JPS60240733A - Thermosettable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Citing Related Applications This application is part of the inventor's co-pending Application No. 507,182, filed June 23, 1983, for "Curable Silicone Polyimide Block Copolymers". This is a continuation application. Also, "Thermosetting silicone polyimide block copolymer" filed on April 30, 1984
See also the inventor's co-pending application for US Pat. These applications, like the present invention, are assigned to the same assignee and are incorporated herein by reference.

BACKGROUND OF THE INVENTION The present invention relates to a platinum catalyst, a norbornane or norbornene silicone block copolymer, and a micro-81H with a norbornane or norbornene silicone block copolymer.
= SiOxH, relating to a thermosetting composition capable of undergoing an addition reaction.

Prior to the present invention, room temperature curable polydiorganosiloxanes, such as silanol-terminated polydimethylsiloxanes, were used in one- or two-pack systems based on moisture-sensitive type crosslinkers used in the composition. In a typical one-pack system, U.S. Pat.
Basically, methyltriacetoxysilane and silanol-stopped polydimethylsiloxane are used, as disclosed in No. 3 & 891. Nirache (N1tzsbe)
The Tunosic system disclosed in US Pat. No. 065.194, et al., requires mixing a silanol-stopped polydimethylsiloxane with a curing catalyst such as ethyl orthosilicate in combination with dibutyltin dilaurate. The two-pack system requires that the curing catalyst be mixed with the silanol-stopped polydimethylsiloxane prior to use.

The above-mentioned one-pack and two-pack room temperature curing Mk button skin yarns 1 are generally fooled.If it is desired to improve the tensile strength of the cured silicone, a reinforcing filler such as a silica filler is added in an amount of 5 to 300 parts per 100 parts of silicone polymer. It is necessary to use the amount of Another method that is effective in improving the toughness of cured silicone polymers is to introduce diarylene siloxy units into the polymer chain to chemically bond with the diarylene siloxy units and create a substantial bond with the diorganosiloxy units. The aim is to create a copolymer composed of Although these methods do improve the modulus (psi') of silicone polymers, these methods are either not economical or elongation (a) x tensile strength psi
) is not as strong as desired in the final product.

The present inventor's co-pending Application No. 56Z609 (filed January 3, 1984) for ``Silicone-polyimide copolymers, condensation curable compositions obtained therefrom, and methods for producing the same'' includes Silicone-polyimide copolymers with terminal silanol or silicon hydride radicals are described which essentially use polyimide. Hydrosilation reaction is used to introduce silicon-hydrogen into the terminal norbornene group of polyimide. The resulting hydrosilyl-terminated polyimide is reacted with a silanol-terminated polydiorganosiloxane in the presence of a catalyst to form a silanol-terminated polydiorganosiloxane-polyimide copolymer. Room-temperature or low-temperature condensation curable compositions using such silanol-terminated copolymers as a base provide cured silicone-curable compositions with improved toughness.
A polyimide copolymer is obtained.

The present inventor's co-pending application for ``Thermosetting Silicone-Polyimide Block Copolymer'' filed on April 30, 1984 states that a free radical initiator such as an organic peroxide is chemically Combined=810. It is disclosed to be useful in carrying out thermal curing of norbornene or norbornane polydiorganosiloxanes which may have H3 units.

The present invention provides a thermosetting silicone-polyimide composition that can be converted into a high-strength elastomer.
For example, an organosilane or organosiloxane fluid,
Chemically bonded=S i O1H.

or = 81 H units can also be obtained by using an effective amount of platinum catalyst to carry out the polyaddition reaction with a norbornane or norbornene silicone block copolymer as hereinafter defined having H units. For example, a mixture of polyvinylarylsilane or vinyl-containing polydiorganosiloxane and a silicon hydride terminated polyimide having formula (1) below can be readily cured when used with a platinum catalyst at temperatures from about 5°C to about 250°C.

BYR? ft' RfuX Here, R-Ra, Y, Q and nti% are defined in the claims, and r has a value of 0 to 2000.

