JPH0356490A - Preparation of silylnorbornane anhydride - Google Patents

Abstract

PURPOSE: To easily obtain the title compd. useful as an adhesion accelerator for a room temp. vulcanizable organopolysiloxane compsn. by reacting a norbornenecarboxylic acid anhydride with a specific silicon hydride in the presence of a platinum catalyst.

CONSTITUTION: A norbornene anhydride represented by formula I [wherein R and R¹-R⁵ are each H or 1-8C alkyl and Z is -O- or C-(R)₂] and a silane represented by formula II [wherein R⁶ is a monovalent (substd.) 1-13C hydrocarbon; X is a hydrolyzing group such as halogen or the like or a siloxane represented by formula III (Y is a group represented by formula IV, cyano, etc.); a, b and c are each 0-3 but b+c is 0-3)] are reacted in the presence of a platinum catalyst to obtain the objective compd. represented by formula V. As the compd. represented by formula II, for example, there is 1,1,3,3- tetramethyldisiloxane or the like. The use amt. of the platinum catalyst is pref. 0.001-0.1% by wt. of the above mentioned reaction mixture.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to silylnorbornane anhydrides and processes for their preparation. More specifically, the present invention provides hydrosilanization of norbornenecarboxylic anhydride with silicon hydride in the form of silane, disiloxane or polysiloxane.
lation) relating to doing something.

Prior to the present invention, indirect methods have been used to synthesize silicon-functional anhydrides, for example in J. R. Pratt
al. J. org. chem. ．． 3 8. 4 2
7 1 (1 9 7 3), a silane is added to an orthoalkyl substituted aromatic hydrocarbon and the alkyl group is then oxidized. Alternatively, L
．． Ya. Moshlnskil et al. S.
S. R. 2 4 4 6 1 6 (1 9 6
9) [Chem. Abstracts. 7 2,
3 2 7 7 7m (1 9 70)], maleic anhydride is reacted with cyclopentadiene attached to the polysiloxane backbone by a carbon-carbon silico linkage to form 5-norbornene-2 .Produces a siloxane functionalized with 3-carboxylic anhydride groups.

The direct reaction of unsaturated anhydrides, such as allylsuccinic anhydride, with trichlorosilane has been described by Waiter Haf'ner.
et al. Chei. Abstracts. 2121
83J, VOl. 91, page 2 4 (1979). Attempts to directly react silicon hydrides with cyclic anhydrides having internal aliphatic unsaturation, such as maleic anhydride and tetrahydrophthalic anhydride, to produce silyl anhydrides have been unsuccessful. Why does the direct hydrosilanization reaction fail with anhydrides with endocyclic unsaturation, such as maleic anhydride, but is successful with aliphatic unsaturated cyclic anhydrides with aliphatic unsaturation in the side chain, such as allylsuccinic anhydride? The reason for this is not completely clear. One possible explanation is that terminal olefins are much more reactive than internal olefins.

Although the cyclic anhydride with internal aliphatic unsaturation normally does not react with silicon hydride, Hydrogen group and monovalent substitution C carbonization (1-13)
(1-13) is a group selected from hydrogen groups, and Z is selected from 101 and C-(R)2]. This is based on the knowledge that silylnorbornane anhydride or dianhydride is easily reacted with silicon hydride to form silylnorbornane anhydride or dianhydride.

DISCLOSURE OF THE INVENTION According to the present invention, a silylnorbornane anhydride of the following formula is provided.

Here, R-R5 and Z are as defined above, and R6 is C(
1-13) selected from monovalent hydrocarbon groups and substituted monovalent hydrocarbon groups, where X is (a) halogen, hydrogen, C alkoxy (1-8) cy, acyloxy, -N (R7) 2 cyano, amido, a hydrolyzable group selected from the group consisting of carbamato, enoxy, imidato, isocyanato, oximato, isocyanate, oximato, thioisocyanato and ureido, (b) of the following formula: (Y) c-S·04-(be.) 2 and (c) a polysiloxane having the following formula: R6 is as defined above, R7 is selected from monovalent hydrocarbon groups, and Y has the following formula: O and (a) group, Y1 is selected from R6 group, Y group and mixed groups thereof, and a is 0-3
b is an integer equal to 0 to 3, C is an integer equal to 0 to 3, the sum of b+c is equal to O to 3, and n is an integer equal to 1 to 2000.

