CA1282534C - Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom - Google Patents
Polyanhydride-siloxanes and polyimide-siloxanes obtained therefromInfo
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- CA1282534C CA1282534C CA000536181A CA536181A CA1282534C CA 1282534 C CA1282534 C CA 1282534C CA 000536181 A CA000536181 A CA 000536181A CA 536181 A CA536181 A CA 536181A CA 1282534 C CA1282534 C CA 1282534C
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- siloxane
- formula
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- anhydride
- monovalent hydrocarbon
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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
- C08G77/48—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
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- 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
RD 17,305 POLYANHYDRIDE-SILOXANES AND
POLYIMIDE-SILOXANES OBTAINED THEREFROM
Abstract of the Disclosure Polyimide-siloxanes are provided resulting from the intercondensation of organic diamines with organosiloxanes having terminal silyl-substituted aromatic organic anhydride groups.
POLYIMIDE-SILOXANES OBTAINED THEREFROM
Abstract of the Disclosure Polyimide-siloxanes are provided resulting from the intercondensation of organic diamines with organosiloxanes having terminal silyl-substituted aromatic organic anhydride groups.
Description
- 1 - RD 17,305 POLYANHYDRIDE-SILOXANES AND
POLYIMIDE-SILOXANE-S OBT~INED THEREFROM
B'ackg'round o'f the Invention Prior to the present invention, various methods were used to make polyimide-siloxanes consisting essentially of chemically combined blocks of polydiorgano-siloxane with polyimide. U.S. Patent 3,325,450, issued June 13, 1967 to Holub, shows the intercondensation of polydiorganosiloxane having terminal diorganoorgano-aminoslloxy units with benzophenone dianhydride resulting in the production of polyimide-siloxane. Another procedure involved the intercondensation of polydiorgano-siloxane having terminal alkyl amino groups with aromatic bis(ether anhydride as shown by U.S. Patent 3,847,867, issued November 12, 1984 to Heath et al. A further example of polyimide-siloxanes is shown by U.S. Patent 4,404,350, issued September 13, 1983 to Ryang, utilizing a norbornane anhydride terminated organopolysiloxanes 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. Pratt et al, Journal of Organic Chemistry, Vol. 38, No. 25, 1973 (4271-4274). A synthesis of the Pratt et al "siloxane anhydride", and siloxane anhydride of the formula - 2 - RD 17,305 f R
~ ~iO ~
~1~ (1) ~`
C -- O
O = C--o , ' where R and n are as defined below, is shown in my UOS. Patent No. 4,709,034, issued November 24, 1987 which is assigned to the same assignee as the present invention. These siloxane anhydrides can be made by e~ecting 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 anhydr de o Formula (1), aromatic anhydride terminated organopolysiloxane of the formula O O
0 \ ~ R ~ Si - O ~ Si - Rl O , (2) O ` O
or equilibrated mixtures thereof, can be used to make polyimide-siloxane by intercondensation with organic diamine having the formula NH2R NH2 ' (3) where R is a C(1_14~ monovalent hydrocarbon radical or a C(l 1~) monovalent hydrocarbon radical substituted with the same or different radicals neutral during inter-condensation, Rl is a C(6 14~ trivalent aromatic organic radical, R2 is a C(2 14~ divalent organic radical, and n is an integer equal to 1 to about 2000 inclusive. In ~M
~L-2~2~
POLYIMIDE-SILOXANE-S OBT~INED THEREFROM
B'ackg'round o'f the Invention Prior to the present invention, various methods were used to make polyimide-siloxanes consisting essentially of chemically combined blocks of polydiorgano-siloxane with polyimide. U.S. Patent 3,325,450, issued June 13, 1967 to Holub, shows the intercondensation of polydiorganosiloxane having terminal diorganoorgano-aminoslloxy units with benzophenone dianhydride resulting in the production of polyimide-siloxane. Another procedure involved the intercondensation of polydiorgano-siloxane having terminal alkyl amino groups with aromatic bis(ether anhydride as shown by U.S. Patent 3,847,867, issued November 12, 1984 to Heath et al. A further example of polyimide-siloxanes is shown by U.S. Patent 4,404,350, issued September 13, 1983 to Ryang, utilizing a norbornane anhydride terminated organopolysiloxanes 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. Pratt et al, Journal of Organic Chemistry, Vol. 38, No. 25, 1973 (4271-4274). A synthesis of the Pratt et al "siloxane anhydride", and siloxane anhydride of the formula - 2 - RD 17,305 f R
~ ~iO ~
~1~ (1) ~`
C -- O
O = C--o , ' where R and n are as defined below, is shown in my UOS. Patent No. 4,709,034, issued November 24, 1987 which is assigned to the same assignee as the present invention. These siloxane anhydrides can be made by e~ecting 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 anhydr de o Formula (1), aromatic anhydride terminated organopolysiloxane of the formula O O
0 \ ~ R ~ Si - O ~ Si - Rl O , (2) O ` O
or equilibrated mixtures thereof, can be used to make polyimide-siloxane by intercondensation with organic diamine having the formula NH2R NH2 ' (3) where R is a C(1_14~ monovalent hydrocarbon radical or a C(l 1~) monovalent hydrocarbon radical substituted with the same or different radicals neutral during inter-condensation, Rl is a C(6 14~ trivalent aromatic organic radical, R2 is a C(2 14~ divalent organic radical, and n is an integer equal to 1 to about 2000 inclusive. In ~M
~L-2~2~
- 3 - RD 17,305 Formula (2), n is preferably 5 to about 2000 inclusive.
