JPS59131629A - Silicone-polyimide copolymer, condensable vulcanizable composition and manufacture - 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 Background of the Invention The present invention relates to silanol-terminated boridiorganone loxane-polyimide copolymers or silicon hydride-terminated boridiorganone rosaquine-polyimide copolymers and room temperature or low temperature condensation vulcanizable compositions obtained therefrom. Articles and methods of manufacturing such materials. More particularly, the present invention relates to hydrolanization of norbornene-terminated polyimide and subsequent reaction of the resulting silicon hydride-terminated polyimide with 7-ranol-terminated polydiorganosiloxane.

Prior to this invention, room temperature vulcanizable lanol-terminated polysiorganosiloxanes, such as silanol-terminated polydimethylsiloxanes, were available in one-package (-deep) or two-package (-
It was available as either a two-component (two-component) system. A typical one-component system is Oeyze-riat U.S. Patent No. 3.135.
．． No. 891, methyltriacetoxysilane and silanol terminated polydimethylsiloxane are used.

U.S. Pat. No. 3.06.5.1 to N1tzsche et al.
The more two-part system shown in No. 94 requires the silanol-terminated polydimethylsiloxane to be formulated with a curing catalyst, such as a combination of ether orthosilicate and dibutyltin dilaurate. In two-component systems, curing.

The catalyst must be mixed with the silanol-terminated polydimethylsiloxane before use.

The one-part and two-part room-temperature vulcanizable compositions described above generally incorporate a reinforcing filler, such as a silica filler, in 0 parts of the silicone polymer when high tensile strength is desired in the resulting cured silicone. One method that can be used to improve the toughness of cured silicone polymers involves the introduction of 7 fullarylene siloxy units into the polymer chain. They produce copolymers consisting essentially only of diorganone loquine units and diary-V Schifoxy units chemically bonded to each other.Although these methods significantly increase the elastic modulus (psi) of the silicone polymer, , is not economical and cannot achieve the high degree of physical properties desired in the final product.

The present invention provides a room temperature or low temperature condensation vulcanizable polydiorganone loxane-polyimide copolymer which, when cured with a conventional room temperature vulcanizable curing catalyst, has a temperature of 100 to 10,000 psi.
They were disappointed to discover that they could produce an elastomer with tensile strength in the range of . These 7-ranol-terminated or silicon hydride-terminated polydiorganosiloxane-polyimide copolymers are composed of polyimide blocks 1 to 99 of the following formula (by weight) and boridiorganone loxane blocks 99 to 99 of the following formula chemically bonded thereto. It is 1% by weight.

R in the formula is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative group thereof, (b) 2 to 20
alkylene groups and cycloalkynones having 20 carbon atoms and 0(2-8) alkylene-terminated polydiorganone a xane, and (C) a group selected from the group consisting of the following formula: % -CxH2X- It is a divalent group represented by (or an integer from 1 to 5)! ll
Q is a divalent C(2-20) organic group selected from the group consisting of CH30H30H3Br Br OH3Br
Br(R3CH3CH3Br Br ORB
Br is a divalent group selected from Br and a divalent organic group of the general formula, p is equal to 0 or 1, and X is a divalent group selected from the following formula: , y is an integer from 1 to 5), R1-R6 are selected from hydrogen and 0(1-8) alkyl groups, R' Fi, the same or different monovalent C '(1-13)
A hydrocarbon group and a monovalent substituted C'(1-13) hydrocarbon group, Y is a divalent group selected from -0- and -C(R2-, n is 0 an integer equal to ~200, where m is an integer equal to 1-2000.

In order to produce the silicon hydride-terminated polydiorganone loxane-polyimide copolymer of the present invention, first, a reaction between an organic diamine, norbornene anhydride and organic dianhydride is carried out according to the reaction formula. Form a norbornene-terminated polyimide.

Here, Q, R, R1, R6, Y and n are as defined above. The aliphatic unsaturated polyimide of formula (3) is then expressed by the following formula.

R7B? 1 (wherein r is O or 1 and R9 is selected from hydrogen and R7) is hydrosilanized with silicon hydride to produce a silicon hydride-terminated polyimide of the following formula (5).

Here R, R1, R? , Y, Q and n are as defined above.