Alternatively, a vinyl-terminated silicon-polyimide block polymer of formula (2) can be cured with silicon hydride as defined below in the presence of an effective amount of a platinum catalyst.

Here, R7 is defined later, R9 is 0 OH, m is an integer having a value of 1 to 100, and X is 1 to 1.
G is an integer having a value of 04, and G is a divalent group formed by reacting a silicon hydride-terminated polyimide of formula () with a vinyl-terminated polydiorganosiloxane of formula (3).

The tensile strength (psi) of the resulting silicone polyimide elastomer copolymers is improved compared to conventional room temperature cured or organic peroxide cured organopolysiloxane elastomers.

DESCRIPTION OF THE INVENTION The thermosetting (i.e., heat curable) composition provided by the present invention consists of the following components.

France) (i) Chemically bonded Mi-SiH or Mi-8i
(a polydiorganosiloxane having 4H1 units, and (ii) a norbornane or norbornene silicone block copolymer having a chemically bonded block selected from a mixture of (i) and a polyimide; (to)) a chemically bonded =SiH Or Mi S i 02
A polyfunctional organosilicon material capable of a polyaddition reaction of (A) 2 involving addition between H3 units (this polyfunctional organosilicon material comprises at least two chemically bonded Mi-SiH or Mi-Si !H, units selected from organosilanes, organopolysilanes, organosiloxanes, organopolysiloxanes, cyclopolyorganosiloxanes and mixtures thereof, and (0) an effective amount of a platinum catalyst.

Examples of groups included in the formula (]) include divalent 02-20 organic groups, which include (a) 6 to 6 carbon atoms;
20 aromatic hydrocarbon groups and their halogenated derivatives; to) alkylene groups and cycloalkylene groups having 2 to 20 carbon atoms; 4-11 alkylene-terminated polydiorganosiloxanes; selected from the class consisting of divalent radicals included.

Q' is selected from the class consisting of:

1 Here, x' is an integer from 1 to 5. Groups included in QK in formula (j) include tetravalent groups selected from the following formulas.

as well as Here, D is selected from the following:

R and -0R100-1 However, BIO is the following formula: %formula% and the following general formula: is selected from the class consisting of divalent radicals of the formula:

II Here, y is an integer from 1 to 5. In the above formula, R1-
Ra is selected from hydrogen and 01-$alkyl group, R1
are the same or different 01-11-valent hydrocarbon groups or substituted at-ts-valent hydrocarbon groups, and Y is a divalent group selected from 10- and -c(R1)- and
n is an integer equal to 0 to 200, R1 is hydrogen and R
7, and p is equal to 0 or 1.

The silicon hydride-terminated polyimide is prepared by heating a mixture of a fulbornene-terminated polyimide of the following formula (4) and a silicon hydride of the following formula (5) in the presence of an inert organic solvent and an effective amount of a platinum catalyst. It can be produced by evaporating and dissipating the organic solvent.

Here, RR'', Y, Q%n and r are as defined above.

Groups included in R1 to R6 in formulas (1) and (4) above include, for example, hydrogen, methyl, ethyl, propyl, butyl, and the like. Groups included in R7 in the above formula include, for example, aryl groups and halogenated aryl-A4 (e.g., t,
phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc.), alkenyl groups (e.g. jr-F!, vinyl, glyl, cyclohexenyl'4'), 0t-
Examples include a alkyl group and halogenated alkyl group (eg, methyl, ethyl, propyl, butyl, octyl group), and the like.

The norbornene-terminated polyimide of formula (41) is

According to the formula below, organic diamine, norbornene anhydride (
(optionally together with norbornene dicarboxylic acid monoalkyl ester) and an organic dianhydride.

Here, Q%R, R''-R' and Y are as defined above.

