GB2168065A - Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom - Google Patents
Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom Download PDFInfo
- Publication number
- GB2168065A GB2168065A GB08521609A GB8521609A GB2168065A GB 2168065 A GB2168065 A GB 2168065A GB 08521609 A GB08521609 A GB 08521609A GB 8521609 A GB8521609 A GB 8521609A GB 2168065 A GB2168065 A GB 2168065A
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- Prior art keywords
- siloxane
- polyimide
- formula
- siloxanes
- polyanhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Polyimide-siloxanes are provided resulting from the intercondensation of organic diamine with organosiloxane having substituents which are aromatic carboxylic anhydride groups. The polyimide-siloxanes can be used as insulation for electrical conductors, adhesives, moulding compounds, coatings for making laminates and tough elastomers.
Description
SPECIFICATION
Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom
Prior to the present invention, various methods were used to make polyimide-siloxanes consisting essentially of chemically combined blocks of polydiorganosiloxane with polyimide. Holub, U.S. Patent 3,325,450 shows the intercondensation of polydiorganosiloxane having terminal diorganoorganoaminosiloxy units with benzophenone dianhydride resulting in the production of polyimide-siloxane. Another procedure involved the intercondensation of polydiorganosiloxane having terminal alkyl amino groups with aromatic bis(ether anhydride) as shown by Heath et al, U.S. Patent 3,847,867. Afurther example of polyimide-siloxanes is shown by Ryang, U.S.Patent 4,404,350, utilizing a norbornane anhydride terminated organopolysiloxane intercondensed with organic diamine and optionally other aromatic bisanhydride.
The present invention is based on my discovery that bis(aromatic anhydride)tetraorganodisiloxane having the formula
can be used to make a polyimide-siloxane by intercondensation with organic diamine having the formula
(2) NH2R2NH2 where R is A C(113) monovalent hydrocarbon radical or substituted C(113) monovalent hydrocarbon radical,
R1 is a C(6,3) trivalent aromatic radical, R2 is a C(2.13) divalent organic radical and n is an integer equal to 1 to 2000 inclusive.
The synthesis of 1 ,3-bis(3,4-dicarboxyphenyl)-1 ,1 ,3,3-tetramethyldisiloxane dianhydride is reported by J.R. Pratt et al, Journal of Organic Chemistry, Vol.38, No.25, 1973(4271-4274). A synthesis of the bis(aromatic anhydride)disiloxane of formula (1), referred to hereinafter as "the siloxane dianhydride, is also shown in my copending application RD-15263. The siloxane dianhydride can be made be effecting reaction between a functionalized disilane and an aromatic acyl halide in the presence of an effective amount of a transition metal catalyst. The resulting halosilyl aromatic anhydride can thereafter be readily hydrolyzed to the corresponding disiloxane dianhydride.
There is provided by the present invention polyimide-siloxane which comprise chemically combined siloxane imide groups of the formula
or a mixture of such siloxane imide groups and imide groups of the formula
where R, R1, R2 and n are as previously defined, R3 is a tetravalent Cut6 3) aromatic organic radical defined below and a is an integer equal to 1 to 200 inclusive.
Radicals included within R of formula (1) are preferably aryl radicals and halogenated radicals, for example, phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc; alkenyl radicals, for example, vinyl, allyl, cyclohexenyl, etc.; C(1.8) alkyl radicals and halogenated alkyl radicals, for example, methyl, ethyl, propyl, butyl, octyl, trifluoropropyl, etc.
Radicals within R' are, for example,
where R is as previously defined, and a is an integer having a value of from 1 to 3 inclusive.
Radicals included within R2 are, for example, divalent C(220 > organic radicals selected from the class consisting of (1) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, C(28) organo teminated polydiorganosiloxane, and (c) divalent radicals included by the formula,
where Q' is a member selected from the class consisting of
and xis a whole number from 1 to 5 inclusive.
Radicals included within R3 of formula (4) are, for example,
where D is a member selected from
where R2 is as previously defined, R4 is selected from hydrogen and R, R5 is a member selected from
and divalent organic radicals of the general formula, (X)m where X is a number selected from the class consisting of divalent radicals of the formulas,
where mis 0 or 1, andy is a whole number from 1 to 5.