The siloxane anhydrides of Formulas (1) and (2) and mixtures thereof also can be equilibrated with cyclo-polydiorganosiloxane of the formula ~ sio ~ (4) R
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 cyclo-polydiorganosiloxane of Formula (4) and triorganosiloxane chain stopper, such as hexamethyldisiloxane. Additional chain stopper such as tetramethyldiphenyldisiloxane, 1,3~divinyltetramethyldisiloxane, or mixtures thereof also can be used.
Statement_of ~he Invent on In accordance with the present invention there is provided polyimidesiloxane having recurring chemically combined imidesiloxane groups comprising the inter-condensation reaction product of (A) siloxane anhydride having chemically combined units of the formula O
/ \ R1 I a \C / (3--) o or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula, ~R)bSiO ( ~ , and (6) (B) organic diamine of Formula (3) where R
The siloxane anhydrides of Formulas (1) and (2) and mixtures thereof also can be equilibrated with cyclo-polydiorganosiloxane of the formula ~ sio ~ (4) R
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 cyclo-polydiorganosiloxane of Formula (4) and triorganosiloxane chain stopper, such as hexamethyldisiloxane. Additional chain stopper such as tetramethyldiphenyldisiloxane, 1,3~divinyltetramethyldisiloxane, or mixtures thereof also can be used.
Statement_of ~he Invent on In accordance with the present invention there is provided polyimidesiloxane having recurring chemically combined imidesiloxane groups comprising the inter-condensation reaction product of (A) siloxane anhydride having chemically combined units of the formula O
/ \ R1 I a \C / (3--) o or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula, ~R)bSiO ( ~ , and (6) (B) organic diamine of Formula (3) where R
- 4 - RD 17,305 and Rl 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 O O
N / \ Rl (SiO) -SiRl/ \ N-R2_ C R R \ /
ll ll O O
or a repeating mixture of such siloxane imide groups and imide groups of the formula O O
ll ll -(N \ R3 / \ N R2) (8) C C
ll ll O O
where R, Rl, R2 and n are as previously defined, R3 is a tetravalent C(6 14) 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 o~ the present invention, there is provided polyimide-siloxane having repeating chemically com~ined group ~ ~825~3~
In another aspect of the present invention, there is provided, polyimide-siloxane which comprise repeating chemically combined siloxane imide groups of the formula O O
N / \ Rl (SiO) -SiRl/ \ N-R2_ C R R \ /
ll ll O O
or a repeating mixture of such siloxane imide groups and imide groups of the formula O O
ll ll -(N \ R3 / \ N R2) (8) C C
ll ll O O
where R, Rl, R2 and n are as previously defined, R3 is a tetravalent C(6 14) 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 o~ the present invention, there is provided polyimide-siloxane having repeating chemically com~ined group ~ ~825~3~
- 5 - RD 17,305 - sio O=C C=O
N /
R (9) N
O=C / ~ C=O
\Rl~
- sio -R
where R, Rl and R2 are as previously defined.
Radicals included within R of Formulas (1-7 and 9) are for example C(l 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 Rl are, for example, ~ ~ (R )b where R4 are monovalent neutral radicals such as C(l 8) alkyl, halo, and C(l ~) alkoxy, and b is an integer having a.value of from 1 to 3 inclusive.