Some examples of organic dianhydrides that may be used in the practice of the present invention to prepare norbornene-terminated polyimides of formula (4) with norbornene anhydride or norbornene dicarboxylic acid monoalkyl esters include, for example, penzophenone dianhydride, pyromellitic acid dianhydride, 2,2-bis[4
-(5,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride 7) l, 4-
(2,3-dicarboxyphenoxy)-4'-(54-
dicarboxyphenoxy)diphenyl-2,2-propane anhydride 1dn, and bisnorbornane siloxane dianhydride of the following formula and mixtures thereof.

Examples of organic diamines that can be used for producing the polyimide block of the silanol-terminated polydiorganosiloxane-polyimide copolymer include O-phenylenediamine, m-phenylenediamine, p-phenylenediamine,
4.4'-diaminodiphenylpropane, 4.4'-diaminodiphenylmethane (usually referred to as 4,4'-methylene dianiline), 4.4'-diaminodiphenylsulfi)" (,A usually 4.4'- Synonymous with thiodianiline),
4.4'-diaminodiphenyl ether (always 4.4'
-oxydianiline), 1,5-diaminonaphthalene, 3'-dimethylbenzidine, 53'-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)toluene, 1,3-diamino -4-isopropylbenzene, 1゜2-bis(3-aminopropoxy)ethane,
Benzidine, m-xylylene diamine, p-xylylene diamine, 2.4-diaminotoluene, 2.6-diaminotoluene, bis(4-aminocyclohexyl)methane, 3-methylhebutamethylenecyahane, 4.4 -dimethylhebutamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine,
2.5-dimethylhexamethylenediamine, 2.5-dimethylhexamethylenediamine, 3-methylhexamethylenediamine, 5-methylnonamethylenediamine, 1.
4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-aminopropyl)sul2ide, N
-Methyl-bis(3-aminopropyl)amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(4-aminobutyl)tetramethyldisiloxane There are siloxanes and mixtures of these diamines.

In addition to the silicon hydride of formula (5), the thermosetting compositions of the present invention also include the silicon hydride described in US Pat. Silicon hydrides containing siloxanes, such as those disclosed in US Pat.

For example, a hydrogenated silicone resin consisting essentially of chemically bonded diorganohydrogenated siloxy units and 8102 units (where the silicon-bonded organo group is the same as R7).
a linear hydrogenated polysiloxane consisting essentially of chemically bonded diorganosiloxy units and said diorganosiloxy units; a linear hydrogenated polysiloxane consisting essentially of chemically bonded diorganosiloxy units and terminal diorganosiloxy units; Siloxane-containing silicon hydrides selected from the class consisting of linear hydrogenated polysiloxane couplers, as well as mixtures thereof, may be used.

Some of the polyvinyldiorganosiloxanes used in the thermosetting organopolycloxane compositions of the present invention are encompassed by the following formula.

Here, R7 is as defined above, and t is 0 or the viscosity of the vinyl siloxane is 100 to 2011.0 at 25°C.
A positive integer with a value sufficient to equal 00 centipoise. A preferred polyvinyl diorgano, /D xane has a terminal unit of the formula:

0*Ha(OHI), 5too,.

This can vary from about α05 to about 45 molar ratios, l114 to
About 2 molar ratios are preferred.

Polyvinyldiorganopolysiloxanes, including both linear and cyclopolysiloxanes, may be prepared by equilibrating a suitable cyclotetrasiloxane with a suitable vinyl-terminated low molecular weight polysiloxane chain terminator. The equilibration catalyst used is preferably a mild acid catalyst such as toluenesulfonic acid or an acid-treated clay such as filtrol. The Filtrol was manufactured by Filtrol Corporation of Los Angeles, California.
) is a sulfonic acid activated clay manufactured and sold by. When equilibration has proceeded until about 85% of the cyclopolysiloxane has been converted to a linear polymer, neutralization of the acid catalyst with a base or, in the case of acid-activated clays, simply furnace-out provides a linear polymer. It is preferred to eliminate excess cyclics so that the linear polymer has a low volatile content and is relatively pure. Alkali metal hydroxides such as potassium hydroxide or sodium hydroxide can also be used as catalysts.