Groups included within R-RS are, for example, halogen, specifically chloro, bromo, and the like. The R-R6 group includes aryl groups and halogenated aryl groups, such as phenyl,
Chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc.; alkenyl groups, such as vinyl, allyl, cyclohexenyl, etc.; C alkyl groups, halogenated alkyls and (1-8) aminoalkyl groups, such as methyl, ethyl, propyl,
Includes butyl, octyl, etc. R7 is a C alkyl group, such as methyl, ethyl, but(1-8) lopyl, and a C aryl group, such as (6-
13) Selected from phenyl, tolyl, etc. When R%R7 is a plurality of groups, these groups may all be the same or may be any two or more of the above groups.

The silylnorbornane anhydride included in formula (2) is
For example:

C.I. C.I. Formula (2) siloxane norborna contained within The anhydrous For example:

0 O O O formula (2) polysiloxane norbo contained within Lunaan anhydride is For example:

Here, R-R6, Z and n are as defined above, m is 0
An integer equal to ~500, the sum of m10 equals 1 to 2000.

According to another aspect of the invention, the norbornene anhydride of formula (1) is reacted with a silane of the formula: There is provided a method for producing a silylnorbornane anhydride encompassed within formula (2), the method comprising:

Through experience, we have found that norbornene anhydride of formula (1) and formula (3
) with silane can be accelerated in the presence of inert organic solvents such as diethylene glycol dimethyl ether, toluene, chlorobenzene, ethylene glycol dimethyl ether, and tetrahydrofuran. If monohydrosilated isomers are formed, longer reaction times and higher temperatures are required for dianhydride formation, such as temperatures in excess of 100°C.

If it is desired to increase the molecular weight of organoborisiloxanes having chemically bonded norbornane anhydride siloxy units bonded to silicon by carbon-silicon bonds, relatively low molecular weight norbornane-substituted siloxanes can be substituted with cyclic siloxanes, such as octamethylcyclotetrasiloxane. and an acid catalyst, such as sulfuric acid. Typical reactions are as follows.

Here, R6 and Z are as defined above, p is a positive integer, and m
' has a value of 3-6.

Hydrosilanization catalysts that can be used in carrying out the present invention include, for example, Karst
edt U.S. Patent No. 3.775.442, Ashby
U.S. Pat. Nos. 3.159.601 and 3.159
．． No. 662 and Lasoreaux, US Pat. No. 3.
220.972. An effective amount of platinum catalyst is based on the amount of ffi in the hydrosilanization reaction mixture or cocondensation mixture, about 0.
001~0. lffi amount% of platinum.

The silylnorbornane anhydride of formula (2) can be combined with an organic diamine, e.g. (2) and such anhydrides and other dianhydrides such as penzophenone dianhydride, pyromellitic dianhydride and aromatic bis(
ether anhydride), it can be used as an intermediate for producing polyimidoborodiorganosiloxane block polymers. Additionally, some of the silylnorbornane anhydrides encompassed within formula (2) can be used as adhesion promoters in room temperature vulcanizable organoborisiloxane compositions.

The following examples are presented by way of illustration and not by way of limitation, to enable those skilled in the art to better practice the invention.

All parts are parts by weight.

Example 1 69.4 g (0.42 mol) of 5-norbornene-2
, 3-dicarboxylic anhydride, 26.8 g (0.2 mol)
1.1.3.3-tetramethyldisiloxane and 1
Karsted, assigned to the same assignee as the present invention, was added with stirring to a mixture of 00 ml of dry chloropenzene.
Ten drops of a 5% platinum catalyst prepared according to US Pat. No. 3,775,442 of T.T. were added. The resulting mixture was heated to 70-80°C for 4 hours with stirring, then to 100-110°C.
Heat to ℃ overnight. After cooling, add carbon plaque,
The solution was stirred for 30 minutes at room temperature. After filtering and removing the solvent with a vacuum pump at 100° C. and adding dry diethyl ether, a white crystalline solid precipitated. Based on the manufacturing method, this product has the formula 5.5'-(1
．． It was 1.3.3-tetramethyl-1.3-disiloxanediyl) monobisnorbornane-2,3-dicarboxylic acid anhydride.

