JPH069779A - Silicone-polyimide copolymer and its manufacturing process - Google Patents

Abstract

PURPOSE: To obtain a silicone-polyimide copolymer giving a low temp. condensation vulcanizable compsn. useful as a sealant for construction, etc., by selecting a specified silanol terminated polydiorganosiloxane-polyimide.

CONSTITUTION: The silanol terminated polydiorganosiloxane-polyimide is represented by formula I is selected {where Z is a divalent group of formula II [where R is a 6-20C (halogenated) arom. hydrocarbon group, 2-20C alkylene, cycloalkylene, 2-8C alkylene terminated polydiorganosiloxane or the like; Q is a group of formula III or the like; R¹-R⁶ are each H or a 1-8C alkyl; Y is -O-or a -C(R¹)₂-; and (n) is 0-200]; R⁷ is a 1-13C (substd.) hydrocarbon group; R³ is H or R⁷; (r) is 0 or 1; (m) is 1-2,000; and (l) is about 1-10⁴}.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silanol-terminated polydiorganosiloxane-polyimide copolymer and a method for producing the same. More particularly, the present invention relates to hydrosilation of norbornene terminated polyimides and subsequent reaction of the resulting silicon hydride terminated polyimides with silanol terminated polydiorganosiloxanes.

[0002]

Prior to the present invention, room temperature vulcanizable silanol-terminated polydiorganosiloxanes, such as silanol-terminated polydimethylsiloxanes, were one package (one-pack) based on the nature of the moisture-sensitive crosslinker used in the composition. Or it was available in either a two-package system. A typical one-part system is Ceyzeriat US Pat. No. 3,13.
Methyltriacetoxysilane and silanol terminated polydimethylsiloxane are used, as shown in US Pat. No. 3,891. Nitzsche et al., U.S. Pat. No. 3,065,19
In a two part system such as that shown in No. 4, it is necessary to formulate a silanol terminated polydimethylsiloxane with a curing catalyst, such as a combination of ethyl orthosilicate and dibutyltin dilaurate. Two-part systems require the curing catalyst to be mixed with silanol-terminated polydimethylsiloxane before use.

[0003]

The one-part and two-part room temperature vulcanizable compositions described above generally provide reinforcing fillers, such as silica fillers, when high tensile strength is desired in the resulting cured silicone. 5 per 100 parts of silicone polymer
It is necessary to use an amount of ~ 300 parts. Another method that can be used to improve the toughness of cured silicone polymers is the introduction of silarylenesiloxy units into the polymer chain so that the diorganosiloxy units and silarylene are chemically bonded to each other substantially. A copolymer consisting only of siloxy units is produced. While these methods significantly increase the modulus (psi) of silicone polymers, they are not economical and do not achieve the high degree of physical properties desired in the final product.

[0004]

SUMMARY OF THE INVENTION The present invention provides a room temperature or low temperature condensation vulcanizable polydiorganosiloxane-polyimide copolymer, when cured with a conventional room temperature vulcanizable curing catalyst, in the range of 100 to 10,000 psi. It was made by the discovery that it produces an elastomer exhibiting a tensile strength of. These silanol terminated or silicon hydride terminated polydiorganosiloxane-polyimide copolymers are
1 to 99% by weight of the polyimide block of Chemical formula 65 and 99 to 1% by weight of the polydiorganosiloxane block of Chemical formula 66 chemically bonded thereto.

[0005]

[Chemical 65]

[0006]

[Chemical formula 66]

R in the formula is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative group, (b) an alkylene group having 2 to 20 carbon atoms and a cycloalkylene group. A group and a C _(2-8) alkylene-terminated polydiorganosiloxane, and (C) Chemical Formula 67 (wherein Q ′ is Chemical Formula 68, Chemical Formula 69, Chemical Formula 70, Chemical Formula 71, and Chemical Formula 7).
A divalent C _(2-20) organic group selected from the group consisting of divalent groups represented by the _{formula (} 2) and x is an integer of 1 to 5 ₎ . , Q is chemical formula 73 and chemical formula 7
4 (D in the formula is: 75, 76, 77, 78, 7
9 and formula 80, R ⁸ is formula 81, formula 82,
Chemical formula 83, chemical formula 84, chemical formula 85, chemical formula 86, chemical formula 87 and a divalent organic group of the general formula: chemical formula 88, p is equal to 0 or 1, and X is chemical formula 89 90, chemical formula 91, chemical formula 92 and chemical formula 93, and y is a tetravalent group selected from y), and R ^{1 to} R ⁶ are hydrogen and Selected from C _(1-8) alkyl groups, R ⁷ is the same or different monovalent C _(1-13) hydrocarbon group and monovalent substituted C _(1-13) hydrocarbon group, and Y is Is a divalent group selected from
Is an integer equal to 0-200 and m is an integer equal to 1-2000.