Platinum catalysts that can be used in the practice of the present invention include, for example, Karstät U.S. Pat.
No. 775.442, U.S. Pat. No. 4159.601 and A. 159.662 to Ashby 1 and U.S. Pat. ) is a platinum complex of an unsaturated siloxane disclosed in US Pat.

Various fillers and pigments can be incorporated into the room temperature curable compositions of the present invention. For example, titanium dioxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, oxidized silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, ground quartz, calcium carbonate, etc. can be used. The amount of filler used can obviously vary within a wide range depending on the intended use. For example, for certain sealant applications, the curable compositions of the present invention may be filler-free. In other applications, for example when the curable compositions of the invention are used in the production of bonding materials, 7 parts per 100 parts of polydiorganosiloxane-polyimide copolymer by weight.
It is also possible to use more than 0.00 parts of filler. For such applications, fillers such as ground quartz, polyvinyl chloride or mixtures thereof can be the primary filler.

Fillers such as those having an average particle size in the range of about 1 to 10 microns are preferred.

The synthesis of the norbornene-terminated polyimide of formula (4) involves mixing approximately equimolar amounts of an organic diamine or dianhydride with an effective amount of chain-terminating norbornene anhydride or norbornene dicarboxylic acid monoalkyl ester (which can be used to adjust the polyimide to a desired molecular weight). can be carried out in a conventional manner using the following methods: During the polymerization of norbornene-terminated polyimides, organic solvents such as orthodichlorobenzene can be used and temperatures ranging from 140°C to 200°C can be used. The reaction can be carried out under an inert atmosphere, such as nitrogen, to minimize undesirable side reactions. Reaction times can vary from less than 30 minutes to up to 3 hours depending on the nature of the reactants and the desired molecular weight of the polyimide.

The silicon hydride-terminated polyimide of formula (1) is prepared by combining the norbornene-terminated polyimide of formula (4) with a suitable silicon hydride of formula (5), such as dihydrogen silane, dihydrogen disiloxane, in the presence of an effective amount of a platinum catalyst. It can be synthesized by reacting with An effective amount of platinum catalyst is about 10-6 to 101 parts platinum per part of hydrosilicide reaction mixture. Suitable inert organic solvents that can be used are, for example, toluene, chlorobenzene and orthodichlorobenzene. It is preferred to carry out the hydrosilicide reaction under substantially anhydrous conditions at temperatures in the range of 0°C to 200'C.

In order to enable those skilled in the art to more easily carry out the invention, the following non-limiting examples are provided to illustrate the invention. All parts are by weight.

Example 1 Norbornene dicarboxylic acid monomethyl ester 19.6
A mixture of 2P (0.1 mol) and 9.9f (5 x 10" mol) of 4,4'-methylene dianiline was dissolved in 50" dry methanol. The solution was refluxed under nitrogen for 2 hours. The solvent was then refluxed under nitrogen for 2 hours. and the residue was heated in an oven under nitrogen for 15 minutes.
Heated to 0°C for 21 hours. Dry the residue with dichloromethane 5
0-, washed with methanol, and dried to obtain 25.7 f of the target product (yield: 98 g). The product was a diimide having the following formula based on the method of preparation.

This was confirmed by spectroscopic data.

The above diimide 0.49F (10-1 mol) and a molecular weight of about 1
5 drops of 5 parts by weight platinum catalyst were added to a solution of silicon hydride-stopped polydimethylsiloxane with 500 td dissolved in 40 td of dry chlorobenzene. The resulting solution contained approximately 3% by weight of platinum, based on the weight of the total solution. This solution was heated to 80° C. for about 8 hours. Thus, it does not contain ole-747 unsaturation (NMR
(as shown in the spectrum) silicon hydride terminated polyimidosiloxane copolymer.