Organic dianhydrides which can be used in combination with the dianhydride of formula (1) in the practice of the present invention are, for example, pyromellitic dianhydride, benzophenone dianhydride, aromatic bis(ether anhydride) of Heath et al and silylnorbornane anhydride as shown by Ryang, U.S. Patent 4,381,396, assigned to the same assignee as the present invention.
Included within the organic formula of formula (2) are compounds such as
m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
4,4'-diaminodiphenyl ether;
1,5-diaminonaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-diaminotoluene;
2,6-diaminotoluene; 2,4-bis(p-amino-t-butyl)toluene; 1,3-diamino-4-isopropylbenzene;
1,2-bis(3-aminopropoxy)ethane;
m-xylylenediamine;
p-xylylenediamine;
bis(4-aminocyclohexyl)methane;
decamethylenediamine;
3-methylheptamethylenediamine;
4,4-dimethylheptamethylenediamine;
2,11 -dodecanediamine;
2,2-dimethylpropylenediamine;
octamethylenediamine;
3-methoxyhexamethylenediamine;
2,5-dimethylhexamethylenediamine;
2,5-dimethylheptamethylenediamine;
3-methylheptamethylenediamine;;
5-methylnonamethylenediamine;
1,4-cyclohexanediamine; 1,1 5-octadecanediamine; bis(3-aminopropyl)sulfide;
N-methyl-bis(3-aminopropyl)amine;
hexamethylenediamine;
heptamethylenediamine;
2,4-diaminotoluene;
nonamethylenediamine;
2,6-diaminotoluene; bis-(3-aminopropyl)tetramethyldisiloxane, etc.
There also can be used in combination with the siloxane dianhydride of formula (1) from 1 to 1000 anhydride equivalents, per anhydride equivalent of siloxane anhydride of formula (1) of siloxane anhydride having the formula,
where R and n are as previously defined. Siloxane anhydride and method for making are shown in my copending application Serial No. 647,332.
The polyimide-siloxanes of the present invention can be synthesized by effecting reaction at temperatures in the range of from 150'Cto 350 C, substantially equal molar amounts of the siloxane dianhydride or a mixture of siloxane dianhydride and organic dianhydride, or siloxane anhydride of formula (5) with the organic diamine in the presence of an inert organic solvent.
Organic solvents which can be utilized are, for example orthodichlorobenzene, meta-cresol, and dipolar aprotic solvent, for example, dimethylformamide, dimethylacidamide, N-methylpyrrolidone. The siloxane dianhydride of formula (1), where n is greater than 1,for example, n' having a value of from about 5 to about 2000, can be made by equilibrating the siloxane dianhydride of formula (1) where n is 1 with cyclopolysiloxanes such as hexaorganocyclotrisiloxane or octaorganocyclotetrasiloxane in the presence of a conventional equilibration catalyst.
The polyimide-siloxane block polymers of the present invention can be used as insulation for electrical conductors, adhesives, molding compounds, coatings for making laminates and tough elastomers.
In order that those skilled in the art will be be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation. AIl parts are by weight.
Example 1
A mixture was heated to reflux temperature consisting of 20.0 grams of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane, 5.1 grams of meta-phenylenediamine and 71 ml of ortho-dichlorobenzene. The mixture was refluxed for 2 hours with water azeotrope constantly being removed. Material started to precipitate from solution and the heating was ceased. There was then added to the mixture, 100 ml of methylene chloride after the solution cooled and the resulting homogeneous product mixture was poured into 500 ml of rapidly stirring methanol. A white product precipitated. The procedure was repeated and additional product was obtained and the resulting product dried in vacuuo. There was obtained 23.4 grams or 100% yield of material. Based on method of preparation, the product was a polyimide-siloxane consisting essentially of chemically combined units of the formula
Analysis by GPC indicates the product has a molecular weight of about 75,000. The polyimide-siloxane also has a Tg of 169 and an IV in chloroform of 0.76. A valuable insulating coating is formed in a copper wire when the wire is dipped into a 10% solution of the polymer in chloroform and allowed to air dry.
Example 2
A mixture of 5 grams of 1 ,3-bis(4'-phthalic anhydride)tetramethyldisiloxane and 20.84 grams of octamethylcyclotetrasiloxane in 50 ml of orthodichlorobenzene containing 0.5 ml of fuming sulfuric acid and 1.0 ml of concentrated sulfuric acid was heated to 11 00C for 18 hours. The mixture was allowed to cool to room temperature and 100 ml of methylene chloride was added and an excess of sodium bicarbonate was introduced to neutralize the acid. The solution was filtered with decolorizing carbon and the solvent removed in vacua. The product was then heated to 80"C under high vacuum 0.01 tory to remove any volatile products.
