic dianhydride, the organic diamine is a mixture of 2,4-tolyldiamine and 2,6-tolyldiamine, and the siloxane monomer is present in a proportion and has a sufficient block size to render the polyimidesiloxane soluble in diglyme.
Claim 28
Dependent Claim
16 words
The process of claim 25 wherein the reaction is conducted in a solvent for the polyimidesiloxane.
Claim 29
Dependent Claim
22 words
The process of claim 26 wherein the solvent is selected from diglyme, triglyme, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or mixtures thereof.
Claim 30
Dependent Claim
13 words
The process of claim 25 wherein the siloxane monomer is a siloxane diamine.
Claim 31
Dependent Claim
130 words
The process of claim 25 wherein the siloxane monomer is a siloxane diamine having the formula ##STR33## 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 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 are independently selected from a substituted or unsubstituted aliphatic monofunctional radical 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 32
Dependent Claim
20 words
The process of claim 29 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 33
Dependent Claim
13 words
The process of claim 30 wherein R' is --CH 2 -- 3 .
Claim 34
Dependent Claim
13 words
The process of claim 25 wherein the siloxane monomer is a siloxane dianhydride.
Claim 35
Dependent Claim
128 words
The process of claim 32 wherein the siloxane monomer is a siloxane dianhydride having the formula ##STR34## wherein R is substituted or unsubstituted aliphatic trifunctional radicals of 1 to 12 carbon atoms or substituted or 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 , are independently selected from a substituted or unsubstituted aliphatic monofunctional radical 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 36
Dependent Claim
20 words
The process of claim 33 wherein R 1 , R 2 , R 3 and R 4 are methyl groups.
Claim 37
Dependent Claim
9 words
The process of claim 34 wherein R is ##STR35##
Claim 38
Dependent Claim
36 words
The process of claim 25 wherein at least a portion of the organic diamine has the formula ##STR36## wherein Ar is an aromatic radical, and R" is at least one of a hydroxyl, carboxyl, or hydrothiol.
Claim 39
Dependent Claim
9 words
The polyimidesiloxane of claim 36 wherein R" is carboxy.
Claim 40
Dependent Claim
44 words
The process of claim 29 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 frm hydroxyl or vinyl.
Claim 41
Dependent Claim
32 words
The process according to claim 38 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 42
Dependent Claim
14 words
The process according to claim 39 the R' is --CH 2 -- 3 .
Claim 43
Dependent Claim
47 words
The process of claim 33 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 44
Dependent Claim
30 words
The process according to claim 41 wherein at least one of R 1 , R 2 , R 3 and R 4 is vinyl and the remainder are methyl groups.
Claim 45
Dependent Claim
10 words
The process according to claim 42 wherein R is ##STR37##
Claim 46
Dependent Claim
30 words
The process wherein the polymidesiloxane product of the process of claim 36 is reacted with a compound comprising at least one of an acrylic-, an ethylenic- or an acetylenic-bearing radical.
Claim 47
Dependent Claim
27 words
The process of 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.
Claim 48
Dependent Claim
27 words
The process of 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.
Claim 49
Dependent Claim
29 words
The process of claim 41 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.
Claim 50
Dependent Claim
15 words
A solution comprising the polyimidesiloxane of claim 1 dissolved in a solvent for the polyimidesiloxane.
Claim 51
Dependent Claim
22 words
The solution of claim 47 wherein the solvent is selected from diglyme, triglyme, 1-methyl-2-pyrrolidinone, tetrahydrofuran, methyl ethyl ketone, phenols or chlorinated solvents.
Claim 52
Dependent Claim
13 words
An article comprising a substrate coated with a polyimidesiloxane according to claim 1.
Claim 53
Dependent Claim
13 words
An article of claim 49 wherein the substrate is a wire or cable.
Claim 54
Dependent Claim
10 words
A film prepared from the polyimidesiloxane according to claim 1.
Claim 55
Dependent Claim
10 words
A fiber prepared from the polyimidesiloxane according to claim 1.
Claim 56
Dependent Claim
11 words
A molded article prepared from a polyimidesiloxane according to claim 1.
Claim 57
Dependent Claim
11 words
An extruded article prepared from a polyimidesiloxane according to claim 1.
Claim 58
Dependent Claim
6 words
A cured composition of claim 1.
Claim 59
Dependent Claim
6 words
A cured composition of claim 14.
Claim 60
Dependent Claim
6 words
A cured composition of claim 23.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-05-08 | 1992-11-07 | 1993-05-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-05-08 | 1996-11-07 | 1997-05-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-05-08 | 2000-11-07 | 2001-05-09 | $7700.00 | Window Closed / Lapsed |