1 part of sanimide copolymer and 1. A mixture was prepared using N5-)rivinyl-1,&3.5.5-pentamethyltrisylxane o, '02 Q@, and the resulting mixture was heated to 150<0>C for 2 hours. A cured silicone polyimide elastomer was obtained.

Example 2 Norbornene dicarboxylic acid monomethyl ester 9.81
f (5X 10"mol'), Henschiff X-)7 tetracarboxylic acid dimethyl ester 9.66f (2,5
0””mol) and 4.4′-methylene dianiline 9.9
1 f (5X10”-2 mol) in dry methanol 100
- The solution was refluxed for 3 hours. After removal of methanol, the residue was heated to 150° C. in an oven under nitrogen flow for 2 hours. The obtained product was dissolved in 50% of plobenzene and poured into 40% of methanol to give f(c, 2!L6f(
An oligoimide with a yield of 98% was obtained, which was washed with methanol and dried. The product obtained based on the manufacturing method had the following formula:

/ \ Silicon hydride-terminated dimethylpolysiloxane 7,34 containing the above oligoimide 1.17 and having a molecular weight of 5300
t Add 5 drops of 5% platinum complex mixture to a solution dissolved in total dry chlorobenzene 4 (ld) and stir the mixture for about 8 hours.
Heated to 0°C. The resulting mixture contained no olefinic unsaturation (as judged by the NMR spectrum). Removal of the solvent yielded a sticky silicon hydride terminated siloxanimide block copolymer.

Following the procedure of Example 1, the silicon hydride terminated siloxane imide block IJ? -100 copies and 1.45-
A mixture of 5 parts of trivinyl-1,1,3,5,5-pentamethyltrisiloxane is heated to 150 DEG C. for 2 hours to obtain a cured elastomeric cloxanimide block copolymer.

Example 3 5-norbornene-2,3-dicarboxylic anhydride 1! L
68f1! l: 2.2-bis[4-(54-dicarboxyphenoxy)phenyl]prop/dianhydride 43.33
A mixture of f and meta-phenylenediamine I
0d solution. The resulting solution was heated to reflux for 2 hours, and that amount of water was continuously removed azeotropically. The obtained solution was poured into methanol 400P and stirred vigorously.

The precipitated product was filtered off, washed with methanol and dried. Based on the method of preparation, the product had the following formula:

648v of the norbornene-stopped polyetherimide was obtained, indicating a yield of 97%.

The above norbornene-stopped polyetherimide 22, Of,
1,1,5.3-tetramethylschiff cI xane a, o
Calstella?t and dry chlorobenzene 40-. (Kargtedt) U.S. Patent No. 47
75.442 was added under a nitrogen atmosphere. The solution was stirred and approximately 12 carbon blanks were added and the solution was stirred for 30 minutes.

The mixture was then filtered and the filtrate poured into 200 ml of dry diethyl ether with vigorous stirring. The nine precipitates obtained were filtered, washed with diethyl ether and dried. Based on the manufacturing method, the precipitate obtained in 98% yield was a silicon hydride terminated polyetherimide having the formula:

The identity of this product was further confirmed by NMR and IR analysis [also.

The above silicon hydride terminated oligoimide t2F.

A mixture consisting of 1 drop of the platinum catalyst of Example 1, 10-chlorobenzene, and 12f vinyl-chain-terminated polydimethylsiloxane having an average molecular number of about 1aOOOO is heated at 80° C. for about 12 hours under substantially anhydrous conditions. heated to. The gummy residue obtained on evaporation of the solvent had an intrinsic viscosity of 0.44 in chloroform at 25°C. Manufacturing method and N
Based on MR data, the product was a vinyl chain-terminated polydimethylsiloxane polyimide block polymer having the formula:

Here, m has already been defined.

A mixture of 10 t of the above silicone-polyimide block polymer and 3 f of a methyl hydrogen fluid having a molecular weight of about 30,000 having a weight factor of 55 methyl hydrogen siloxane chemically bonded thereto was heated to 80 DEG C. under vacuum for 12 hours during an open period. A tough silicone polyimide elastomer was obtained.