The identity of the above dianhydride is determined by NMR, IR, mass spectrometry and further confirmed by elemental analysis.

0.57g of the above 5. 5' - (1. 1.
3. A mixture of 3-tetramethyl-1,3-disiloxanediyl)-bisnorbornane-2,3-dicarboxylic anhydride, 1.289 g of penzophenone tetracarboxylic dianhydride and 5 ml of dimethylformamide was added to 991sr methylene dianiline and 5ml
of dimethylformamide under nitrogen while stirring. The resulting solution was stirred at room temperature for 2 hours.

Pour a portion of this solution into a glass dish and heat it in a furnace at 80 °C under nitrogen.
for 1 hour and then at 150° C. for 2 hours. Tg-
A silicone-polyimide copolymer having a temperature of 243°C was obtained. This copolymer is useful as a high temperature insulator for gold conductors.

Example 2 A mixture of 8.36 g of 5-norbornene-2,3-dicarboxylic anhydride, 44.8 g of α,ω-dihydrogen polydimethylsiloxane with an average molecular weight of 1790, and lOml of chlorobenzene was added to the mixture of 10 drops of platinum catalyst were added under nitrogen atmosphere. Stir the mixture overnight60~
Heated to 80°C. After cooling, add carbon black,
The solution was stirred for 30 minutes at room temperature. The resulting mixture was filtered and the solvent was removed under vacuum at 100° C., yielding a colorless viscous oil. Based on the manufacturing method, a norbornane anhydride end-capped polydimethylsiloxane of the following formula was obtained.

The identity of the above material was further confirmed by NMR analysis.

0.53 g of the above polysiloxane dianhydride, 0.725
g of penzophenone dianhydride and 5 ml of dimethylformamide into a mixture of 0.496 g of methylene dianiline and 5 ml of dimethylformamide;
Added with stirring under nitrogen. The resulting solution was stirred at room temperature for 2 hours.

The resulting solution was then poured into a glass dish and heated in a furnace under nitrogen for 80 mL.
It was dried at 150°C for 1 hour and then at 150°C for 2 hours. Tg-
A film having a temperature of 271°C was obtained. Based on the manufacturing method, this product is a block copolymer. This block copolymer is useful as a polyimide impact modifier.

Example 3 1.64 g (10'mol) of 5-norbornene-2,3
- A mixture of dicarboxylic anhydride, 1.5 g (1.6 X 10-2 mol) dimethylchlorosilane, 5 drops of the catalyst of Example 1 and 39 ml toluene was sealed under anhydrous conditions and kept at 60-80°C overnight. Heated. After removing the volatiles under vacuum, the residue was analyzed by NMR, IR and GC/mass spectrometry, which confirmed the quantitative formation of 5-dimethylchlorosilylnorbornane-2,3-dicarboxylic anhydride. Ta. HNMR S (in CDC13, 7.25
ppm internal standard) 3.43 (2H, m), 2.85
(2H, m), 1. 90-1. 58
(4H, m), 0. 90 (IH, t)
,0. 42 (3H,S) and 0.37
(3H,S); IR (analyzed as is without dilution) 2
960,2870.1850 and 1770cm
-'. Mass (strength%) 260 (M+2.1.4%), 2
58 (M”, 2.9), 192 (8.6), 159
(28.5), 95 (60.3), 93 (100)
, 66 (97.4). For further purification, the product was dissolved in H2O (
0.2g) at 0°C, and then stirred at room temperature for 2 hours. Remove volatiles and store the residue under vacuum at 200 °C.
The mixture was heated for 2 hours. After adding dry diethyl ether, a white precipitate (1.8 g, 80% yield) was collected and dried.

The spectroscopic data of the product is 5.5'-
The data were the same as for (1.1,3.3-tetramethyl-1.3-disiloxanediyl)-bisnorbornane-2.3-dicarboxylic anhydride.