There was obtained a clear viscous oil which was a polydimethylsiloxane having an average of about 16 chemically combined dimethylsiloxy units with terminal dimethyl silicon anhydridesiloxy units. Based on method of preparation and proton NMR and IR analysis, the product has the following formula,
Example 3
A mixture of 50 ml of toluene, 7 grams of bis-(phthalic anyydride)tetramethyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 pJl of a fluoromethane sulfonic anhydride and 16 Wl of water was heated to 67 . After 48 hours, the resulting homogeneous solution was cooled to room temperature and the acid neutralised with 300 milligrams of anhydrous magnesium oxide.Approximately 100 ml of methylene chlorine was introduced into the mixture and the solution was filtered using decolorizing carbon. The mixture was stripped of solvent used in vacuo and the resulting viscous oil was heated to 80"C under 0.01 torr vacuum to remove any volatile cyclosiloxanes. No sublimation of phthalic anhydride was observed, indicating that equilibration occurred without end group cleavage. There was obtained 21.4 grams of a clear viscous oil representing 59% of isolated yield. Based on method of preparation and proton NMR yield and infrared analysis the product was a polydimethylsiloxane having an average of about 27 chemically combined dimethylsiloxy units and terminal dimethylsiloxy phthalic anhydride siloxy units.
A mixture of 5 grams of the above equilibrated siloxane dianhydride, 4 grams of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane and 1.24 grams of metaphenylene diamine as heated to reflux in 30 ml of orthodichlorobenzene in the presence of a catalytic amount of 4-N,N-dimethylaminopyridine. Water was formed during the reaction and it was removed continuously during the 2 hour heating period. After cooling, an additional 75 ml of methylene chloride was added to the mixture to redissolve precipitated product. The mixture was then poured into methanol and product was precipitated twice, separated and then dried. There was obtained 2 grams of a product which was dissolved in 10 ml of chloroform. There was obtained a 10 micron transparent thermoplastic elastomeric film when the product was cast.Based on method of preparation the product was a polyimide-siloxane consisting essentially of chemically combined units of the formula
where x and y are positive integers within the definition of n as previously defined. GPC analysis established that the polyimide-siloxane has a molecular weight of about 173,000 and an IV of 1.2 in chloroform. It was found that the polyimide-siloxane could be readily extruded onto copper wire and exhibited valuable insulating and dielectric properties.
Example 4
A mixture containing 5 grams of the equilibrated siloxane dianhydride described in Example 3, 1.7 grams of benzophene dianhydride and 1,24 grams of m-phenylenediamine were heated to reflux in 30 ml of o-chlorobenzene in the presence of a catalytic amount of 4-dimethylaminopyridine. Water was removed continuously during the two hour heating period. A product was isolated in a manner similar to that described in Example 3. Based on the method of preparation the product was a polyimide-siloxane consisting essentially of chemically combined units ofthe formula
where x, y andtare a defined in Example 3.
Example 5
To a 25 ml methylene chloride solution containing 0.5 grams of 4-dichloromethylsilylphthalic anhydride was added a 5 fold molar excess of water. After drying and removal of the solvent in vacuo, there was obtained a quantitative yield of a methyl siloxane having pendant silylphthalic anhydride groups within the scope of formula 5, as shown by NMR and IR analysis. The methylsiloxane was added to 5 grams of a polydimethylsiloxane fluid having terminal dimethylsiloxy phthalic anhydride units and an average of 27 chemically combined dimethylsiloxy units. The mixture was dissolved in 50 ml oftoluene and 2 drops of concentrated sulfuric acid was then added.The resulting solution was heated for 4 hours at 80"C. After cooling, 50 ml of methylene chloride was added and the solution neutralized with sodium bicarbonate, followed by drying and removal of the solvent in vacuo. To the resulting silicone fluid was added 0.5 grams of m-phenylenediamine and the mixture heated to remove water. The resulting cross-linked polymer was a tough rubber with valuable insulating and dielectric properties.