Example 4 5-norbornene-2,3-dicarboxylic anhydride69.
5 f (0,42 mol), 1.1.3.3-tetramethyldisiloxane 218? (alpha 2 mol) and dry chlorobenzene (Karstella) (U.S. Pat. No. 477 of Karstedt'I) with stirring.
No. 5,442 (assigned to the same company as the present invention)
10 drops of 5% platinum catalyst prepared according to the method were added to the mixture. The resulting mixture was heated at 70° for 4 hours with stirring.
Heated to 80°C and then 100°-110°C overnight.

After cooling, carbon black was added and the solution was stirred at room temperature for 30 minutes. After filtration, the solvent was removed using a vacuum pump at 100°C and dry diethyl ether was added to precipitate a white crystalline solid. Based on the manufacturing method, the product has the formula 5
, 5'-(1,4,5-3-tetramethyl-1,1.-containing 3-disiloxanediyl)-bis-norbornane-2,
It was a 3-dicarboxylic anhydride.

Oo 0.01 mol of the above dianhydride, 1.55.7-tetravinyl-1. K 5. One drop of 96-thiosulfuric acid is added to a mixture of 01 mole of 7-tetramethylcyclotetrasiloxane α and 005 mole of octamethylcyclotetrasiloxane dissolved in 50 mK of dry mToluene, and the resulting solution is refluxed for 2 hours. After cooling, carbon black was added and the solution was heated to 100'
Heat to C for 1 hour.

Evaporation in a furnace gives a colorless oil. Based on the production method, a methylvinylpolysiloxane with terminal norbornane anhydride groups is obtained.

To a solution of 5 X 10-3 moles of methylene dianiline and 5-dimethylformamide, with stirring under nitrogen, 10-3 moles of the above norbornane anhydride methylvinylsiloxane, 4 X benzophenonetetracarboxylic dianhydride.
A mixture of 10@-1 mol and 5d of dimethylformamide is added and the resulting mixture is stirred at 50 DEG C. for 2 hours to obtain a silicon-amic acid copolymer. The solution was then poured into a glass dish and placed in an oven mold for 80 minutes under nitrogen flow.
Dry for 1 hour at 150°C and 2 hours at 150°C. Based on the manufacturing process, a silicone polyimide block copolymer is obtained which has dimethylsiloxy units and methylvinylsiloxy units in the siloxane block.

A mixture of the above silicone polyimide block copolymer 1Of and the methyl hydrogen fluid 3f of Example 3 is heated in an oven at 80°C under vacuum for 12 hours to obtain a tough silicone polyimide elastomer.

Although the above examples relate to only 2.3 examples of the numerous variations that can be used to make the curable siloxanimide block copolymers of the present invention, the present invention relates to a much larger number of different heat-curable It should be understood that the present invention is intended to relate to platinum-containing siloxanimide block copolymers and methods of making the same.

Patent Applicant: 1st, 1st, 1st, 1st, 1st, 1st
('J630) Kaji Ikunuma

Claims (1)