[0008]

[Chemical formula 67]

[0009]

[Chemical 68]

[0010]

[Chemical 69]

[0011]

[Chemical 70]

[0012]

[Chemical 71]

[0013]

[Chemical 72]

[0014]

[Chemical formula 73]

[0015]

[Chemical 74]

[0016]

[Chemical 75]

[0017]

[Chemical 76]

[0018]

[Chemical 77]

[0019]

[Chemical 78]

[0020]

[Chemical 79]

[0021]

[Chemical 80]

[0022]

[Chemical 81]

[0023]

[Chemical formula 82]

[0024]

[Chemical 83]

[0025]

[Chemical 84]

[0026]

[Chemical 85]

[0027]

[Chemical 86]

[0028]

[Chemical 87]

[0029]

[Chemical 88]

[0030]

[Chemical 89]

[0031]

[Chemical 90]

[0032]

[Chemical Formula 91]

[0033]

[Chemical Formula 92]

[0034]

[Chemical formula 93]

[0035]

[Chemical 94]

[0036]

[Chemical 95]

In order to prepare the silicon hydride-terminated polydiorganosiloxane-polyimide copolymer used in the present invention, first the reaction between the organic diamine, norbornene anhydride and organic dianhydride is carried out by the following reaction formula: According to the above procedure, a norbornene-terminated polyimide is formed.

[0038]

[Chemical 96]

Here, Q, R, R ^{1 to} R ⁶ , Y and n are as defined above. The aliphatic unsaturated polyimide of Formula 96 is then hydrosilanated with the silicon hydride of Formula 97 (where r is 0 or 1 and R ⁹ is selected from hydrogen and R ⁷ ) to give the hydrogenation of Formula 98. Produces a silicon-terminated polyimide.

[0040]

[Chemical 97]

[0041]

[Chemical 98]

Here, R, R ^{1 to} R ⁷ , Y, Q and n are as defined above.

The silanol-terminated polydiorganosiloxane-polyimide copolymer of the present invention has the chemical formula 99 (wherein Z is a divalent group represented by the chemical formula 65). Of silicon hydride terminated polyimide
With silanol terminated polydiorganosiloxane in the presence of an effective amount of a condensation catalyst (described below). Where R
⁷ , R ⁹ , r and m are as defined above, and l is an integer of about 1-10 ⁴ .

[0044]

[Chemical 99]

[0045]

[Chemical 100] The groups contained in R ^{1 to} R ⁶ in Chemical formulas 65, 96 and 97 are, for example, hydrogen, methyl, ethyl, propyl, butyl and the like. The group contained in R ⁷ is, for example, an aryl group or a halogenated aryl group, specifically phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc .; an alkenyl group, specifically vinyl, allyl, cyclohexenyl, etc .; C _(1-8) alkyl group and halogenated alkyl group, specifically, methyl, ethyl, propyl,
Butyl and octyl.

[0046]

According to the use of the present invention, on a weight basis: (A) 100 parts of a silanol-terminated polydiorganosiloxane-polyimide copolymer of formula 99, (B) 0.002
A condensation vulcanizable composition is provided which comprises -10 parts curing agent, (C) 0-5 parts condensation catalyst, and (D) 0-3000 parts silanol terminated polydiorganosiloxane of formula (7).

Curing agents that can be used in the above condensation vulcanizable composition include, for example, methyltriacetoxysilane, methyl-tris- (2-ethylhexaneoxy) -silane, and
01 hardener.