Although the above examples are directed to only a few of the very many variables which can be utilized in making the polyimide-siloxanes of the present invention, it should be understood that the present invention is directed to a much broader variety of polyimide-siloxanes which can be made by effecting reaction between siloxane dianhydride of formula (1) and organic diamine of formula (2) and optionally in the presence of organic dianhydride as shown in the description preceding these examples.
Claims (9)
1. Polyanyhydride-siloxane selected from
where R is a C < 113) monovalent hydrocarbon radical or substituted C(1.13) monovalent hydrocarbon radical, R is a C(1-13) trivalent aromatic organic radical, n is an integer equal to 1 to 2000 inclusive and n' has a value of from about 5 to about 2000.
2. A polyanhydride-siloxane in accordance with claim 1, where R is CH3- and R1 is
3. Polyanhydride-siloxane having the formula
4. Polyanhydride siloxane having the formula,
where n has a value of 1 to 2000 inclusive.
5. Polyimide-siloxane which comprises chemically combined siloxane-imide groups of the formula
or a mixture of such siloxane imide groups and imide groups of the formula
where R is a C(113) monovalent hydrocarbon radical or substituted C(113) monovalent hydrocarbon radical, R is a C(613) trivalent aromatic organic radical, R2 is a C(213) divalent organic radical R3 is a tetravalent C(13) aromatic organic radical defined below and a is an integer equal to 1 to 200 inclusive.
6. A polyimide-siloxane in accordance with claim 1 ,where R is methyl, R1 is
and R2is
7. Polyimide-siloxanes having the formula
where x andy are positive integers within the definition of n.
8. Polyimide-siloxanes having the formula
Nhere x, y and 7 are positive integers within the definition of n.
9. Poiyanhydride-siloxanes as claimed in claim 1 substantially as hereinbefore described.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67872584A | 1984-12-05 | 1984-12-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8521609D0 GB8521609D0 (en) | 1985-10-02 |
| GB2168065A true GB2168065A (en) | 1986-06-11 |
| GB2168065B GB2168065B (en) | 1990-04-25 |
Family
ID=24723992
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8521609A Expired - Lifetime GB2168065B (en) | 1984-12-05 | 1985-08-30 | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
| GB9001009A Expired - Lifetime GB2224742B (en) | 1984-12-05 | 1990-01-17 | Polyanhydride-siloxanes and polymide-siloxanes obtained therefrom |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9001009A Expired - Lifetime GB2224742B (en) | 1984-12-05 | 1990-01-17 | Polyanhydride-siloxanes and polymide-siloxanes obtained therefrom |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS61159425A (en) |
| FR (2) | FR2581648B1 (en) |
| GB (2) | GB2168065B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2190918A (en) * | 1986-05-09 | 1987-12-02 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
| GB2200647A (en) * | 1987-02-05 | 1988-08-10 | Gen Electric | Polyimide-siloxanes, method of making and use |
| EP0386547A2 (en) * | 1989-03-06 | 1990-09-12 | General Electric Company | Silicone-polycarbonate block copolymers |
| EP0386549A2 (en) * | 1989-03-06 | 1990-09-12 | General Electric Company | Aromatic polyester-siloxane block copolymers and method for making |
| EP0415204A2 (en) * | 1989-08-18 | 1991-03-06 | Wacker-Chemie Gmbh | Functional anhydride groups containing organo(poly)siloxanes, process for their preparation and their use |
| GB2194544B (en) * | 1986-09-02 | 1991-06-19 | Gen Electric | Imidopolysiloxanes and method for making |
| EP0497484A1 (en) * | 1991-01-25 | 1992-08-05 | General Electric Company | Solvent resistant silicone polyimides |
| US5376733A (en) * | 1993-03-24 | 1994-12-27 | Shin-Etsu Chemical Co., Ltd. | Precursor composition capable of yielding a polyimidesilicone resin |