The silanol-terminated polydiorganone loxane-polyimide copolymer of the present invention has the following formula: (2 in the formula C is a divalent group represented by the formula (1)), and in order to produce it, the following formula: The reaction between the silicon hydride-terminated polyimide of (5) and the silanol-terminated polydiorganone loxane of the following formula is carried out in the presence of an effective amount of a condensation catalyst (described below).

Here, R7, R9, r and m are as defined above, and t is an integer of about 1 to 104.

Groups included in R1 to R6 in formulas (1), (3) and (4) are, for example, hydrogen, methyl, ethyl, propyl, butyl and the like. Groups included in R7 include, for example, aryl groups and non-rogenated aryl groups, specifically haphenyl,
Chlorophenyl, tolyl, quinryl, biphenyl, naphthyl, etc.: alkenyl groups, specifically vinyl, allyl,
Chlorohexenyl, etc.; 0(1-8) alkyl group and 10genated alkyl group, specifically methyl, ethyl,
Propyl, butyl, octyl, etc.

[
A condensation vulcanizable composition comprising 1002 to 10 parts of a curing agent, (C) 0 to 5 parts of a condensation catalyst, and (D) 0 to 3000 parts of a silanol-terminated polydiorganosiloxane of formula (7) is provided. .

In the present invention, curing agents that can be used in the condensation vulcanizable composition include, for example, methyltriacetoxysilane, methyl-tris-(2-ethelhexaneoxy)-silane and the following formula: (7) Curing of % formula % (8) R7 in formula (8) is a 0(1-8) aliphatic organic group selected from the group consisting of 5m, R10hfurkyl, alkyl ether, alkyl ester, alkyl ketone, and alkyl ether as defined above; or C(
+-1g aralkyl group, xia amyloxy,
Amido, amino, carnomado, enoxy, halo, imidato, incyanato, ketoximado, oximado, theoininanato and C) - ureio "b is an integer equal to 0-, a ten is an integer from 0 to 4 equal.

In addition to the curing agent of formula (8), the condensation vulcanizable composition of the present invention contains an alkoxy functional group of the following formula: Polymer crosslinking agents can also be used.

In the present invention, a condensation catalyst can be used to accelerate the curing of the condensation vulcanizable composition, and in some cases, hydrogenation of the 7-ranol-terminated boridiorganone loxane of formula (6) and the formula (5) Condensation with silicon-terminated polyimide can be promoted. For example, per 100 parts of the silanol-terminated polydiorganosiloxane-polyimide copolymer 0
．． 0.001 to 1 part of condensation catalyst can be used. As condensation catalysts, tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethquine, carbomethquine phenyltin trisuberate, isobutyltin triceroate, dimethyltin dibutate, dimethyltin dineodeconate, triethyltin are used. Tartrate, dibutyltin dipenzoate, tin onate,! Examples include naphthinate, butyltintri-2-ethylhekynate, and tinbutyrate. Suitable condensation catalysts are tin compounds, among which dibutyltin diacetate is particularly preferred.

Examples of titanium compounds include Lely, 1,3-propanedioquine titanium bis(ether acetoacetate), 1,3-
Propanedioquine titanium bis(acetylacetonate)
, diimpropoquine titanium bis(acetylacetonate), titanium naphthenate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, enaltriethanolaminetetanate. Additionally, Weyenberg U.S. Patent No. 3.334.067
The β-dicarbonyl titanium compounds shown in the above can be used as condensation catalysts in the present invention.

Zirconium compounds such as zirconium octoate can also be used.

Further examples of metal condensation catalysts include lead 2-ethyl octoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, antimony octoate, Examples include bismuth naphthenate, zinc naphthenate, and zinc stearate.

Examples of non-metallic condensation catalysts include hexylammonium acetate and benzyltrimethylammonium acetate.

In addition to the deep condensation vulcanizable curing agents described above, in the practice of the present invention, the compounds described in U.S. Pat. No. 3,127,363 to Nltzchθ et al. Curing agents that can form a two-part condensation vulcanizable composition with better properties than those described above can also be used.