[0048]

[Chemical 101]

R ^{7 in} Chemical Formula 101 is as defined above, R ¹⁰
Is a C _(1-8) aliphatic organic group or C _(7-13) aralkyl group selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, and X is acyloxy, amide , Amino, carbamato, enoxy, halo, imidato, isocyanato,
A group which is liberated by hydrolysis selected from the group consisting of ketoximato, oximato, thioisocyanato and ureido groups, a is an integer equal to 0-4, b is an integer equal to 0 or 1, and the sum of a + b is 0-4. equal.

In addition to the curing agent of Formula 101, the condensation vulcanizable composition of the present invention also includes an alkoxy-functional crosslinker of Formula 102 (wherein R ⁷ , R ¹⁰ and b are as defined above). Can be used.

[0051]

[Chemical 102]

A condensation catalyst can be used to accelerate the cure of the condensation vulcanizable composition and, in some cases, accelerate the condensation of the silanol-terminated polydiorganosiloxane of Formula 99 with the silicon hydride-terminated polyimide of Formula 98. can do. For example, 0.001 to 1 per 100 parts of the silanol-terminated polydiorganosiloxane-polyimide copolymer.
Some condensation catalysts can be used. As the condensation catalyst, tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, tin octoate,
Examples include isobutyltin tricelloate, dimethyltin dibutyrate, dimethyltin dinedeconeate, triethyltin tartrate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, tin butyrate. Suitable condensation catalysts are tin compounds, of which dibutyltin diacetate is particularly preferred.

Examples of the titanium compound include 1,3-propanedioxytitanium bis (ethylacetoacetate), 1,3-propanedioxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetonate), titanium naphthenate. , Tetrabutyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, ethyl triethanolamine titanate can be used. In addition, Weyenberg, US Pat. No. 3,334,34
A β-dicarbonyltitanium compound as shown in No. 067 can be used as the condensation catalyst in the present invention.

Zirconium compounds such as zirconium octoate can also be used.

Still another example of the metal condensation catalyst is 2
-Lead ethyl octanoate, iron 2-ethylhexanoate, 2-
Examples thereof include cobalt ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, antimony octoate, bismuth naphthenate, zinc naphthenate, and zinc stearate.

Examples of non-metal condensation catalysts are hexyl ammonium acetate and benzyl trimethyl ammonium acetate.

In addition to the above-mentioned one-pack type condensation vulcanizing curing agent, in the practice of the present invention, it is added to a silanol-terminated polydiorganosiloxane-polyimide copolymer to obtain Ni.
Curing agents capable of forming two-part condensation vulcanizable compositions such as those shown in U.S. Pat. No. 3,127,363 to tzche et al. can also be used.

Examples of organic dianhydrides that can be used in the present invention to form the norbornene-terminated polyimide of formula 96 with the norbornene anhydride chain terminating monomer are benzophenone dianhydride, pyromellitic dianhydride, 2, 2
-Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (2,3
-Dicarboxyphenoxy) phenyl] propane dianhydride, 4- (2,3-dicarboxyphenoxy) -4'-
(3,4-dicarboxyphenoxy) diphenyl-2,
2-propane dianhydride and the bisnorbornane siloxane dianhydride of Formula 103, and mixtures thereof.

[0059]

[Chemical 103]

Organic diamines that can be used to form the polyimide block of the silanol terminated polydiorganosiloxane-polyimide copolymer include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino. Diphenylpropane,
4,4'-diaminodiphenylmethane (usually 4,4'-
Methylenedianiline), 4,4'-diaminodiphenyl sulfide (usually called 4,4'-thiodianiline), 4,4'-diaminodiphenyl ether (usually called 4,4'-oxydianiline) ), 1,
5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine 2,4-bis (β
-Amino-t-butyl) toluene, 1,3-diamino-
4-isopropylbenzene, 1,2-bis (3-aminopropoxy) ethane, benzidine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, bis (4- Aminocyclohexyl) methane, 3-methylheptamethylenediamine, 4,4 dimethylheptamethylenediamine, 2,1
1-dodecanediamine 2,2-dimethylpropylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-
Methylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-cyclohexanediamine 1,12
-Octadecanediamine, bis (3-aminopropyl)
Sulfide, N-methyl-bis (3-aminopropyl)
Amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine,
Bis (3-aminopropyl) tetramethyldisiloxane, bis (4-aminoptyl) tetramethyldisiloxane, and mixtures of these diamines.