Radicals included within R2 are, for example, divalent C(2 20) organic radicals selected from the class consisting of C(6 20) aromatic hydrocarbon radicals, halogenated C(6 20) aromatic hydrocarbon radicals, alkylene radicals, and cycloalkylene radicals, C(2 8) ;3~L
N /
R (9) N
O=C / ~ C=O
\Rl~
- sio -R
where R, Rl and R2 are as previously defined.
Radicals included within R of Formulas (1-7 and 9) are for example C(l 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 Rl are, for example, ~ ~ (R )b where R4 are monovalent neutral radicals such as C(l 8) alkyl, halo, and C(l ~) alkoxy, and b is an integer having a.value of from 1 to 3 inclusive.
Radicals included within R2 are, for example, divalent C(2 20) organic radicals selected from the class consisting of C(6 20) aromatic hydrocarbon radicals, halogenated C(6 20) aromatic hydrocarbon radicals, alkylene radicals, and cycloalkylene radicals, C(2 8) ;3~L
- 6 - RD 17,305 organo terminated polydiorganosiloxane, and divalent radicals included by the formula, ~O ~ Q' ( O }
where Q' is a member selected from the class consisting of O O
-O- , -C- , -S- -S- , and -CxH2x where x is a whole number from 1 to 5 inclusive.
Radicals included within R3 of Formula (6) are, for example, and ~ D
where D is a member selected from O O O O o -O- , -S-, -CNR2NC- , -C- , -oR60- and COR60C, where R2 is as previously defined, R5 is selected from hydrogen and R, R6 is a member selected from ~ ' {~
~ ' ~
~L~825~4 - 7 - RD 17,305 C(CH3) 3 Br CH3 Br Br and divalent organic radicals of the general formula, ~ (X)m~
where X is a member selected from the class consisting of divalent radicals of the formulas, O O
,.
y 2y ~ C , -S-, and -S-, where m is 0 or 1, and y is a whole number equal to from 1 to 5.
Organic dianhydrides which can be used in combination with the siloxane anhydrides of Formulas (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 the aforementioned U.S. Patent 3,847,867 and silylnorbornane anhydride as shown by U.S. Patent 4,381,396, issued April 26, 1983 to Ryang, assigned to the same assignee as the present invention.
Included within the organic diamines of formula ~3) are compounds or mi~tures thereof such as m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
~L~8Z5~
where Q' is a member selected from the class consisting of O O
-O- , -C- , -S- -S- , and -CxH2x where x is a whole number from 1 to 5 inclusive.
Radicals included within R3 of Formula (6) are, for example, and ~ D
where D is a member selected from O O O O o -O- , -S-, -CNR2NC- , -C- , -oR60- and COR60C, where R2 is as previously defined, R5 is selected from hydrogen and R, R6 is a member selected from ~ ' {~
~ ' ~
~L~825~4 - 7 - RD 17,305 C(CH3) 3 Br CH3 Br Br and divalent organic radicals of the general formula, ~ (X)m~
where X is a member selected from the class consisting of divalent radicals of the formulas, O O
,.
y 2y ~ C , -S-, and -S-, where m is 0 or 1, and y is a whole number equal to from 1 to 5.
Organic dianhydrides which can be used in combination with the siloxane anhydrides of Formulas (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 the aforementioned U.S. Patent 3,847,867 and silylnorbornane anhydride as shown by U.S. Patent 4,381,396, issued April 26, 1983 to Ryang, assigned to the same assignee as the present invention.
Included within the organic diamines of formula ~3) are compounds or mi~tures thereof such as m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
~L~8Z5~
- 8 - RD 17,305 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)tetramethyldisiloxane, etc.
The polyimide-siloxanes of the present invention can be synthesized by effecting reaction at temperatures in the range of from 150C to 350C, substantially equal ~8253~L
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)tetramethyldisiloxane, etc.
The polyimide-siloxanes of the present invention can be synthesized by effecting reaction at temperatures in the range of from 150C to 350C, substantially equal ~8253~L
- 9 - RD 17,305 molar amounts of the siloxane anhydride, 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, dimethyl-acidamide, 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-siloxanes 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 exan~ples are given by way of illustration and not by way of limitation. All parts are by weight.