Examples of organic dianhydrides that can be used in the present invention with the norbornene anhydride chain-terminating monomer to form the norbornene-terminated polyimide of formula (3) include penzophenone dianhydride, pyromellitic dianhydride, 2, 2-bis[4
-(3,a-dicarboxyphenoquine)phenyl]propannianhydride, 2,2-pisC4-C2,3-dicarboxyphenoxy)phenyl]furopannianhydride, 4-(
2,3-dicarboxyphenoxy)-a'-(s, a-
dicarboxyphenoxy)diphenyl-2,2-propane dianhydride and bisnorbornane dianhydride of the formula: and mixtures thereof.

Organic diamines that can be used to form the polyimide block of the silanol-terminated polydiorganone loxane-polyimide copolymer include, for example, 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4.4'- Diaminodiphenylpropane, 4,4'-diaminophenylmethane (commonly referred to as 4,4'-methylenedianiline), 4,4'-diaminodiphenyl sulfide (commonly referred to as 4.4'-diaminodiphenyl sulfide).
(referred to as 4'-thiodianiline), 4,4'-diaminodiphenyl ether (referred to as 4'-oxydianiline), 1,5-diaminonaphthalene, 3'-dimethylbenzidine, 45' -dimethoxybenzidine, 1.3-diamino-4-isopropylbenzene, 1.
2-bis(5-aminopropoxy)ethane, benzidine, m-xylylene diamine, p-xylylene diamine, 2,4-cyamite, luene, 2,6-cyamitoluene, bis(4-aminopropoxy) Mekuni〆, 3-methylnonamethylenediamine, 4.4-dimethylheptamethylenediamine, 2.11-
Dodecanediamine, 2.2-dimethylpropylenediamine, octamethinonediamine, 3-methquinhexamethinonediamine, 2.5-dimethylhexamethinonediamine, 2.5-dimethylheptamethylenediamine, 6-methylhegetamethylene Diamine, 5-methylnonamethylene diamine, 1,4-cyclohexane diamine, 1,12-octadecane diamine, bis(3-aminopropyl) sulfide, N-methyl-
Bis(3-aminopropyl)amine, hexamethylenediamine, -heptamethylenediamine, nonanonarediamine, decanonalenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(4-aminobutyl)tetramethyldisiloxane siloxanes, and mixtures of these diamines.

In the present invention, examples of silicon hydrides of formula (4) that can be used to introduce silicon hydride functional groups into polyimides having aliphatic unsaturated norbornene groups include diorganosilane, specifically dimethylsilane. , diphenyl 7 run, 1,
Examples include 1,3,3-tetramethyldisiloxane.

7-ranol-terminated polydiorganosiloxane of formula (6)
The silanol-terminated polydiorganosiloxane of formula (7) that can be used in combination with the silicon hydride-terminated polyimide to prepare the polyimide copolymer has a viscosity in the range of about 10 to 400.000 centipoise measured at about 25°C. , particularly in the range of about 1000 to 250,000 centipoise. To produce these silanol-terminated fluids, relatively high molecular weight organopolysiloxanes,
For example, dimethylboriaoxane is treated with water in the presence of a mineral acid or basic catalyst. Diolglass rosilanes, such as dimethyldichloro7rane, diphenyldichlorosilane,
Hydrolysis of methylvinyldichlorosilane, methylfluoropropyldichlorosilane, methylcyanoethyldichlorosilane, or mixtures thereof can produce low molecular weight polymers. The subsequent equilibration results in a higher molecular weight organopolysiloxane. Organopolysiloxanes can also be treated with steam under pressure or by other methods as described in US Pat. No. 2,607,792 and British Patent No. 835,790.

7-ranol-terminated polydiorganosiloxane of formula (6)
Examples of condensation catalysts that can be used to make polyimide copolymers include platinum catalysts, specifically Karstedt U.S. Pat. No. 5.775.442, Aehby U.S. Pat. No. 662 and Lamoreaux, U.S. Pat. No. 3.220,97.
There is an unsaturated siloxane platinum structure as shown in No. 2. An effective amount of platinum catalyst is about 10-4 to 0.1 wt.[1%] platinum based on the weight of the curable hydrosilanization mixture.