An example of a silicon hydride of formula 97 which can be used in the present invention to introduce a silicon hydride functional group into a polyimide having an aliphatic unsaturated norbornene group is a diorganosilane, specifically dimethyl. Examples include silane, diphenylsilane, and 1,1,3,3-tetramethyldisiloxane.

The silanol-terminated polydiorganosiloxane of formula 100 which can be used in combination with the above silicon hydride terminated polyimide to prepare the silanol-terminated polydiorganosiloxane-polyimide copolymer of formula 99 has a viscosity measured at about 25 ° C. Preferably in the range of about 10 to 400,000 centipoise, especially about 1000 to 250,000 centipoise. To produce these silanol terminated fluids, relatively high molecular weight organopolysiloxanes such as dimethylpolysiloxane are treated with water in the presence of a mineral acid or base catalyst. Hydrolysis of diorganohalosilanes such as dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, methylfluoropropyldichlorosilane, methylcyanoethyldichlorosilane or mixtures thereof can produce low molecular weight polymers. Subsequent equilibration yields a higher molecular weight organopolysiloxane. Organopolysiloxanes may be treated with steam under pressure or as described in US Pat. No. 2,607,79.
It can also be processed by other methods described in No. 2 and British Patent No. 835,790.

Examples of condensation catalysts that can be used to form the silanol-terminated polydiorganosiloxane-polyimide copolymer of Formula 99 include platinum catalysts, specifically Karstedt US Pat. No. 3,775,442, Ashby. There are unsaturated siloxane platinum complexes such as those shown in US Pat. Nos. 3,159,601 and 3,159,662 and Lamoreaux US Pat. No. 3,220,972.
An effective amount of platinum catalyst is about 10 ^{-4 to} 0.1 wt% platinum, based on the weight of the curable hydrosilation mixture.

Various fillers and pigments may be incorporated into the room temperature vulcanizable composition. For example, titanium dioxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, fumed silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, quartz powder, calcium carbonate and the like can be used. It is clear that the amount of filler used can be varied within wide limits depending on the intended use. For example, in sealant applications, the curable compositions of the present invention can be used without fillers. For other uses, such as when the curable composition of the present invention is used to make a binder, it is possible to use a large amount of filler, such as 700 parts by weight or more per 100 parts by weight of polydiorganosiloxane-polyimide copolymer. it can. In such applications, the filler can be a major component, preferably a bulking agent having an average particle size in the range of about 1 to 10 microns, such as quartz powder, polyvinyl chloride or mixtures thereof.

The condensation vulcanizable composition can also be used as a building sealant and caulking compound. Therefore, the exact amount of filler will depend on such factors as the application for which the organopolysiloxane composition is intended to be used, the type of filler used (ie, filler density and particle size). It is preferred to use from 5 to 300 parts of filler per 100 parts of silanol-terminated organopolysiloxane (which may include up to about 35 parts of reinforcing filler, such as fumed silica filler).

The silicon hydride terminated polyimide of Formula 98 can be used as an adhesion promoter in room temperature vulcanizable organopolysiloxane compositions. The silanol-terminated polydiorganosiloxane-polyimide copolymer of Chemical Formula 99 can be used as an impact modifier in the room temperature vulcanizable organopolysiloxane composition as described above.

The condensation vulcanizable polydiorganosiloxane-polyimide copolymer composition comprises a silanol-terminated polydiorganosiloxane-polyimide copolymer (hereinafter referred to as "99") containing a curing agent, a condensation catalyst and, if desired, a crosslinking agent. It can be produced by mixing with a silanol-polyimide copolymer ").

An effective amount of the curing agent as described above can be used in the condensation vulcanizable composition.
It depends on whether a one-part system is desired or a two-part system is desired, or whether the curing agent used produces acidic or substantially neutral by-products. For example, when an acyloxy curing agent such as methyltriacetoxysilane is used, good results are obtained by using 0.002 to 10 parts of methyltriacetoxysilane per 100 parts of silanol-polyimide copolymer. The curing agent represented by Chemical formula 101 can be used in the proportion of 0.002 to 10 parts of the curing agent per 100 parts of the silanol-polyimide copolymer. The cross-linking agent as shown in Chemical formula 102 is also
Can be used in a proportion of 0 to 10 parts of crosslinking agent per 100 parts of silanol-polyimide copolymer. The condensation catalyst can also be used in the ratio as described 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 optionally be mixed with curing agents, condensation agents and condensation agents. It can be introduced into the silicone-polyimide copolymer before, simultaneously with, or after the introduction of the catalyst and the like.

