GB2224742A - Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom - Google Patents
Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom Download PDFInfo
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- GB2224742A GB2224742A GB9001009A GB9001009A GB2224742A GB 2224742 A GB2224742 A GB 2224742A GB 9001009 A GB9001009 A GB 9001009A GB 9001009 A GB9001009 A GB 9001009A GB 2224742 A GB2224742 A GB 2224742A
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- siloxane
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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
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- 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
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- 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
Description
2,2_ 2 4 7 4 '02 - I POLYANHYDRIDE-SILOXANES AND POLYIMlDE-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 polydiorganosiloxane7 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. A further 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.
RD-15973 The present invention is based on my discovery that bis(aromatic anhydride)tetraorganodisiloxane having the formula (1) 0 c 0 R +si-0] Si-R I, 1 n 1..1 c R R 0 can be used to make a polyimide-siloxane by intercondensa10 tion with organic diamine having the formula (2) NH 2 R 2 NH 2 where R is a C (1-13) monovalent hydrocarbon radical or sub- stituted C (1-13) monovalent hydrocarbon radical, R 1 is a - 2 c (6-13) trivalent aromatic organic radical, R 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 anhy dride)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 by 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 halo silyl aromatic anhydride can thereafter be readily hydro lyzed to the corresponding disiloxane dianhydride.
1 RD-15973 There is provided by the present invention polyimide-siloxane which comprise chemically combined siloxane imide groups of the formula 5.
2 (3) -N R (IiO)n-1R N-R c R R or a mixture of such silaxane imide groups and imide groups of the formula (4) is Y1 3,"" C"' 2 "",N-R)a c 11 0 where R, R 1, R 2 and n are as previously defined, R 3 is a tetravalent C (6-13) 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 radials and halogenated aryl 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.
1 RD-15973 Radicals included within R 1 are, for example, 00 0 0 (R) a where R is as previously defined, and a is an integer having 5 a value of from 1 to 3 inclusive.
Radicals included within R z are, for example, divalent C(2-2.) organic radicals selected from the'class consisting of (1) aromatic hydrocarbon radicals having from 6-20 carbon atoms and halogenated derivatives thereof, (bl 10 alkylene radicals and cycloalkylene radicals having from 2-20 carbon atoms, C (2-8) organo terminated polydiorganosiloxane, and (c) divalent radicals included by the formula, -(D-Q i--& where Q' is a member selected from the class consisting of is for example,
0 0 11 -0- 0 -- ' -S- 11 v g -S-, and -C X H 2x and x is a whole number from 1 to 5 inclusive.
R Radicals included within R 3 of formula (4) are, 1 1 RD-15973 and 1 -Gofl, &D, 5 where D is a member selected from 9 0 0 0 1 2 11 1 5 115 4 V4 R where R 2 is as previously defined, R 5 is selected from hydrogen and R,. R 5 is a member selected from CH 3 CH 3 CH 1 0 - p 0 0-- CH 3 CH 3 0 F CH CH 3 Br CH 3 Br Br CH 3 0 0 Br Br CH, Br C (CH ) 20 3 2 r Br and divalent organic radicals of the general formula, (X) m RD-15973 where X is a member selected from the class consisting of divalent radicals of the formulas, 0 -c. H - - g-# -9-, and -S-, y 2Y ' 8 where m is 0 or 1, and y is a whole number from 1 to 5.
Organic dianhydrid-as which can be used in combination with the siloxane dianhydride of formula (1) in-the practice of the present invention are, for example, pyromel 10 litic dianhydride, benzophenone dianhydride, aromatic bis7 (ether anhydride) of Heath et al and sily1norbornane anhydride as shown by Ryang, U.S. Patent 4,381,396, assigned to the same assignee as the present invention.
Included within the organic diamines of formula is (2) are compounds such as m-phenylenediamine; p-phenylenediAmine; 4,4'-diaminodiphenylpropane; 4,4'- diaminodipenylmethane; benzidine; 4,4'-diaminodiphenyl sulfide; 4,4'- diaminodiphenyl sulfone; 4,4'-diaminodiphenyl ether; 1,5diaminonaphthalene; 3,3'-dimethylbenzidine; 3,3'-dimethoxybenzidine; 2,4diaminotoluene; 2,6-diaminotoluene; RD-15973 is 2,4-bis(p-amino-t-butyl)toluene; 1,3-diamino-4-isopropylbenzene; 1,2bis(3-aminopropoxy)ethane; m-xylylenediamine; p-xylylenediamine; bis(4aminocyclohexyl)methane; decamethylenediamine; 3-methylheptamethylenedi ' amine; 4,4-dimethylheptamethylenediamine; 2,11-dodecanediamine; 2,2dimethylpropylenediamine; octamethylenediamine; 3methoxyhexamethylenediamine; 2,5-dimethylhexamethylenediamine; 2,5dimethylheptamethylenediamine; 3-methylheptamethylenediamine; 5methylnonamethylenediamine; 1,4-cyclohexanediamine; 1,15octadecanediamine; bis(3-aminopropyl)sulfide; N-methyl-bis(3aminopropyl)amine; hexamethylenediamine; heptamethylenediamine; 2,4diaminotoludne; nonamethylenediamine; 2,6-diaminotoluene; bis-(3-amino propyl)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, 1 RD-15973 (5) --os i 1 0 0 c 0 j where R and n are as previously defined. Siloxane anhydride 5 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 1SO'C to 350% 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.:he presence of an inert organic solvent.