Various fillers and pigments can be incorporated into the room temperature vulcanizable compositions of the present invention. For example, titanium dioxide, zirconium silicate, silica airgel, iron oxide, diatomaceous earth, heated silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, quartz powder, carunium carbonate, etc. can be used. It is clear that the amount of filler used can vary within wide limits depending on the intended use. For example, in wet-land applications, the curable compositions of the present invention can be used without fillers. In other applications, for example when the curable composition of the present invention is used in the production of binders, the polydiorganosiloxane-polyimide copolymer 1 part by weight
Larger amounts of filler can be used, such as 00 parts per Schiff or more. In such applications, the filler may be primarily an extender, such as quartz powder, polyvinyl chloride, or mixtures thereof, preferably having an average particle size in the range of about 1 to 10 microns.

The condensation vulcanizable compositions of the present invention can also be used as architectural sealants and caulking compounds. Therefore, the exact amount of filler will depend on factors such as the intended use of the organopolysiloxane composition, the type of filler used (ie, the density and particle size of the filler). 100 parts of silanol-terminated organoporin loxane #) 5-3
00 parts of filler (up to about 65 parts of reinforcing filler,
It is preferable to use a filler material (which may for example contain a heated filler).

The silicon hydride terminated polyimide of formula (5) can be used as an adhesion promoter in room temperature vulcanizable organopolysiloxane compositions. The 7lanonyl-terminated polydiorgano-70-xane-polyimide copolymer of formula (6) can be used as an impact modifier in the conventional room temperature vulcanizable organopolysiloxane compositions described above.

In carrying out the present invention, the condensation vulcanizable polydiorganosiloxane-polyimide copolymer composition includes a curing agent,
It can be produced by mixing a condensation catalyst and optionally a crosslinking agent with the silanol-terminated polydiorganosiloxane-polyimide copolymer of formula (6) (hereinafter referred to as "silanol-polyimide copolymer").

In the condensation vulcanizable composition of the present invention, an effective amount of the above-mentioned curing agent can be used. depending on whether it generates acidic or substantially neutral by-products.

When using a 91Lt c.7 siloxy curing agent such as methyltriacetoxysilane, good results can be obtained by using 1002 to 10 parts of methyltriacetoxysilane per 100 parts of the silanol-polyimide copolymer. A curing agent as represented by formula (8) can be used in a ratio of 0.002 to 10 parts of curing agent per 100 parts of silanol-polyimide copolymer. A crosslinking agent of formula (9) can also be used in combination with a curing agent of formula (3) at a ratio of Jo to 10 parts of crosslinking agent per 100 parts of silanol-polyimide copolymer. Condensation catalysts can also be used in the proportions mentioned above.

As mentioned above, the condensation vulcanizable composition can also be combined with various fillers, pigments and extenders, and these fillers, pigments and extenders can be optionally combined with curing agents, condensation catalysts and the like. It can be introduced into the silicone-polyimide copolymer before, simultaneously with, or after introduction.

The norbornene-terminated polyimide of formula (3) is synthesized by conventional methods using equimolar amounts of an organic diamine and an organic dianhydride in an effective amount of the chain sufficient to produce the desired molecular weight of the polyimide. This can be done by using it with norbornene anhydride for termination. During the polymerization of the norbornene-terminated polyimide, organic solvents such as 0-dichlorobenzene can be used and temperatures in the range 140-200°C can be used. The reaction can be carried out in an inert atmosphere, such as in an atmosphere, to minimize undesirable side reactions. The reaction time can vary from 30 minutes or less to 3 hours depending on the nature of the reactants, the desired molecular weight of the polyimide, etc.

The silicon hydride-terminated polyimide of formula (5) can be prepared by reacting the norbornene-terminated polyimide of formula (3) with a suitable silicon hydride of formula (4), such as dihydrogen silane or dihydrogen zinoxane. It can be synthesized by carrying out the synthesis in the presence of An effective amount of platinum catalyst is about 10-6 to 10-3 parts of platinum in 1 part of a hydrosilanation reaction mixture consisting of norbornene-terminated polyimide, silicon hydride, and an inert organic solvent, the inert organic solvent being about 10-3 parts of platinum in 1 part of a hydrosilanation reaction mixture consisting of norbornene-terminated polyimide, silicon hydride, and an inert organic solvent. is 10-50% by weight
Sufficient bone fines can be used to produce a mixture of.