The synthesis of the norbornene-terminated polyimide of Formula 96 is carried out by conventional methods to produce approximately equimolar amounts of organic diamine and organic dianhydride in an effective amount to terminate the chain to a desired molecular weight of the polyimide. It can be done by using with norbornene anhydride. During the polymerization of norbornene-terminated polyimide, organic solvents such as o
-Dichlorobenzene can be used and 140-200 ° C
Temperatures in the range of can be used. The reaction in an inert atmosphere,
For example, it can be carried out under nitrogen to minimize unwanted side reactions. The reaction time can vary from less than 30 minutes to 3 hours depending on the nature of the reactants, the desired molecular weight of the polyimide, and the like.

The silicon hydride-terminated polyimide of formula 98 is prepared by reacting the norbornene-terminated polyimide of formula 96 with a suitable silicon hydride of formula 97 such as dihydrogensilane or dihydrogendisiloxane in the presence of an effective amount of platinum catalyst. It can be synthesized by carrying out below. An effective amount of platinum catalyst is about 10 ^-6 to 10 ^-3 parts of platinum per part of hydrosilation reaction mixture consisting of norbornene terminated polyimide, silicon hydride and an inert organic solvent, the inert organic solvent having a solid content of 10 parts. Sufficient to produce -50% by weight of the mixture can be used. Suitable inert organic solvents are, for example, chlorobenzene and o-dichlorobenzene. The hydrosilation reaction is conducted under substantially anhydrous conditions, 1
It is preferably carried out at a temperature in the range of 5 to 90 ° C.

The silanol-polyimide copolymer is prepared by reacting the silicon hydride-terminated polyimide of Chemical Formula 98 with the silanol-terminated polydiorganosiloxane of Chemical Formula 1
It can be achieved by carrying out at a temperature in the range of 5-150 ° C. in the presence of an effective amount of copolymerization catalyst. Suitable copolymerization catalysts include, for example, amines, alkali metal fluorides, colloidal nickel, zinc chloride, platinum or rhodium complexes, dibutyltin diacetate, etc., depending on the mutual solubility of the reactants, neutral solvents that accelerate the reaction. , With dichloromethane, chlorobenzene, o-dichlorobenzene, etc., or without such a solvent.

The condensation vulcanizable silicone-polyimide composition can also be blended with a silanol terminated polydiorganosiloxane of formula 100 as described above. The compounding can be carried out under substantially anhydrous conditions at temperatures in the range of about 15 to 200 ° C or higher. The cured silicone-polyimide copolymer thus obtained has high strength,
It can be used in various applications requiring a high-performance heat-resistant elastomer.

[0074]

EXAMPLES In order that those skilled in the art may readily practice the present invention, the following examples of the present invention are given by way of illustration and not limitation. All "parts" are by weight.

[0075]

Example 1 13.68 g of 5-norbornene-2,3
-A mixture of dicarboxylic anhydride and 43.33 g of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 13.51 g of m-
A solution of phenylenediamine and 100 ml of o-dichlorobenzene was added over 10 minutes under nitrogen.
The resulting solution was heated under reflux for 2 hours, during which water was continuously azeotropically removed. The resulting solution was poured into 400 ml of methanol and stirred vigorously. The product was precipitated, filtered, washed with methanol and dried. Based on the method of manufacture, the product had Formula 104.

[0076]

[Chemical 104]

64.8 g of the above norbornene-terminated polyetherimide was obtained with a yield of 97%.

To a mixture of 22.0 g of the above norbornene-terminated polyetherimide, 4.0 g of 1,1,3,3-tetramethyldisiloxane and 40 ml of dry chlorobenzene, Karstedt US Pat. 442
5 drops of 5% platinum catalyst prepared according to No. 5 was added in a 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 and the filtrate was poured into 200 ml dry diethyl ether with vigorous stirring. A precipitate was obtained, which was filtered, washed with diethyl ether and dried. Based on the method of preparation, the precipitate obtained in 98% yield was the silicon hydride terminated polyetherimide of Formula 105.