Example 4 1 drop of 96% sulfuric acid to 2.75 g of the dianhydride of Example 3,
Added to a mixture of 10.7 g octamethylcyclotetrasiloxane and 50 ml dry toluene. The resulting solution was refluxed for 2 hours. After cooling, carbon black was added and the solution was heated to 100° C. for 1 hour. Passage and evaporation gave a colorless viscous oil. Based on the method of manufacture, the product was an anhydride-terminated polydimethylsiloxane having the formula:

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

Example 5 6.57r (0.04 mol) of 5-norbornene-2
．． 3-dicarboxylic anhydride, 61.3 g of methylhydrogen-dimethylsiloxane copolymer (3.4% by weight of (H)C
H3S=O and MW-30.000), 10
0 ml of chlorobenzene and 10 drops of Example 1 pt
The catalyst solution was heated to 80° C. overnight. After adding the carbon black, the mixture was stirred at room temperature for 1 hour. Filtration and evaporation of the low boiling material under vacuum gave a colorless viscous residue. Based on the method of preparation, the product was a norbornane anhydride functionalized polysiloxane having the formula:

Product identity was further confirmed by NMR and IR.

U.S. Pat. No. 3,541,04 to Beers et al., assigned to the same assignee as the present invention, using 10 parts of the above norbornane anhydride-functionalized polysiloxane blend as an adhesion promoter.
Blend with 100 parts of room temperature vulcanizable polydimethylsiloxane as shown in No. 4.

Example 6 The procedure of Example 1 was repeated. However, 0.02 mol of 5-norbornene-2,3-dicarboxylic anhydride and 0.02 mol of 5-norbornene-2,3-dicarboxylic anhydride.
24 moles of disiloxane were used.

The resulting mixture was stirred at 60-80°C for 8 hours. At the end of the procedure, a colorless viscous oil was obtained in quantitative yield. Based on the method of manufacture, this product was O2. Product identity was confirmed by NMR and IR. This compound has been found to be useful as an adhesion promoter for room temperature vulcanizable compositions.

Although the above examples refer only to a few of the numerous examples that may be included in the practice of this invention, the present invention provides the following examples: It should be understood that a very wide variety of silylnorbornanes are concerned, including polysiloxanes. These materials are produced by hydrosilanizing norbornene anhydride of formula (1) with silicon hydride of formula (3).

In addition to monoanhydrides and dianhydrides as shown in formula (2), silylnorbornane anhydrides having the following formula are also included within the scope of the present invention.

O where R-R6 X and Z are as defined above, d is equal to 0 or 1<, e is equal to 0 to 2, and d+e
The sum of is equal to 1 or 2.

Claims (1)

[Claims] 1. The reaction between norbornene anhydride of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and the silane of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc. A method for producing silylnorbornane anhydride included in the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ which consists of carrying out in the presence of. However, X is (a) halogen, hydrogen, C_(_1_-_8_) alkoxy, acyloxy, -N(R^6)_2, cyano, hydrogen, amide, amino, carbamate, enoxy, imidato, isocyanato, oxymato, isocyanate, a hydrolyzable group selected from the group consisting of oximato, thioisocyanato, and ureido; (b) a siloxane having the following formula: etc. ▼ is a group selected from the group consisting of polysiloxanes having _1_3_) hydrocarbon group and monovalently substituted C_(_1_-_1_3_) hydrocarbon group, Y is selected from a group having the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼ and (a) group, Y ^1 is R^
6 groups, Y groups and mixed groups thereof, and Z is -
selected from O- and C-(R)_2, where a is an integer equal to 0 to 3, b is an integer equal to 0 to 3, c is an integer equal to 0 to 3, and the sum of b+c is 0 to 3. Equally, n is 1
is an integer equal to ~2000. 2. The anhydride-terminated diorganosiloxane of the following formula: ▲Mathematical formulas, chemical formulas, tables, etc. are equilibrated with the cyclopolydiorganosiloxane of the following formula: ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ in the presence of an acid catalyst. A method for producing a dianhydride-terminated polydiorganosiloxane, the method comprising reacting the dianhydride-terminated polydiorganosiloxane. However, R~R^5 are hydrogen and C_(_1_-_8_)
is a group selected from alkyl, and R^6 is a monovalent C_(
_1_-_1_3_) hydrocarbon group and monovalent substituted C_(
_1_-_1_3_) hydrocarbon group, Z is -
selected from O- and C-(R)_2, m' is 3-6
has the value of