As suitable inert organic solvents it is possible to use, for example, chlorobenzene and 0-dichlorobenzene. Hydron run reaction under substantially anhydrous conditions, 15-9
Preferably, it is carried out at a temperature in the range of 0°C.

The silanol-polyimide copolymer is produced by reacting a silicon hydride-terminated polyimide of formula (5) with a silanol-terminated polydiorganosiloxane of formula (7) at 15 to 150°C.
This can be achieved by carrying out the reaction at a temperature within the range of 100 to 1000 ml in the presence of an effective amount of a copolymerization catalyst.

Suitable copolymerization catalysts include, for example, amines, alkali metals), colloidal nickel, zinc chloride, platinum or rhodium complexes, dibutyltin diacetate, etc., depending on the mutual solubility of the reactants, and neutral to accelerate the reaction. It can be used with or without solvents such as dichloromethane, chlorobenzene, 0-dichlorobenzene.

The condensation vulcanizable silicone-polyimide composition can also be blended with a 7-ranol-terminated polydiorganosiloxane of formula (7) as described above. Compounding can be carried out under substantially anhydrous conditions at temperatures ranging from about 15 to 2,000 degrees Fahrenheit or higher. The cured silicone-polyimide copolymer thus obtained can be used in a variety of applications requiring high strength, high performance, heat resistant elastomers.

To enable those skilled in the art to easily carry out the invention,
The following non-inventive embodiments are presented by way of illustration and not by way of limitation. All parts are by weight.

Example 1 1568? 5-norbornene-2,3-dicarfonic anhydride and 2,2-bis[4-(3,
Mixture of 4-dicarboxyphenoxy)phenyl]propanihydride was added over 10 minutes under nitrogen to a solution of 4.13.51y of m-7 22-diamine and 0.100 ml(7)o-dichlorobenzene. The resulting solution was heated to reflux for 2 hours to continuously azeotropically remove the disclosure. The resulting solution was poured into 400 methanol,
Stir vigorously. The product was precipitated, filtered, washed with methanol and dried. Based on the manufacturing method 1, the product had the following formula:

64,8? The above norbornene-terminated polyetherimide was obtained with a yield of 97%.

22, Of the above norbornene-terminated polyetherimide, 4. Of 1.1. A mixture of 3-tetramethyldisiloxane and 4 Qtnt of dry chlorobenzene was prepared using Karetedt U.S. Patent No. 5.775.44.
Five drops of 5% platinum catalyst prepared according to No. 2 were added under nitrogen atmosphere. The solution was stirred and heated to 70°C for about 12 hours. Add carbon black to the resulting mixture at room temperature,
The solution was stirred for 30 minutes. The mixture was then filtered 1' and the p solution was poured into a 200-g dry diethyl needle with vigorous stirring. A precipitate was obtained which was filtered, washed with diethyl needle and dried. Based on the manufacturing method, yield 9
The precipitate obtained at 8% was a silicon hydride terminated polyetherimide of the formula:

Identification of the product by Th NMR and In-g
We confirmed further.

5.58f of the above silicon hydride terminated polyetherimide,
The above Karstedt
One drop of a 5% solution of catalyst was added under nitrogen. The resulting solution was heated to 80°C for 3 hours. Infrared analysis confirmed the absence of silicon hydride in the resulting mixture. Evaporation of the solvent from the mixture gave an opaque residue with a viscosity of 146.200 centipoise. Based on the method of manufacture, this opaque residue was a 7-ranol-terminated polydimethylsiloxane-polyetherimide block copolymer of the formula:

Margin below this page However, X is an integer of 3 or more.

Under substantially anhydrous conditions, 1.0 gram mole of the above-mentioned Ranol-terminated silicone-bolyetheride Z-docopolymer K was mixed with methyltrinotoxyC'7, followed by dibutyltin diacetate-1 of α12 and dibutyltin diacetate-1 of α32. Dibutylamine was added. The obtained mixture was heated to 1 in an environment with a humidity of 58%.
I left it for a week. A tack-free cured block copolymer was thus obtained which exhibited a tensile strength of 146 psi and an elongation of 630 inches.