[0079]

[Chemical 105]

The identity of the product was further confirmed by NMR and IR analysis.

To a mixture of 5.58 g of the above silicon hydride terminated polyetherimide, 34.02 g of silanol terminated polydimethylsiloxane (silanol content 0.31% by weight) and 30 ml of dry dichloromethane was added the above Karste.
One drop of a 5% solution of dt 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. The solvent was evaporated from the mixture to give an opaque residue with a viscosity of 146,200 centipoise. Based on the method of preparation, the opaque residue was a silanol terminated polydimethylsiloxane-polyetherimide block copolymer of Formula 106.

[0082]

[Chemical formula 106]

However, x is an integer of 3 or more.

The silanol-terminated silicone-polyetherimide copolymer was mixed under substantially anhydrous conditions with 1.0 gram mol of methyltrimethoxysilane, followed by 0.1 g dibutyltin diacetate and 0.3 g. Dibutylamine was added. The resulting mixture has a humidity of 58%
It was left for 1 week under the environment. A tack free cured block copolymer is thus obtained, which has a tensile strength of 146
It exhibited psi and an elongation of 630%.

The above procedure was repeated using a silanol-terminated polydimethylsiloxane having a viscosity of 146,000 centipoise (25 ° C.) instead of the silanol-terminated polydimethylsiloxane-polyetherimide block copolymer. A cured product having a tensile strength of 49 psi and an elongation of 300% was obtained.

[0086]

EXAMPLE 2 A mixture of 9.91 g (0.05 mol) of methylene dianiline, 19.62 g (0.01 mol) of 5-norbornene-2,3-dicarboxylic acid monomethyl ester and 100 ml of dry methanol was added to N2. It was refluxed for 2 hours in _2. After removing the solvent, the residue was heated in an oven at 150 ° C. for 2 hours under N ₂ . The white solid obtained was dissolved in CH ₂ Cl ₂ , poured into 400 ml of methanol and stirred vigorously. Based on the method of preparation, bis (norbornene imide) was obtained, which was filtered, washed with methanol and dried. The bisimide of Chemical formula 107 was obtained with a yield of 98%.

[0087]

[Chemical formula 107]

To a solution of 100 ml of dry chlorobenzene and 5.26 g (1 × 10 ^-2 mol) of the above bis (norbornene imide) under nitrogen, 4 g (3 × 10 ^-2 mol).
1,1,3,3-tetramethyldisiloxane and Ka
P shown in U.S. Pat. No. 3,715,334 to rstedt
5 drops of a 5% solution of t catalyst were added. 60 ~
Heated to 80 ° C. overnight. After removing excess 1,1,3,3-tetramethyldisiloxane, carbon black was added to the solution. The mixture was stirred for 1 hour and then filtered. Based on the production method, a silicon hydride terminated bisimide of Chemical formula 108 was obtained.

[0089]

[Chemical 108]

The above silicon hydride-terminated bisimide was added to 15.2
3 g silanol-terminated polydimethylsiloxane (OH content 2.6% by weight) and 3 mg ClRh (PPh ₃ ).
(However, ph is a phenyl group), Then, it heated at 80 degreeC for 2 hours. Removal of the solvent gave a clear, very viscous residue. Based on the method of preparation, this residue was a silanol-terminated bisimide siloxane of Formula 109.

[0091]

[Chemical 109]

However, y is an integer of 11 or more. The residue was subsequently mixed with 0.1 g of methyltriacetoxysilane and then Bu ₂ Sn (OAc) ₂ was added. The obtained mixture was left for one week in an environment of 58% humidity. The cured material was a clear rubber with significantly improved toughness and elongation.

[0093]

EXAMPLE 3 To prepare a norbornene-terminated bisimide, 174 g isophoronediamine and 328 g norbornene dicarboxylic acid anhydride were added to 1800 ml N-.
Dissolved in methylpyrrolidone and 600 ml toluene. The reaction mixture was heated for 12 hours to remove water. The mixture was then heated to remove toluene and some of the N-methylpyrrolidone. The residue was poured into 40% isopropanol. The beige solid thus obtained was collected by filtration and dried.