A mixture, consisting of 20.0 grams of 1,3-bis(4'-phtha]ic anhydride)tetramethyldisiloxane, 5.1 grams of meta-phenylenediamine and 71 ml of ortho-dichlorobenzene was heated to reflux temperature~ 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 th~ 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 vacuo. There was obtained 23.4 grams or 100~ yield of ~E3253~
Organic solvents which can be utilized are, for example orthodichlorobenzene, meta-cresol, and dipolar aprotic solvent, for example, dimethylformamide, dimethyl-acidamide, 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-siloxanes 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 exan~ples are given by way of illustration and not by way of limitation. All parts are by weight.
A mixture, consisting of 20.0 grams of 1,3-bis(4'-phtha]ic anhydride)tetramethyldisiloxane, 5.1 grams of meta-phenylenediamine and 71 ml of ortho-dichlorobenzene was heated to reflux temperature~ 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 th~ 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 vacuo. There was obtained 23.4 grams or 100~ yield of ~E3253~
- 10 - RD 17,305 material. Based on method of preparation, the product was a polyimide-siloxane consisting essentially of chemically combined units of the formula O O
H ~ N ~ ~ C~
Analysis by GPC indicates the product has a molecular weight of about 75,000. The polyimide~siloxane has a Tg of 169C and an IV in chloroform of 0.76. A valuable 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.
A mixture of 5 grams of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane and 20.84 grams of octamethylcyclotetrasiloxane in 50 ml o orthodichloro-benzene containing 0.5 ml of uming sulfuric acid and1.0 ml of concentrated sulfuric acid was heated to 110C
or 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 80C under high vacuum 0.01 torr to remove any volatile products. There was obtained a clear viscous oil which was a polydimethyl-siloxane having an average of about 16 chemically combineddimethylsiloxy units with terminal dimethyl silicon anhydridesiloxy units. Based on method of preparation and proton NMR and IR analysis, the product had the following formula, ~2~325~4 - 11 - RD 17,305 O / ~ CH3 CH3 CH3 ~ \
\ c ~ si(o-si ~ o-si--~ ~c /
3 3 CH3 o EXAMPLE_3 A mixture of 50 ml of toluene, 7 grams of bis-(phthalic anhydride)tetramethyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 ~1 of a fluoromethane sulfonic anhydride and 26Jul of water was heated to 67C.
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 80C 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, proton NMR, and infrared analysis the product was a polydimethylsiloxane having an average of 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 meta-phenylene 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 ~82~3~
\ - 12 - RD 17,305 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 _ ~ S ~nS~
~\ ~5 OSi~
where r and 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.
_.
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-phenylene-diamine were heated to reflux in 30 ml of o-chlorobenzene - 13 - RD 17,305 in the presence of a catalytic amount of 4-dimethylamino-pyridine. 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 O O
~ ,. ..
1 3 ~ N N/ ~ CIH3 iH3 _ ~o~si~c/,~ ~i(o-si)y _ 3 O , ~ O CH3 CH3 t ~J ' ~
where t and u are as defined for r and s in Example 3.
EX~MPLE 5 To 25 ml of a methylene chloride solution containing 0.5 grams of 4-dichloromethylsilylphthalic anhydride was added a 5 fold molar e~cess of water.
Aftar 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 1, as shown by NMR and IR analysis.
The methylsiloxane was added to 5 grams of a polydimethyl-siloxane fluid having terminal dimethylsiloxy phthalic anhydride units and an average of 27 chemically combined dimethylsiloxy units. The mixture was dissolved in 50 ml ~82534 - 14 - RD 17,305 of toluene and 2 drops of concentrated sulfuric acid was then added. The resulting solution was heated for 4 hours at 80C~ 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.
There was heated to 75C, 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 75C for 15 hours. Filtration of the catalyst and removal of the toluene solvent in vacuo gave a trimethylsiloxy terminated copolymer contain-2Q ing 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 aminopropyltetramethyl-disiloxane to produce a tough cross-linked thermoplastic silicone elastomer.
''EX'A~lPLE' 7 A mixture of 30 gm (0.11 mole) of hexachloro-disilane and 23 gm (0.!1 moles~ of trimellitic anhydride acid chloride is reacted at 145C under a nitrogen 3Q atmosphere in the presence of 1 mole palladium (11) on silica gel. Car~on monoxide is evolved and tetra-chlorosilane is removed continuously as it forms. Vacuum distillation of the resulting mixture is found to provide 4-trichlorosilylphthalic anhydride.