The above steps? , was repeated using silanol-terminated polydimethyl 70xane having a viscosity of 146,000 centipoise (25°C) in place of the silanol-terminated polydimethylsiloxane-polyetherimide copolymer. A cured product was obtained exhibiting a tensile strength of 49 psi and an elongation of 300 inches.

Example 2 9, 91? (0,05 mol) of methinone dianiline, 19.62 f (101 mol) of 5-norbornene-2+3-dicarboxylic acid monomethyl ester and 10
A mixture of 0 wt dry methanol was refluxed in R2 for 2 hours. After removing the solvent, the residue was heated in an oven with N2
The mixture was heated to 150° C. for 2 hours.

The resulting white solid was dissolved in ftca2cz2 and 4
The mixture was poured into 00-methanol and stirred vigorously. Based on the production method, bis(norbornene imide) is obtained,
This was filtered, washed with methanol, and dried. A bisimide of the following formula was obtained in a yield of 98%.

111 111 0 0 In nitrogen, 100 m of dry chlorobenzene and! 11.2
6 r (I X 10-2 mol) + 7) To the above solution of his(norbornene imide) was added 41F (3X 10-2 mol) of 1,1,3.3-tetramethyldisiloxane and Karstedt, US Pat. 715.33
Five drops of a 5% solution of PT catalyst shown in No. 4 were added. The resulting solution was heated at 60-80°C overnight. excessive 1,
After removing the 1.43-tetramethyldisiloxane, carbon dioxide was added to the solution. The mixture was stirred for 21 hours and then filtered. Based on the manufacturing method, a silicon hydride terminated bisimide of the following formula was obtained.

Margin below this page 15.23 ft of the above silicon hydride terminated bisimide Upon removal, a clear, very viscous residue was obtained.

Based on the method of manufacture, this residue was a silanol-terminated bisimidone loxane of the formula:

However, y is an integer of 11 or more. Subsequently, the residue was reduced to 0.
1f of methyltriacetoxy7 run, then B
u2Sn(OAQ)2 was added. The resulting mixture was left for one week in an environment with a humidity of 58 degrees. The cured material was a clear rubber with significantly improved toughness and elongation.

Example 3 To prepare a norbornene-terminated bisimide, 174
9 of isophorone diamine and 3281 of norbornene dicarboxylic acid anhydride were dissolved in 11800-〇N-methylpyrrolidone and 600 rnl of toluene. The reaction mixture was heated for 12 hours to remove water. The mixture was then heated to remove some of the toluene and N-methylpyrrolidone. The residue was poured into 40% ingropanol. The page-colored solid thus obtained was collected by filtration and dried.

4 & 2 of the above inholonorbornene-terminated diimide,
A solution of 20 ppm platinum catalyst and 200-polobenzene was diluted with 32.6 F tetramethyldisiloxane at 8
After treatment at 0-100℃ for 6 hours, inphorondiimide dihydrosiloxane? generated. about 732 diimidohydrone loxane with a silanol-terminated polydimethylsiloxane fluid having an average of about 3 chemically bonded 70x units in about 1:1 and 1:2 molar ratios in the presence of a platinum catalyst. , at a temperature of 50-60° C. to produce a silanol-terminated boridiorganone loxane-polyimide copolymer within the range of formula (6).

202 7-ranol-terminated polydimethylsiloxane-polyimide copolymer made from a mixture having a ratio of 2 moles of silanol-terminated dinotylsiloxane to 1 mole of diimidohydrone loxane, 100f silanol-terminated polydimethylsiloxane (viscosity 120-18 Q, OQ O centipoise), 47 methyltrimethoxysilane, O, 5t
A condensation curable mixture was prepared under anhydrous conditions from 100% dihexylamine and 0.3% dibutyltin diacetate.

When exposed to air, this RTV composition had a 10 to 1
It cured within 6 minutes. A test piece ft was prepared and the hard awn (Simaa A), elongation (row) and tensile strength pθ1) were measured. I got the following results.

Hardness: 17
Biro 72 Tensile vomiting
143 An RTV composition was made by repeating the above procedure except that it did not include the silanol-terminated polydiorganone loxane-polyimide copolymer of the present invention.

I got the following results.