[Claims] 1. (A) (+) Chemically bonded =SiH or 28
a polyorganosiloxane having 10*Hs units, and a norbornane silicone block copolymer having chemically bonded blocks selected from (ii) a mixture of (i) and polyimide, (B) chemically bonded =81■ or a810 goose H3
It is possible to perform polyaddition reactions with
a polyfunctional organosilicon material having at least two chemically bonded =SiH or =SiOIH units and selected from organosilanes, organopolysilanes, organosiloxanes, organopolysiloxanes and cyclopolyorganosiloxanes, and (0) A thermosetting composition comprising an effective amount of a platinum catalyst. 2. A thermosetting composition comprising a norbornene-stopped polyimide, silicon hydride, and an effective amount of a platinum catalyst. (v) The thermosetting composition according to claim 2, wherein the norbornene-stopped polyimide is norbornene-stopped polyetherimide. 4. The thermosetting composition according to claim 2, wherein the silicon hydride is silicon hydride siloxane. 5 Vinyl-stopped poly(norbornane imidosiloxane)
2. A thermosetting composition according to claim 1, comprising a silicon hydride siloxane, and an effective amount of a platinum catalyst. 6. A thermosetting composition comprising a norbornane-terminated polyimide chain-terminated with silicon hydride, a poly(vinyldiorganosiloxane), and an effective amount of a platinum catalyst. Z The thermosetting composition according to claim 6, wherein the norbornane-terminated polyimide chain-terminated with silicon hydride is a norbornane-terminated polyetherimide chain-terminated with silicon hydride. 7. The thermosetting composition according to claim 6, wherein the poly(vinyldiorganosiloxane) is a polydiorganosiloxane chain-terminated with vinyl. 9. The thermosetting composition according to claim 6, wherein the poly(vinyldiorganosiloxane) is a vinyl-containing cyclodiorganosiloxane. ICL (A) Silicon hydride-stopped polyimide 100 of the formula: 03) Consisting essentially of diorganosiloxy units of the formula chemically combined with vinylorganosiloxy units of the formula, about 10% at 25°C ~200. A thermosetting silicone polyimide copolymer composition comprising 1 to 200 parts by weight of a poly(vinyldiorganosiloxane) having a viscosity of OOO centipoise, and (0) an effective amount of a platinum catalyst, in which R is C-rich organic group, (a) aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative, (b) 2 to 20 carbon atoms
and a Ct-4 alkylene-terminated polydiorganosiloxane having ), Q is a tetravalent group, and (wherein D is 1 R -OR") 0- (wherein RIG is a divalent group selected from 0HsBr BrCH3Br Br ) and the general formula: (wherein X is a divalent group of the formula: (y is an integer from 1 to 5) p equals 0 or 1), R1-R6 are hydrogen and a
selected from t-S alkyl groups, R7 is the same or different at-ts-valent hydrocarbon groups and substituted ('1-13-
a valent hydrocarbon group, R4 is selected from hydrogen and R7, Y is a divalent group selected from 10- and -C(RX)2-, and n is an integer equal to 0 to 200; Ash,
r is an integer equal to 0 to 2000]. 11, polyvinylorganosiloxane is 1,45-)
11. The composition according to claim 10, characterized in that IJ vinyl-1,1, & 5,5-pentamethyltrisiloxane. 12. The composition according to claim 10, wherein the polyvinylorganosiloxane is vinyl-terminated polydimethylsiloxane. 15 (A) A thermosetting silicone polyimide copolymer composition comprising 100 parts by weight of a vinyl-stopped silicone polyimide of the formula: ω) 1 to 200 parts by weight of a silicon hydride siloxane, and (0) an effective amount of a platinum catalyst. However, in the above formula, R7 is the same or different at-ts
-valent hydrocarbon group and substituted C! The trivalent hydrocarbon group Teary, R''Vi-OH20H, -TheaF), Gd, is a divalent group, and is a divalent group that combines a silicon hydride-terminated polyimide of the formula: % with a vinyl-terminated polydiorganosiloxane of the formula: R7R7. RFi is a divalent Ox-to organic group formed by reacting (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivatives; (b) 2 carbon atoms; ~20
an alkylene group and a cycloalkylene group having c,
-1 alkylene-terminated polydiorganosiloxanes, as well as formula (C): wherein Q' is selected from the class consisting of (wherein X' is an integer from 1 to 5) divalent radicals selected from the class consisting of QFi, tetravalent radicals and ), and a divalent group of the general formula: (wherein, are selected from hydrogen and at-S alkyl groups, and R7 is the same or different at-ts-valent hydrocarbon groups and substituted at-ts-valent hydrocarbon groups. a group, R8 is selected from hydrogen and R7,
Y is a divalent group selected from 10- and -c(nl)1-, n is an integer equal to 0 to 200, and r is 0
~2000].