~ydrolysis of the 4-trichlorosilylphthalic anhydride provides a cross-linked resin having the formula ~Z82~
- 15 - RD 17,305 C--C
O=C~ Si1.5 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 siloxy-phthalic anhydride units chemically combined with dimethylsiloxy units. A cured polyimidesiloxane is formed by intercondensing the silicone fluid with ~-aminopropyltetramethyldisiloxane.
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.
H ~ N ~ ~ C~
Analysis by GPC indicates the product has a molecular weight of about 75,000. The polyimide~siloxane has a Tg of 169C and an IV in chloroform of 0.76. A valuable 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.
A mixture of 5 grams of 1,3-bis(4'-phthalic anhydride)tetramethyldisiloxane and 20.84 grams of octamethylcyclotetrasiloxane in 50 ml o orthodichloro-benzene containing 0.5 ml of uming sulfuric acid and1.0 ml of concentrated sulfuric acid was heated to 110C
or 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 80C under high vacuum 0.01 torr to remove any volatile products. There was obtained a clear viscous oil which was a polydimethyl-siloxane having an average of about 16 chemically combineddimethylsiloxy units with terminal dimethyl silicon anhydridesiloxy units. Based on method of preparation and proton NMR and IR analysis, the product had the following formula, ~2~325~4 - 11 - RD 17,305 O / ~ CH3 CH3 CH3 ~ \
\ c ~ si(o-si ~ o-si--~ ~c /
3 3 CH3 o EXAMPLE_3 A mixture of 50 ml of toluene, 7 grams of bis-(phthalic anhydride)tetramethyldisiloxane, 29 grams of octamethylcyclotetrasiloxane and 75 ~1 of a fluoromethane sulfonic anhydride and 26Jul of water was heated to 67C.
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 80C 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, proton NMR, and infrared analysis the product was a polydimethylsiloxane having an average of 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 meta-phenylene 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 ~82~3~
\ - 12 - RD 17,305 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 _ ~ S ~nS~
~\ ~5 OSi~
where r and 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.
_.
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-phenylene-diamine were heated to reflux in 30 ml of o-chlorobenzene - 13 - RD 17,305 in the presence of a catalytic amount of 4-dimethylamino-pyridine. 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 O O
~ ,. ..
1 3 ~ N N/ ~ CIH3 iH3 _ ~o~si~c/,~ ~i(o-si)y _ 3 O , ~ O CH3 CH3 t ~J ' ~
where t and u are as defined for r and s in Example 3.
EX~MPLE 5 To 25 ml of a methylene chloride solution containing 0.5 grams of 4-dichloromethylsilylphthalic anhydride was added a 5 fold molar e~cess of water.
Aftar 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 1, as shown by NMR and IR analysis.
The methylsiloxane was added to 5 grams of a polydimethyl-siloxane fluid having terminal dimethylsiloxy phthalic anhydride units and an average of 27 chemically combined dimethylsiloxy units. The mixture was dissolved in 50 ml ~82534 - 14 - RD 17,305 of toluene and 2 drops of concentrated sulfuric acid was then added. The resulting solution was heated for 4 hours at 80C~ 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.
There was heated to 75C, 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 75C for 15 hours. Filtration of the catalyst and removal of the toluene solvent in vacuo gave a trimethylsiloxy terminated copolymer contain-2Q ing 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 aminopropyltetramethyl-disiloxane to produce a tough cross-linked thermoplastic silicone elastomer.
''EX'A~lPLE' 7 A mixture of 30 gm (0.11 mole) of hexachloro-disilane and 23 gm (0.!1 moles~ of trimellitic anhydride acid chloride is reacted at 145C under a nitrogen 3Q atmosphere in the presence of 1 mole palladium (11) on silica gel. Car~on monoxide is evolved and tetra-chlorosilane is removed continuously as it forms. Vacuum distillation of the resulting mixture is found to provide 4-trichlorosilylphthalic anhydride.
~ydrolysis of the 4-trichlorosilylphthalic anhydride provides a cross-linked resin having the formula ~Z82~
- 15 - RD 17,305 C--C
O=C~ Si1.5 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 siloxy-phthalic anhydride units chemically combined with dimethylsiloxy units. A cured polyimidesiloxane is formed by intercondensing the silicone fluid with ~-aminopropyltetramethyldisiloxane.