Hardness 9 Elongation 328 Tensile strength
53 These results demonstrate that the silanol-terminated polydimethylsiloxane-polyimide copolymers impart superior physical properties to conventional room temperature vulcanizable organopolysiloxane compositions.

Example 4 The procedure of Example 3 was repeated. However, in this example, a silanol-terminated polydinonarunoxane-polyimide copolymer prepared from a mixture of silicon hydride-terminated diimide and silanol-terminated polydimethylsiloxane in a 1=1 molar ratio was used. 7 kg of this lanol-terminated polydimethylsiloxane-polyimide was blended with the components of the room temperature vulcanizable composition of Example 3. However, in this example, the viscosity is 20 to 5 Q, 000
Seiteboaz silanol-terminated polydimethylsiloxane was used. In addition, hiemed silica treated with octamethylcyclotetrasiloxane and disilazane was added to the above mixture at a rate of 5 parts by weight and 10 parts by weight, respectively, based on the weight of the total mixture. These mixtures were cured under atmospheric conditions as described in Example 3;
The following results were obtained. "15% filler" and "1-10% filler" refer to filler-containing compositions as described above,
Hardness, elongation and tensile strength are as defined above.

5% filler 10% filler hardness 62
35 growth 255
269 tensile strength 331 2
The above procedure was repeated except that the 55 silanoyl terminated polydi/ternoxane-polyimide copolymer was not used in the formulation. I got the following results.

5-chi filler 10% filler hardness 22
27 growth 288
251 Tensile strength 168 23
1 These results demonstrate that significantly increased toughness is imparted to cured room temperature vulcanizable organoporin loxane compositions as a result of incorporating the silanol-terminated polydimethylsiloxane-polyimide copolymers of the present invention. There is.

Although the above examples are only a few examples of the numerous condensation vulcanizable 7 silicone-polyimide copolymers that include room temperature vulcanizable and low temperature vulcanizable compositions within the scope of the present invention, the present invention The silanol-terminated polydiorganone loxane-polyimide copolymer was combined with a curing agent as shown in formula (8) and a crosslinking agent as shown in formula (9) depending on the desired VC, and then kneaded. It should be understood that a wide range of condensation vulcanizable compositions can be obtained by use in combination with a condensation catalyst. The invention further provides a silicon hydride terminated polyimide of formula (5) and a silicon hydride-terminated polyimide of formula (5) which are useful materials for producing condensation vulcanizable compositions that can be converted into high strength silicone-polyimide copolymers in the cured state. (Also involved in 6-Nranol-polyimide copolymer.

Claims (1)