| US9926338B2 (en) | 2015-05-27 | 2018-03-27 | Wacker Chemical Corporation | Carboxylic acid functional siloxanes of defined structure |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2679059B2 (en) * | 1987-09-24 | 1997-11-19 | 日本合成ゴム株式会社 | Method for producing curable polymer |
| JPS6485220A (en) * | 1987-09-25 | 1989-03-30 | Hitachi Chemical Co Ltd | Protective coating material composition for semiconductor device |
| US4939223A (en) * | 1988-10-05 | 1990-07-03 | Nippon Steel Chemical Co., Ltd. | Silicon-modified polyimides |
| GB2290299B (en) * | 1994-06-17 | 1998-01-14 | Ball Burnishing Mach Tools | Anti-lubricant compositions |
| JP4771414B2 (en) | 2006-02-15 | 2011-09-14 | 信越化学工業株式会社 | Polyimide silicone resin and thermosetting composition containing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847867A (en) * | 1971-01-20 | 1974-11-12 | Gen Electric | Polyetherimides |
| US4381396A (en) * | 1982-07-07 | 1983-04-26 | General Electric Company | Silynorbornane anhydrides and method for making |
| US4404350A (en) * | 1982-07-07 | 1983-09-13 | General Electric Company | Silicone-imide copolymers and method for making |
| US4709054A (en) * | 1984-09-04 | 1987-11-24 | General Electric Company | Silylation method and organic silanes made therefrom |
-
1985
- 1985-08-30 GB GB8521609A patent/GB2168065B/en not_active Expired - Lifetime
- 1985-11-25 FR FR8517368A patent/FR2581648B1/en not_active Expired
- 1985-12-05 JP JP27265385A patent/JPS61159425A/en active Granted
-
1986
- 1986-04-10 FR FR8605104A patent/FR2581070B1/en not_active Expired
-
1990
- 1990-01-17 GB GB9001009A patent/GB2224742B/en not_active Expired - Lifetime
-
1993
- 1993-02-15 JP JP2461193A patent/JPH069781A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2190918B (en) * | 1986-05-09 | 1991-01-09 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
| GB2190918A (en) * | 1986-05-09 | 1987-12-02 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
| GB2194544B (en) * | 1986-09-02 | 1991-06-19 | Gen Electric | Imidopolysiloxanes and method for making |
| GB2200647A (en) * | 1987-02-05 | 1988-08-10 | Gen Electric | Polyimide-siloxanes, method of making and use |
| FR2610634A1 (en) * | 1987-02-05 | 1988-08-12 | Gen Electric | NOVEL POLYIMIDE-SILOXANES, PROCESSES FOR THEIR PREPARATION AND ARTICLES CONTAINING THEM |
| EP0386547B1 (en) * | 1989-03-06 | 1994-04-06 | General Electric Company | Silicone-polycarbonate block copolymers |
| EP0386547A2 (en) * | 1989-03-06 | 1990-09-12 | General Electric Company | Silicone-polycarbonate block copolymers |
| EP0386549A2 (en) * | 1989-03-06 | 1990-09-12 | General Electric Company | Aromatic polyester-siloxane block copolymers and method for making |
| EP0386549A3 (en) * | 1989-03-06 | 1991-04-24 | General Electric Company | Aromatic polyester-siloxane block copolymers and method for making |
| EP0415204A2 (en) * | 1989-08-18 | 1991-03-06 | Wacker-Chemie Gmbh | Functional anhydride groups containing organo(poly)siloxanes, process for their preparation and their use |
| EP0415204A3 (en) * | 1989-08-18 | 1992-01-02 | Wacker-Chemie Gmbh | Functional anhydride groups containing organo(poly)siloxanes, process for their preparation and their use |
| EP0497484A1 (en) * | 1991-01-25 | 1992-08-05 | General Electric Company | Solvent resistant silicone polyimides |
| US5376733A (en) * | 1993-03-24 | 1994-12-27 | Shin-Etsu Chemical Co., Ltd. | Precursor composition capable of yielding a polyimidesilicone resin |
| US9926338B2 (en) | 2015-05-27 | 2018-03-27 | Wacker Chemical Corporation | Carboxylic acid functional siloxanes of defined structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551618B2 (en) | 1993-08-03 |
| GB9001009D0 (en) | 1990-03-14 |
| GB8521609D0 (en) | 1985-10-02 |
| FR2581648A1 (en) | 1986-11-14 |
| FR2581070B1 (en) | 1989-08-25 |
| JPS61159425A (en) | 1986-07-19 |
| FR2581648B1 (en) | 1989-06-30 |
| FR2581070A1 (en) | 1986-10-31 |
| JPH069781A (en) | 1994-01-18 |
| GB2224742A (en) | 1990-05-16 |
| GB2168065B (en) | 1990-04-25 |
| GB2224742B (en) | 1990-10-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20050829 |