Organic solvents which can be utilized are, for -example orthodichlorobetizene, 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 4 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 pre25 sent invention can be used as insulation for electrical 9 RD- 15973 conductors, adhesives, molding compounds, coatings for making laminates and tough elastomers.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation. All 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 mix- ture, 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 1007. yield of material. Based on method of preparation, the product was a polyimide-siloxane consisting essentially of chemically combined units of the formula 4 -g- RD-15973 0 go 0 c CH N 7113 "i30 C/ S i,., 0 c U 9 3 0 0 H 3 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'O.76. A valuable insulating coating is formed on a copper wire when the wire is dippe4 into a 10% solution of the polymer in chloroform and allowed to air dry.
1 10 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 1100C for IS 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 wih decolorizing carbon and the sol- vent removed in vacuo. The product was then heated to SO'C under high vacuum 0.01 torr 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 RD-15973 proton NMR and IR analysis, the product had the following formula, 0 n ' 0 c to H CH C\ 0 0. 3 ?113 1 3 0 0 c si 0-si 1 L- 1 16 1 LC C 0 - - CH 3 L1 3 Lon 3 Examt)1e 3.
It 0 A mixture of 50 ml of toluene, 7 grams of.bis(phthalic anyydride)tetramethyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 pl of a fluoromethane sulfonic anhydride and 26 pl of water was heated to 67'. After 48 hours, the resulting homogeneous solution was cooled to room temperature and the acid neutralized with 300 milligrams of anhydrous magnesium oxide. Approximately 100 ml of methylene chloride was introduced into the mixture and the solution was filtered using decolorizing carbon. The mix ture was stripped of solvent in vacuo and the resulting viscous oil was heated to BOOC under 0.01 torr vacuum to remove any volatile cyclosiloxanes. No subiimation of phthalic anhydride was ob ' served, indicating that equilibra- tion 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 and infrared analysi-s the product was a polydimethylsiloxane having an average of about 27 chemicaily combined dimethylsiloxy units and terminal dimethylsiloxy phthalic anhydride siloxy units.
RD- 15973 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 was heated to reflux in 30 ml of orthodichloroben- zene 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 0 0 om c c CH 3 1 (Osi) n OS i- ú c pe \\C:I)-Si 0 0 3 --' 0 0 4 If cl CH ?H - c C.
3 ---J, 0 n n siosiL 4 1 1 C/ ki CH CH 3 0 X 99 where x and y are positive integers within the definition of n as previously defined. GPC analysis established that the polyimide-siloxane had a molecular weight of about 173,000 and an IV of 1.2 in chloroform. It was found that the y RD-15973 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 benzophenone dianhydride and 1.24 grams of m-phenylenediamine were heated to reflux in 30 ml of ochlorobenzene in the presence of a catalytic amount of 4dimethylaminopyri- dine. 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 of the formula 0 #I c is 7 '%N 3 --o-si_ c// 1 go 1_. CH 3 0 1 1 0 01 N / C"- 13 SM 1 % 3 \\ c., ( i (O-S 1 i -z I. CH CH Z 0 3 43y 0 0 't 0 a - c 91 )-NI C-, \ c 0 T N- IP / 1 c 0.0 X where x, y and Z are as defined in Example 3.
RD-15973 Example 5.
To a 25 ml methylene chlorilde solution containing 0.5 grams of 4dichloromethylsilylphthalic 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 of toluene and 2 drops of concentrated sulfuric acid was then added. The resulting solution was heated for 4 hours at 800C. After cooling, 50 ml of methyl- ene 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-lin)ed polymer was a tough rubber with valuable insulating and dielectric proper.ties.
Although the ab6ve 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 q 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.
RD-15973
Claims (5)
1. Polyanhydride-siloxane selected from 7 is 0 11 1.."C I C " 1 R -0 R=-f S i 0+_---T-S i - R %,," 1 n c R c 11 0 8 where R is a C R 1 -+si -01 n O=C C=0 monovalent hydrocarbon radical or sub (1-13) stituted C (1-13) monovalent hydrocarbon radical, R 1 is a c trivalent aromatic organic radical, n is an integer (6-13) 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 CH3and R 1 is q -1:
3. Polyanhydride-siloxane having the formula -is- RD- 15973 0 11 0 c 09 H H CH 3 C, 0 7 3 3 1 0 0 1.c:t -S'(0-"-)-1-60-S'LC CC 11 CH H CH 11 0 3 3 3 0 4. Polyanhydride siloxane having the formula, CH 3 W.
0 C-0 le 0 where n has a value of 1 to 2000 inclusive.
5. Polyimide-siloxane which..comprises chemically combined siloxane-imide groups of the formula 0 0 R c 1. 1 2 -N R (SiO) -SiR 1 n 1- 1.11, R fl 4 0 or a mixture of such siloxane imide groups and imide groups of the formula RD- 15973 where R is a C stituted C I' C._1 - 2 R N R:-a 0 (1-13) trivalent (1-13) monovalent hydrocarbon radical or submonovalent hvdrocarbon radical R 1 is a C (6-13) aromatic organic radical, R2 is a C (2-13 divalent organic radical R 3 is a tetravalent C aro (6-13) matic 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, R 1 is and R 2 is -0 7 _ 7. Polyimide-siloxanes having the formula 4 1 CH CH C 1 3 1 --(-osi) OS iA 1 n 1 t-11 3 CH 3 0 -"' 0 1.1 at 0 1,9 c C 0 U c N / 1 K 3 0 '%&C" _ 1 1. 0 CH 3 y 0 11 C-., CH ?H c 001 0 1 3 0 Siosi 0 1 1 of CH CH 0 3 3 0 X where x and y are positive integers within the definition of n.
y 8. Polyimide-siloxanes having the formula 0 I I, c CH 1 \N 3 0- Si_ C.,/ 1 to L. CH 3 0 1 0 01 / C'- H CH N 3 1 3 i (O-Si c 1 -z It CH CH 0 3 q3Y 0 0 #1 0 c ER 1 1 OrN C N f I@ c., X.( cc 0 c).0 where x, y and_ -Z- are positive integers within the definition of.n.
Polyanhydride-siloxanes as claimed in claim 1, gubstantially as hereinbefore described.
1 Cl - Amendments to the claims have been filed as follows An anhydride-siloxane selected from [A] organasiloxy anhydride having chemically combined units of the formula F R 1 1 R 0=c--, "'-'C_C) fl and [B] anhydride-siloxane consisting essentially of 5 to 2000 chemically combined diorganosiloxy units and a mixture of terminal units of the formula R c C R 11 0 and organosiloxy anhydride units of [A], where R and the organic radicals of the diorganosiloxy units are selected from C(1-13) monovalent hydrocarbon radicals and substituted C(1-13) monovalent hydrocarbon radicals, R' is a C(1-13) trivalent aromatic organic radical, n is an integer of to 2 to 2000 inclusive.
- pt 0 - 2. Polyanhydride-siloxane having the formula R 1 (_5j.0_)n 1 (D 0 , 1 -0/ 11 0 where R is a C(1-13) monovalent hydrocarbon radical or a substituted C(1- 13) monovalent hydrocarbon radical and n is an integer equal to 2 to 2000 inclusive.
3.
Polyanhydride-methylsiloxane as claimed in claim 2.
4. An anhydridemethylsiloxane consisting essentially of 5 to 2000 chemically combined dimethylsiloxy units and a mixture of terminal units of the formula Cw- ' J 1 -5 ' 1 C- 3 0 :p and methylsiloxy phthalic anhydride having chemically units of the formula 0H3 1 -5j-01 C=0 1 -LI EI n and n is an integer equal to 2 to 2000 inclusive
5.
Anhydride-siloxane as claimed in claim 1 substantially as hereinbefore described in the Example.
Published 1990 at The Patent Office, State House, 6671 High Holborn. London WCIR4TP. Further copies maybe obtained from The Patent Office. Sales Branch. St Mary Cray. Orpington. Kent BR5 3RD Printed by MLiltiplex techniques ltd. St Mary Cray. Kent. Con 1 87
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67872584A | 1984-12-05 | 1984-12-05 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9001009D0 GB9001009D0 (en) | 1990-03-14 |
| GB2224742A true GB2224742A (en) | 1990-05-16 |
| GB2224742B GB2224742B (en) | 1990-10-03 |
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 Before (1)
| 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 |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPS61159425A (en) |
| FR (2) | FR2581648B1 (en) |
| GB (2) | GB2168065B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0497484A1 (en) * | 1991-01-25 | 1992-08-05 | General Electric Company | Solvent resistant silicone polyimides |
| GB2290299A (en) * | 1994-06-17 | 1995-12-20 | Ball Burnishing Mach Tools | Anti-lubricant compositions |
| EP1842870A2 (en) | 2006-02-15 | 2007-10-10 | Shin-Etsu Chemical Company, Ltd. | Polymide silicone resin and thermosetting composition comprising the same |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2659534B2 (en) * | 1986-05-09 | 1997-09-30 | ゼネラル・エレクトリック・カンパニイ | Polyanhydride-siloxane and polyimide-siloxane obtained therefrom |
| US4795680A (en) * | 1986-05-09 | 1989-01-03 | General Electric Company | Polyimide-siloxanes, method of making and use |
| DE3715313A1 (en) * | 1986-09-02 | 1988-03-10 | Gen Electric | IMIDOPOLYSILOXANES AND METHOD FOR THEIR PRODUCTION |
| 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 |
| US4945147A (en) * | 1989-03-06 | 1990-07-31 | General Electric Company | Aromatic polyester-siloxane block copolymers and method for making |
| US4945148A (en) * | 1989-03-06 | 1990-07-31 | General Electric Company | Silicone-polycarbonate block copolymers |
| DE3927312A1 (en) * | 1989-08-18 | 1991-02-21 | Wacker Chemie Gmbh | ANHYDRIDE-FUNCTIONAL ORGANO (POLY) SILOXANE, METHOD FOR THE PRODUCTION AND USE OF THIS ORGANO (POLY) SILOXANE |
| JP2764674B2 (en) * | 1993-03-24 | 1998-06-11 | 信越化学工業株式会社 | Polyimide silicone resin precursor composition |
| US9926338B2 (en) | 2015-05-27 | 2018-03-27 | Wacker Chemical Corporation | Carboxylic acid functional siloxanes of defined structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404350A (en) * | 1982-07-07 | 1983-09-13 | General Electric Company | Silicone-imide copolymers and method for making |
| GB2164041A (en) * | 1984-09-04 | 1986-03-12 | Gen Electric | Silylation method |
Family Cites Families (2)
| 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 |
-
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
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404350A (en) * | 1982-07-07 | 1983-09-13 | General Electric Company | Silicone-imide copolymers and method for making |
| GB2164041A (en) * | 1984-09-04 | 1986-03-12 | Gen Electric | Silylation method |
Non-Patent Citations (4)
| Title |
|---|
| Abstracts of 165th Natio * |
| ACS Org.Cont.Plast.Chem. * |
| Chem.Abs.Vol.82.No.16.19 * |
| J.Org.Chem.Vol.38.No.25. * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0497484A1 (en) * | 1991-01-25 | 1992-08-05 | General Electric Company | Solvent resistant silicone polyimides |
| GB2290299A (en) * | 1994-06-17 | 1995-12-20 | Ball Burnishing Mach Tools | Anti-lubricant compositions |
| GB2290299B (en) * | 1994-06-17 | 1998-01-14 | Ball Burnishing Mach Tools | Anti-lubricant compositions |
| EP1842870A2 (en) | 2006-02-15 | 2007-10-10 | Shin-Etsu Chemical Company, Ltd. | Polymide silicone resin and thermosetting composition comprising the same |
| EP1842870A3 (en) * | 2006-02-15 | 2010-01-13 | Shin-Etsu Chemical Company, Ltd. | Polymide silicone resin and thermosetting composition comprising the same |
| US7781541B2 (en) | 2006-02-15 | 2010-08-24 | Shin-Etsu Chemical Co., Ltd. | Polyimide silicone resin and thermosetting composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2581070A1 (en) | 1986-10-31 |
| GB2224742B (en) | 1990-10-03 |
| FR2581070B1 (en) | 1989-08-25 |
| GB8521609D0 (en) | 1985-10-02 |
| GB9001009D0 (en) | 1990-03-14 |
| FR2581648A1 (en) | 1986-11-14 |
| FR2581648B1 (en) | 1989-06-30 |
| JPH0551618B2 (en) | 1993-08-03 |
| GB2168065B (en) | 1990-04-25 |
| JPH069781A (en) | 1994-01-18 |
| GB2168065A (en) | 1986-06-11 |
| JPS61159425A (en) | 1986-07-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20050829 |