GB2190918A - Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom - Google Patents
Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom Download PDFInfo
- Publication number
- GB2190918A GB2190918A GB08619909A GB8619909A GB2190918A GB 2190918 A GB2190918 A GB 2190918A GB 08619909 A GB08619909 A GB 08619909A GB 8619909 A GB8619909 A GB 8619909A GB 2190918 A GB2190918 A GB 2190918A
- Authority
- GB
- United Kingdom
- Prior art keywords
- siloxane
- formula
- units
- anhydride
- monovalent hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Polyimide-siloxanes are provided resulting from the intercondensation of organic diamine with organosiloxane having terminal silyl-substituted aromatic organic anhydride groups.
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. A further example of polyimide-siloxanes is shown by Ryang, U.S.Patent 4,404,350, utilizing a norbornane an hydride terminated organopolysiloxane intercondensed with organic diamine and optionally other aromatic bisanhydride.
The synthesis of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyl disiloxane dianhydride is shown by J.R.
Prater et al, Journal of Organic Chemistry, Vol.38, No. 25, 1973 (4271-4274). A synthesis of the Prater et al "siloxane anhydride", and siloxane anhydride of the formula
WHERE R and n are as defined below, is shown in my copending application Serial No. 765,089, filed August 13, 1985, which is assigned to the same assignee as the present invention and incorporated herein by reference. These siloxane an hydrides 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 and thereafter hydrolyzing the resulting halosilyl aromatic anhydride.
The present invention is based on my discovery that siloxane an hydride of Formula (1), aromatic anhydride terminated organopolysiloxane of the formula
or equilibrated mixtures thereof, can be used to make polyimide-siloxane by intercondensation with organic diamine having the formula
NH2R2NH2 (3) where R is a C(114) monovalent hydrocarbon radical or a C(,~14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R1 is a C(Sa4) trivalent aromatic organic radical, R2 is a C(2~,4) divalent organic radical, and n is an integer equal to 1 to about 2000 inclusive. In Formula (2), n is preferably 5 to about 200 inclusive.
The siloxane anhydride of Formulas (1) and (2) and mixtures thereof also can be equilibrated with cyclopolydiorganosiloxane of the formula
where R is as previously defined and P is an integer equal to 3 to 8 inclusive, or siloxane anhydride of Formula (1) can be equilibrated with a mixture of cyclopolydiorganosiloxane of Formula (4) and triorganosiloxane chain stopper, such as hexamethyldisiloxane. Additional chain stopper such as tetramethyldiphenyldisilox ane, 1 ,3-divinyltetramethyldisiloxane, or mixtures thereof also can be used.
In accordance with the present invention there is provided polyimidesiloxane having recurring chemically combined imidesiloxane groups comprising the intercondensation reaction product of
(A) siloxane anhydride having chemically combined units of the formula
or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula,
(R) bSiOo t and (6) (B) organic diamine of formula (3) where R and R1 are as previously defined, a is a whole number equal to 0 to 2 inclusive and b is a whole number equal to 0 to 3 inclusive.
In another aspect of the present invention, there is provided, polyimide-siloxane which comprise repeating chemically combined siloxane imide groups of the formula
or a repeating 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 Cm6,4) aromatic organic radical defined below n is as previously defined and c is an integer equal to 1 to 200 inclusive.
In a further aspect of the present invention, there is provided polyimide-siloxane having repeating chemically combined groups of the formula
where R and R2 are as previously defined.
Radicals included within R of Formulas (1-7 and 9) are for example C(,~8) alkyl radicals and halogenated alkyl radicals, for example, methyl, ethyl, propyl, butyl, octyl, trifluoropropyl, etc.; alkenyl radicals, for example, vinyl, allyl, cyclohexenyl, etc.; aryl radicals and halogenated aryl radicals, for example, phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc.;
Radicals included within R1 are, for example,
where R4 are monovalent neutral radicals such as C(,~8) alkyl, halo, and C(,~8) alkoxy, and b is an integer having a value of from 1 to 3 inclusive.
Radicals included within R2 are, for example, diva lent C(220) organic radicals selected from the class consisting of C(6-20) aromatic hydrocarbon radicals, haiogenated C(20) aromatic hydrocarbon radicals, alkylene radicals, and cycloalkylene radicals, C(28) organo terminated polydiorganosiloxane, and divalent radicals included by the formula,
where Q' is a member selected from the class consisting of -0-
-S- , and CxH2x , and xis a whole number from 1 to 5 inclusive.
Radicals included within R3 of Formula (6) are, for example,
where D is a member selected from -0- , -S-
-OR6O- and
where R2 is as previously defined, R5 is selected from hydrogen and R, R6 is a member selected from
and divalent organic radicals of the general formula,
where Xis a member selected from the class consisting of divalent radicals of the formulas, -CyH2y~,
and -S- where m is O or 1, andy is a whole number equal to from 1 to 5.
Organic dianhydrides which can be used in combination with the siloxane anhydride of Formula (1) and (2) or mixtures thereof 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 diamines of formula (3) are compounds such as
m-phendylenediamine;
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; 1,15-octadecanediamine;
bis(3-aminopropyl)sulfide;
N-methyl-bis(3-aminopropyl)amine;
hexamethylenediamine;
heptamethylenediamine;
2,4-diaminotoluene;
nonamethylenediamine;
2,6-diaminotoluene; bis-(3-aminopropyl )tetramethyldisiloxa ne, etc.
The polyimide-siloxanes of the present invention can be synthesized by effecting reaction at temperatures in the range of from 1 500C to 350"C, substantially equal molar amounts of the siloxane an hydride, or a mixture of siloxane anhydride and organic dianhydride, 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 (2), 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 (2) where n is 1 with cyclopolysiloxanes such as hexaorganocyclotrisiloxane or octaorganocyclotetrasiloxane in the presence of a conventional equilibration catalyst.
Some of the polyimide-siloxane can be block polymers and 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 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 at a 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 additionai 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. Avaluable insulating coating is formed on 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 110"C 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 vacuo. The product was then heated to 800C 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 proton NMR and IR analysis, the product had the following formula,
Example 3
A mixture of 50 ml of toluene, 7 grams of bis(phthalic anhydride)tetramethyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 pl of a fluoromethane sulfonic anhydride and 26,at of water was heated to 670C. 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 mixture was stripped of solvent 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 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 was heated to reflux in 30 ml of orthodichlorobenzene in the presence of a catalytic amount of 4-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 rand s 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 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 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 of the formula
whereat and u are as defined for rand sin 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 las shown by NMR and IR analysis. The methylsiloxane was added to 5 grams of a polydimethylsiloxane fluid having terminal dimethylsiloxy phthaiic 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 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.
Example 6
There was heated to 75"C, a 50 ml toluene solution of 3.0 g of 4-phthalicanhydride, methylsiloxane of
Example 5,3.0 g of octamethylcyclotetrasiloxane, and 6 mg of hexamethyldisiloxane as a chain terminator. A catalytic amount of Nafion acidic resin was introduced and the mixture heated to 75"C for 15 hours. Filtration of the catalyst and removal of the toluene solvent invacuo gave a trimethylsiloxy terminated copolymer containing dimethylsiloxy and 4-phthalicanhydride, methylsiloxy units. NMR and infrared analysis were consistent with the copolymer structure. The polymer was readily cross-linked with a polyamine such as gamma aminopropyltetramethyldisiloxane to produce a tough cross-linked thermoplastic silicone elastomer.
Example 7
A mixture of 30 gm (0.11 mole) of hexachlorodisilane and 23 gm (0.11 moles) of trimellitic anhydride acid chloride is reacted at 145"C under a nitrogen atmosphere in the presence of 1 mole palladium (11) on silica gel.
Carbon monoxide is evolved and tetrachlorosilane is removed continuously as it forms. Vacuum distillation of the resulting mixture is found to provide 4-trichlorosilylphthalic anhydride.
Hydrolysis of the 4-trichlorosilylphthalic anhydride provides a cross-linked resin having the formula
A mixture of 4-trichlorosilylphthalic anhydride and dimethyldichlorosilane is cohydrolyzed in water to produce a silicone fluid. The silicone fluid consists essentially of chemically combined siloxyphthalic anhydride units chemically combined with dimethylsiloxy units. A cured polyimidesiloxane is formed by intercondensing the silicone fluid with a-aminopropyltetramethyidisiloxane.
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 anhydride and organic diamine as shown in the description preceding these examples.
Claims (22)
1. Polyimide siloxane having recurring chemically combined imidesiloxane groups comprising the intercondensation reaction product of
(A) siloxane anhydride having chemically combined units of the formula,
or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula
(R)b SiO##### , and
(B) organic diamine of the formula
NH2R2NH2, where R is a C(1~14 > monovalent hydrocarbon radical or a C(1~14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R1 is a C( > 14) trivalent aromatic organic radical, R2 is a C(214) divalent organic radical, a is a whole number equal to 0 to 2 inclusive and b is a whole number equal to 0 to 3 inclusive.
2. Polyimide siloxane comprising repeating groups selected from the class consisting of,
a mixture thereof, and mixtures of such groups with imide groups of the formula
where R is selected from the class consisting of C(,~14) monovalent hydrocarbon radicals and C(1~14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R1 is a C(S14) trivalent aromatic organic radical, R2 is a C(214) divalent organic radical, R3 is a tetravalent C(1~14) aromatic organic radical and n is an integer equal to 1 to about 2000 inclusive.
3. Polyimide-siloxane which comprises chemically combined siloxane-imide repeat groups of the formula
or a mixture of such siloxane imide groups and imide groups of the formula
where R is a C(1-14) monovalent hydrocarbon radical or substituted C(1~14) monovalent hydrocarbon radical, R is a C( > 14) trivalent aromatic organic radical, R2 is a C(2-13) divalent organic radical R3 is a tetravalent C( > 13) aromatic organic radical, a is an integer equal to 1 to 200 inclusive, and n is an integer equal to 1 to about 2000 inclusive.
4. Polyimide-siloxane in accordance with claim 1, where R is methyl, R1 is
and R2 is
5. Polyimide-siloxanes having the formula
where rand s are positive integers.
6. Polyimide-siloxanes having the formula
where t and u are positive integers.
7. Polyanhydride siloxane having from about 5 to about 2000 chemically combined units comprising a mixture of silyl anhydride units of the formula
and organosiloxane units of the formula
(R) 2S iO4 d T where R is selected from a C(1~14) monovalent hydrocarbon radicals and monovalent C(1~14) hydrocarbon radicals substituted with neutral radicals, c is a whole number equal toO to 2 inclusive and d is an integer equal to 1 to 3 inclusive.
8. A polyimide-siloxane reaction product comprising the polyanhydride siloxane of claim 7 and an organic diamine of the formula
N H2R2N H2, where R is a C(214) divalent organic radical.
9. A polyimide-siloxane reaction product in accordance with claim 8 from the reaction of polyanhydridesiloxane of claim 7, organic diamine and organic dianhydride.
10. A polyanhydride-siloxane in accordance with claim 7, where R is CH3- and R1 is
11. Polyanhydride-siloxane having the formula
12. Polyanhydride siloxane having the formula,
where n has a value of 1 to 2000 inclusive.
13. Polyanhydride siloxane having the formula
where R is a member selected from the class consisting of a C(,~14) monovalent hydrocarbon radical or substituted C(1~14) monovalent hydrocarbon radical and n is an integer equal to 1 to 2000 inclusive.
14. Anhydride-siloxane selected from the class consisting of
(A) anhydride-siloxane having from about 5 to about 2000 diorganosiloxy units chemically combined with
terminal units of the formula
(B) organosiloxy anhydride having chemically combined units of the formula,
(C) anhydride-siloxane consisting essentially of chemically combined diorganosiloxy units and a mixture of
terminal units of (A) and organosiloxy anhydride units of (B), where the organo radicals of the diorganosiloxy units of (A) and (C) and R are members selected from the class consisting of C(1~13) monovalent hydrocarbon radicals and substituted C(,~13) monovalent hydrocarbon radicals, R1 is a C( > 13) trivalent aromatic orgmanic radical and n is an integer equal to 1 to 2000 inclusive.
15. Anhydride-methylsiloxane selected from the class consisting of
(A) anhydride methylsilxoane having from about 5 to about 2000 dimethylsiloxy units and terminal units of
the formula
(B) methylsiloxy phthalic anhydride having chemically combined units of the formula,
(C) anhydride methylsiloxane consisting essentially of chemically combined dimethylsiloxy units and a
mixture of terminal units of (A) and methylsiloxy phthalic anhydride units of (B) and n is an integer equal
to 1 to 2000 inclusive.
16. Polyanhydride siloxane comprising chemically combined an hydride siloxane units of the formula
where R is a member selected from the class consisting of C(,~14) monovalent hydrocarbon radicals and C(114 monovalent hydrocarbon radicals C(,~14) monovalent hydrocarbon radicals substituted with neutral radicals,
R1 is a C( > 14) trivalent aromatic organic radical, and eisa whole number equal toO or 1.
17. Polyanhydride siloxane comprising anhydride siloxane units of the formula,
chemically combined with organosiloxane units of the formula
(R) gSiO(4 ), where R is a C(1~14) monovalent hydrocarbon radical or a C(1~14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R1 is a C( > a4) trivalent aromatic organic radical, f is a whole number equal toO or 1 and g is an integer equal to 1 to 3 inclusive.
18. Silylanhydride siloxane comprising chemically combined units of the formula,
19. Silyl anhydride siloxane comprising chemically combined units oftheformula
where R is a C(,~14) monovalent hydrocarbon radical or a C(1~14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation.
20. Polyanhydride siloxane in accordance with claim 17, where R is methyl.
21. Polyimide siloxane according to claim 1, substantially as herein described.
22. Polyimide siloxane substantially as described in any one of the specific Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86116286A | 1986-05-09 | 1986-05-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8619909D0 GB8619909D0 (en) | 1986-09-24 |
| GB2190918A true GB2190918A (en) | 1987-12-02 |
| GB2190918B GB2190918B (en) | 1991-01-09 |
Family
ID=25335063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8619909A Expired - Lifetime GB2190918B (en) | 1986-05-09 | 1986-08-15 | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
Country Status (4)
| Country | Link |
|---|---|
| JP (2) | JP2659534B2 (en) |
| CA (1) | CA1282534C (en) |
| FR (1) | FR2598426B1 (en) |
| GB (1) | GB2190918B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2200647A (en) * | 1987-02-05 | 1988-08-10 | Gen Electric | Polyimide-siloxanes, method of making and use |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485220A (en) * | 1987-09-25 | 1989-03-30 | Hitachi Chemical Co Ltd | Protective coating material composition for semiconductor device |
| JP2543729B2 (en) * | 1987-11-18 | 1996-10-16 | 東レ・ダウコーニング・シリコーン株式会社 | Phthalates modified organopolysiloxane and method for producing the same |
| US4829131A (en) * | 1988-02-09 | 1989-05-09 | Occidental Chemical Corporation | Novel soluble polymidesiloxanes and methods for their preparation and use |
| US4895968A (en) * | 1988-10-24 | 1990-01-23 | General Electric Company | Acid equilibration method for organcpolysiloxanes having carbon-silicon-bonded aromatic organic radicals |
| US5362837A (en) * | 1993-07-26 | 1994-11-08 | General Electric Company | Preparation of macrocyclic polyetherimide oligomers from bis(trialkylsilyl) ethers |
| EP3063227B1 (en) * | 2013-10-31 | 2020-09-02 | Dow Silicones Corporation | Cross-linked composition and method of forming the same |
| WO2015066161A1 (en) * | 2013-10-31 | 2015-05-07 | Dow Corning Corporation | Cross-linked composition and method of forming the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2168065A (en) * | 1984-12-05 | 1986-06-11 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4330666A (en) * | 1980-09-19 | 1982-05-18 | General Electric Company | Method for making polyetherimides |
| US4404350A (en) * | 1982-07-07 | 1983-09-13 | General Electric Company | Silicone-imide copolymers and method for making |
| US4381396A (en) * | 1982-07-07 | 1983-04-26 | General Electric Company | Silynorbornane anhydrides and method for making |
| GB8512738D0 (en) * | 1984-09-04 | 1985-06-26 | Gen Electric | Silylation method |
| US4709054A (en) * | 1984-09-04 | 1987-11-24 | General Electric Company | Silylation method and organic silanes made therefrom |
| JPH0551618A (en) * | 1991-08-19 | 1993-03-02 | Nkk Corp | Desiliconizing method for molten iron |
-
1986
- 1986-05-30 FR FR8607775A patent/FR2598426B1/en not_active Expired - Lifetime
- 1986-05-30 JP JP61123855A patent/JP2659534B2/en not_active Expired - Lifetime
- 1986-08-15 GB GB8619909A patent/GB2190918B/en not_active Expired - Lifetime
-
1987
- 1987-05-01 CA CA000536181A patent/CA1282534C/en not_active Expired - Fee Related
-
1995
- 1995-10-11 JP JP7288103A patent/JP2670250B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2168065A (en) * | 1984-12-05 | 1986-06-11 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2200647A (en) * | 1987-02-05 | 1988-08-10 | Gen Electric | Polyimide-siloxanes, method of making and use |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2598426A1 (en) | 1987-11-13 |
| JP2670250B2 (en) | 1997-10-29 |
| GB8619909D0 (en) | 1986-09-24 |
| JPH08208841A (en) | 1996-08-13 |
| CA1282534C (en) | 1991-04-02 |
| GB2190918B (en) | 1991-01-09 |
| JPS62263227A (en) | 1987-11-16 |
| JP2659534B2 (en) | 1997-09-30 |
| FR2598426B1 (en) | 1993-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4795680A (en) | Polyimide-siloxanes, method of making and use | |
| EP0113357B1 (en) | Silicone-imide copolymers and method for making | |
| US4808686A (en) | Silicone-polyimides, and method for making | |
| AU6142886A (en) | Flame retardant wire coating compositions | |
| US4604442A (en) | Organopolysiloxane-polyamide block polymers and method for making | |
| GB2168065A (en) | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom | |
| US4522985A (en) | Heat curable silicone-polyimide block copolymers | |
| US4794153A (en) | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom | |
| US4517342A (en) | Heat curable compositions | |
| US4139547A (en) | Silicone containing bis-thioether aromatic amines | |
| CA1282534C (en) | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom | |
| JPH0553822B2 (en) | ||
| JPH0546375B2 (en) | ||
| US4634610A (en) | Heat curable silicone polyimide compositions | |
| JPH06128375A (en) | Polydiorganosiloxane for silicone-imide copolymer | |
| DE3618714B4 (en) | New polyanhydride siloxane and polyimide-siloxane polymers - prepd. from polyanhydride siloxane and organic di:amine, useful for moulding, coating etc. | |
| USRE30677E (en) | Silicone containing bis-thioether aromatic amines | |
| EP0268080A1 (en) | Polyetherimides and method for making | |
| CA1274648A (en) | Flame retardant wire coating compositions | |
| JPH0552340B2 (en) | ||
| DE3542346A1 (en) | Polyanhydride siloxane(s) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20060814 |