46.2 g of the above isophorone norbornene terminated diimide, 20 ppm platinum catalyst and 200 ml
Was treated with 32.6 g of tetramethyldisiloxane at 80-100 ° C. for 6 hours to produce isophorone diimidedihydrosiloxane. About 73g
Of the diimide hydrosiloxane with a silanol-terminated polydimethylsiloxane fluid having an average of about 3 chemically bonded siloxy units in a molar ratio of about 1: 1 and 1: 2 in the presence of a platinum catalyst of 50-60. Condensation at a temperature of ° C produced a silanol terminated polydiorganosiloxane-polyimide copolymer within the range of 99.

20 g of silanol-terminated polydimethylsiloxane-polyimide copolymer made from a mixture having a ratio of 2 mol silanol-terminated dimethylsiloxane to 1 mol diimidehydrosiloxane, 100 g silanol-terminated polydimethylsiloxane (viscosity 120-180,00).
0 centipoise), a condensation curable mixture was prepared under anhydrous conditions from 4 g of methyltrimethoxysisilane, 0.5 g of dihexylamine and 0.3 g of dibutyltin diacetate.

The RTV composition cured within 10-16 minutes when exposed to air. Hardness (Shore A), Elongation (%) and Tensile Strength (psi)
Was measured. The following results were obtained.

Hardness 17 Elongation 372 Tensile Strength 143

Except that the silanol-terminated polydiorganosiloxane-polyimide copolymer of the present invention is not included.
The above procedure was repeated to make an RTV composition. The following results were obtained.

Hardness 9 Elongation 328 Tensile strength 53

These results show that the silanol terminated polydimethylsiloxane-polyimide copolymer provides excellent physical properties to conventional room temperature vulcanizable organopolysiloxane compositions.

[0101]

Example 4 The procedure of Example 3 was repeated. However, in this example, a silanol terminated polydimethylsiloxane-polyimide copolymer prepared from a mixture of a silicon hydride terminated diimide and a silanol terminated polydimethylsiloxane in a 1: 1 molar ratio was used. This silanol terminated polydimethylsiloxane-polyimide was further compounded with the components of the room temperature vulcanizable composition of Example 3. However, in this example, the viscosity is 20 to 5
A 10,000 centipoise silanol terminated polydimethylsiloxane was used. In addition, fumed silica treated with octamethylcyclotetrasiloxane and disilazane was added to the above mixture in proportions of 5% and 10% by weight, respectively, based on the weight of the total mixture. These mixtures were cured under atmospheric conditions as described in Example 3 with the following results. "5% filler" and "10% filler" mean the filler-containing composition described above, and the Shore A hardness, elongation and tensile strength are as defined above.

[0102]

Silanol-terminated polydimethylsiloxane-
The above procedure was repeated, except that the polyimide copolymer was not used in the formulation. The following results were obtained.

[0104]

These results indicate that the cured room temperature vulcanizable organopolysiloxane composition is provided with significantly increased toughness as a result of the introduction of the silanol-terminated polydimethylsiloxane-polyimide copolymer of the present invention. ing.

Although the above examples only show a few examples of a very large number of condensation vulcanizable silicone-polyimide copolymers containing room temperature vulcanizable and low temperature vulcanizable compositions within the scope of the present invention, The present invention provides a silanol-terminated polydiorganosiloxane-polyimide copolymer in combination with a curing agent as shown in Formula 101 and optionally a crosslinker as shown in Formula 102, and further in combination with a condensation catalyst. It should be understood that it is responsible for the broader range of condensation vulcanizable compositions that can be obtained when used together. The present invention further provides a silicon hydride-terminated polyimide of Chemical Formula 98 and a chemical formula 99 which are useful materials for producing a condensation vulcanizable composition that can be converted to a high strength silicone-polyimide copolymer in the cured state. It is also involved in silanol-polyimide copolymers.