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 (20)
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)bSiO , and (B) organic diamine of the formula 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 inter-condensation, R1 is a C(6-14) trivalent aromatic organic radical, R2 is a C(2-14) 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, - 17 - RD 17,305 a mixture thereof, and mixtures of such groups with imide groups of the formula where R is selected from the class consisting of C(1-14) monovalent hydrocarbon radicals and C(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R1 is a C(6-14) trivalent aromatic organic radical, R2 is a C(2-14) 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 - 18 - RD 17,305 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, R1 is a C(6-14) trivalent aromatic organic radical, R2 is a C(2-13) divalent organic radical, R3 is a tetravalent C(6-13) 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 - 19 - RD 17,305 where r and s are positive integers.
6. Polyimide-siloxanes having the formula where t and u are positive integers.
- 20 - RD 17,305
- 20 - RD 17,305
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 where R is selected from a C(1-14) monovalent hydro-carbon radicals and monovalent C(1-14) hydrocarbon radicals substituted with neutral radicals, c is a whole number equal to 0 to 2 inclusive and d is an integer equal to 1 to 3 inclusive.
8. A polyimide-siloxane intercondensation reaction product comprising the polyanhydride siloxane of claim 7 and an organic diamine of the formula NH2R2NH2 , where R is a C(2-14) divalent organic radical.
9. A polyimide-siloxane reaction product in accordance with claim 8 resulting from the inter-condensation of polyanhydride-siloxane of claim 7, organic diamine and organic dianhydride.
10. A polyanhydride-siloxane in accordance with claim 7, where R is CH3- and R1 is - 21 - RD 17,305
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(1-14) 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 - 22 - RD 17,305 (A) anhydride-siloxane having rrom 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(1-13) monovalent hydrocarbon radicals, R1 is a C(6-13) trivalent aromatic organic radical and n is an integer equal to 1 to 2000 inclusive.
15. Anhydride-methylsiloxane selected from the class consisting of (A) anhydride methylsiloxane having from about 5 to about 2000 dimethylsiloxy units and terminal units of the formula - 23 - RD 17,305 (B) methylsiloxy phthalic anhydride having chemically combined units of the formula, , and (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 anhydride siloxane units of the formula , where R is a member selected from the class consisting of C(1-14) monovalent hydrocarbon radicals and C(1-14) monovalent hydrocarbon radicals and C(1-14) monovalent hydrocarbon radicals substituted with neutral radicals, - 24 - RD 17,305 R1 is a C(6-14) trivalent aromatic organic radical, and e is a whole number equal to 0 or 1.
17. Polyanhydride siloxane comprising anhydride siloxane units of the formula, , chemically combined with organosiloxane units of the formula , 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 inter-condensation, R1 is a C(6-14) trivalent aromatic organic radical, f is a whole number equal to 0 or 1 and g is an integer equal to 1 to 3 inclusive.
18. Silylanhydride siloxane compirising chemically combined units of the formula, .
19. Silyl anhydride siloxane comprising chemically combined units of the formula where R is a C(1-14) monovalent hydrocarbon radical or a C(1-14) monovalent hydrocarbon radical substituted with - 25 - RD 17,305 the same or different radicals neutral during intercondensation.
20. Polyanhydride siloxane in accordance with claim 17, where R is methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86116286A | 1986-05-09 | 1986-05-09 | |
| US861,162 | 1986-05-09 |
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| Publication Number | Publication Date |
|---|---|
| CA1282534C true CA1282534C (en) | 1991-04-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000536181A Expired - Fee Related CA1282534C (en) | 1986-05-09 | 1987-05-01 | Polyanhydride-siloxanes and polyimide-siloxanes obtained therefrom |
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| Country | Link |
|---|---|
| JP (2) | JP2659534B2 (en) |
| CA (1) | CA1282534C (en) |
| FR (1) | FR2598426B1 (en) |
| GB (1) | GB2190918B (en) |
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| US4795680A (en) * | 1986-05-09 | 1989-01-03 | General Electric Company | Polyimide-siloxanes, method of making and use |
| 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 |
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| 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 |
| GB2168065B (en) * | 1984-12-05 | 1990-04-25 | Gen Electric | Polyanhydride-siloxanes and polyimide-siloxanes obtained 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
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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 |
| GB2190918A (en) | 1987-12-02 |
| GB2190918B (en) | 1991-01-09 |
| JPS62263227A (en) | 1987-11-16 |
| JP2659534B2 (en) | 1997-09-30 |
| FR2598426B1 (en) | 1993-02-19 |
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