[Claims] 1. A condensation vulcanizable composition containing a silanol-terminated polydiorganone loxane-polyimide copolymer. . 2. (4) 100 parts by weight of 7 lanoyl-terminated boridiorganone loxane-polyimide copolymer, (B) 0.002-10 parts by weight of curing agent, (C) 0-5
A condensation vulcanizable composition containing parts by weight of a condensation catalyst, and (D) 0 to 3000 parts by weight of 7-ranol-terminated polydiorgano-70xane. & The condensation vulcanizable composition according to claim 1, which is curable at room temperature. 4. The condensation vulcanizable composition according to claim 1, which is curable with moisture. 5 The curing agent has the following formula: % formula %) () (R7 in the formula is the same or different monovalent C'(1-13)
a hydrocarbon group or a monovalently substituted "(1-13) hydrocarbon group, where RIG is selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone, and alkyl cyano group" (1-8) fatty a C(7-13) aralkyl group, and X is selected from the group consisting of acyloxy, amido, amine, carbamado, enoxy, halo, imidato, incyanato, ketoximado, ocynmato, thioincyanato, and ureido groups. The room-temperature vulcanizable composition according to claim 1, which is an alkoxysilane represented by a hydrolyzable 12F1 number, an integer equal to Om, and the sum of 10s is equal to 0 to 4. & The following formula: [In the formula, R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its -Rogenich derivative group, Ω32
Alkylene groups with ~20 carbon atoms and 7 chloroalkylene groups and 0(2-6) 7 Ruki L/7
Terminated polydiorganosiloxane, and (C) the following formula: %
represented by the formula % (wherein Q' is selected from the group consisting of 10-5-a-1-8-1-day- and 1-CXH2-, and X is an integer from 1 to 5) Q is a divalent C(2-20) organic group selected from the group consisting of divalent groups (wherein D is selected from 10-1-S-5 +1 1111 RROQ , R8 is CHB [3) is CH3nr Br0H3B
r Br and a divalent group selected from divalent organic groups of the general formula: where p is equal to 0 or 1, or of the following formula: %10yH2ar, -c-1-5-1- 〇- and -8
-1 divalent group, y is an integer from 1 to 5)
is a tetravalent group selected from, R1-R6 are hydrogen and C! (1-s) selected from alkyl groups, F17 is the same or different monovalent 0(1-13) hydrocarbon group and monovalent substituted 0(1-13) hydrocarbon group selected from rosy, R9 is selected from hydrogen and R7 and Y is a divalent group selected from 10- and -0, n is an integer equal to 0 to 200, and r is an integer equal to 0 or 1]. A silicon hydride-terminated polyimide having the following formula: 1 [2 in the formula is a divalent group having the following formula: I ((a) is an aromatic group having 6 to 20 carbon atoms group hydrocarbon group and its no-logenated derivative group, (b) 2-20
alkylene and cycloalkylene groups and C('2-8) alkylene-terminated polydiorganocloxanes having C atoms, and ((! tertiary formula: (in the formula, Q' is -0-l-0-1 -s-5-8- and 1111 0 0 - Cx"2x-, xFi, 1
Q is a divalent 0(2-20) organic group selected from the group consisting of divalent groups represented by -2 0 11II 1l -ONRNC-1-c-1-ocoR”oc- and -
〇R80-'+ 1111RR
OO, 'R11 is a divalent group selected from divalent organic groups of the formula: and p is equal to 0 or 1, and X is a divalent group of the formula: and y is an integer from 1 to 5), Hl -B 6 is hydrogen and C! (1-B) selected from alkyl groups, R7 is the same or different monovalent C(1-13) hydrocarbon group and monovalent substituted 0(+-13) hydrocarbon group, R9
is selected from hydrogen and R7, Y is a divalent group selected from 10- and -0(R')2-, n is an integer equal to 0 to 200, r is O, and fc is 1 m is an integer equal to from 1 to 2000, and t is an integer having a value from about 1 to 104. The room temperature vulcanizable composition according to claim 1, wherein the curing agent is tritoxy-N-methylacetamidosilane. 9. The room temperature vulcanizable composition according to claim 1, wherein the curing agent is methyltriacetoxy 7-ran. 10. Silicon hydride terminated polyimide with the following formula: % formula %. 11. 7-ranol [terminal polydimeternoxane-polyimide copolymer] of the following formula: (X in the formula is an integer of 3 or more). 12. The condensation vulcanizable composition according to claim 1, which contains methyltrimethquine silane. 13. Polyimide blocks 1 to 99 of the following formula: and 99 to 1% by weight of boridiorganone loxane blocks of the following formula chemically bonded thereto, [wherein R is (a ) aromatic hydrocarbons having 6 to 20 carbon atoms and their no-rogenated derivative groups, (b)2
an alkylene group and a cycloalkynone group having ~20 carbon atoms and a C(2-8) alkyl V-terminated polydiorganosiloxane, and (C) the following formula: % formula % (in the formula, Q' is -0- 5-c-1-s-1-8- and 1-CxH2x-, or an integer from 1 to 5); is a divalent C(2-20) organic group in which Q is (Dbaoo o o
. II II II II II-
〇-5-S-1-C! NRNO-1-C-1-C-OR
80C-1 R and -OR"O-, R8 is a divalent group selected from divalent organic groups of the general formula: and p is O"
! or equal to 1, X is a tetravalent group selected from the following formula: (1-8) selected from alkyl groups, R7 is the same or different monovalent ':' (1-13) hydrocarbon group and monovalent substituted '(1-13) hydrocarbon group 6D,
Y is a divalent group selected from 10- and -(!(R1)z-, n is an integer equal to 0 to 200, and m is an integer equal to 1 to 2000), ranol or hydrogen Silicone-terminated polydiorganone loxane-polyimide copolymer.