Claims (4)

[Claims] 1. The following chemical formula 1: [Z in the chemical formula 1 is the following chemical formula 2: Wherein R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, (b) an alkylene group having 2 to 20 carbon atoms, and A cycloalkylene group and a C _(2-8) alkylene-terminated polydiorganosiloxane, and (c) the following chemical formula 3: (Q 'in Chemical formula 3 is selected from the group consisting of Chemical formula 4, Chemical formula 5, Chemical formula 6, Chemical formula 7, and Chemical formula 8 and x is an integer of 1 to 5) [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] A divalent C selected from the group consisting of divalent groups represented by
_(2-20) an organic group, Q is a chemical _formula 9 or a chemical formula 10 [Chemical 10] (D in the formula is expressed in Chemical formula 11, Chemical formula 12, Chemical formula 13, Chemical formula 14, Chemical formula 1
5 and chemical formula 16, [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] R ⁸ is chemical formula 17, chemical formula 18, chemical formula 19, chemical formula 20, chemical formula 21, chemical formula 2
2, Chemical Formula 23 and General Formula 24: [Chemical 18] [Chemical 19] [Chemical 20] [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] Is a divalent group selected from the divalent organic groups of, p is equal to 0 or 1, and X is of the following formulas 25, 26, 27, 28 and 29: [Chemical formula 26] [Chemical 27] [Chemical 28] [Chemical 29] Is a tetravalent group selected from the group consisting of divalent groups, wherein y is an integer of 1 to 5), R ^{1 to} R ⁶ are selected from hydrogen and a C _(1-8) alkyl group, R ⁷ is the same or different monovalent C _(1-13) hydrocarbon group and monovalent substituted C _(1-13) hydrocarbon group, R ⁹ is selected from hydrogen and R ⁷ , and Y is A divalent group selected from 31 [Chemical 31] n is an integer equal to 0 to 200, r is an integer equal to 0 or 1, m is an integer equal to 1 to 2000, and l is an integer having a value of about 1 to 10 ⁴ ] Terminated polydiorganosiloxane polyimide. 2. The silanol-terminated polydiorganosiloxane polyimide is represented by the following formula: The polyimide according to claim 1, which is a silanol-terminated polydimethylsiloxane-polyimide copolymer (wherein x is an integer of 3 or more). 3. The following chemical formula 33: [Wherein R is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, (b) 2
Alkylene and cycloalkylene groups having 20 carbon atoms and C _(2-8) alkylene-terminated polydiorganosiloxane, and (c) (Q ′ in the formula is selected from the group consisting of: 35, 36, 37, 38 and 39, and x is an integer of 1 to 5) [Chemical 36] [Chemical 37] [Chemical 38] [Chemical Formula 39] A divalent C selected from the group consisting of divalent groups represented by
_(2-20) an organic group, Q is a chemical _formula 40 and a chemical formula 41 [Chemical 41] (In the formula, D is a chemical formula 42, a chemical formula 43, a chemical formula 44, a chemical formula 45, a chemical formula 46
And are selected from the following: [Chemical 43] [Chemical 44] [Chemical formula 45] [Chemical formula 46] [Chemical 47] R ⁸ is chemical formula 48, chemical formula 49, chemical formula 50, chemical formula 51, chemical formula 52, chemical formula 5
3, Chemical Formula 54 and General Formula 55: [Chemical 49] [Chemical 50] [Chemical 51] [Chemical 52] [Chemical 53] [Chemical 54] [Chemical 55] Is a divalent group selected from the group consisting of divalent organic groups, wherein p is equal to 0 or 1, and X is the following formula 56, formula 57, formula 58, formula 59 and formula 60: [Chemical 57] [Chemical 58] [Chemical 59] [Chemical 60] Is a tetravalent group selected from the group consisting of divalent groups, wherein y is an integer of 1 to 5), R ^{1 to} R ⁶ are selected from hydrogen and a C _(1-8) alkyl group, R ⁷ is the same or different monovalent C _(1-13) hydrocarbon group and monovalent substituted C _(1-13) hydrocarbon group, R ⁹ is selected from hydrogen and R ⁷ , and Y is A divalent group selected from 62 [Chemical formula 62] n is an integer equal to 0 to 200, r is an integer equal to 0 or 1], and a silicon hydride terminated polyimide represented by the following formula: (Wherein R ⁷ is the same or different monovalent C _(1-13) hydrocarbon group and monovalent substituted C _(1-13) hydrocarbon group, and m is an integer equal to 1 to 2000), a silanol-terminated polydiorgano A method of making a silanol terminated polydiorganosiloxane-polyimide copolymer comprising reacting with a siloxane in the presence of an effective amount of condensation contact. 4. The silicon hydride terminated polyimide has the following chemical formula: embedded image The method according to claim 3, which is represented by: