JP2805998B2 - Acid anhydride group-containing silane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silane coupling agent such as polyimide resin or polyimide having an acid anhydride group, a double bond and a hydrolyzable alkoxy group in a molecule. The following general formula (I) useful for raw materials such as resins (Wherein R and R 'are the same or different monovalent hydrocarbon groups, m is an integer of 1 to 3, and n is 0.1, or 2). And its manufacturing method.

[Problems to be solved by conventional technology and invention]

Conventionally, as an acid anhydride group-containing silane compound, an alkoxysilyl group-substituted-5-norbornene-2,3-dicarboxylic anhydride (Shologon et al., Zh. Obshch. Khim., Vol. 45, N.
o.3.pp.579-585,1975), 5-alkoxysilyl group-substituted-norbornane-2,3-dicarboxylic anhydride (Table 1)
-501208), alkoxysilyl group-containing propyl-substituted succinic anhydride (Japanese Patent Publication No. 63-37119), 4-alkoxysilyl-substituted 1,2,3,6-tetrahydrophthalic anhydride (Japanese Patent Application No. 199855, JP-A-1-129510)
However, there is a demand for an acid anhydride group-containing silane compound which can be more effectively used as a silane coupling agent such as a polyimide resin or a raw material such as a polyimide resin.

[Means and actions for solving the problem]

The present inventor has conducted intensive studies to meet the above-mentioned demands, and as a result, the following general formula (II) (Wherein, R and R ′ are the same or different monovalent hydrocarbon groups, m is an integer of 1 to 3, and n is 0.1, or 2). By reacting silane with maleic anhydride, the following general formula (I) (Wherein, R, R ', m and n have the same meanings as described above). It has been found that a novel acid anhydride group-containing silane compound represented by the following formula is easily obtained.

This acid anhydride group-containing silane compound has an acid anhydride group, a double bond and a hydrolyzable alkoxy group in a molecule, and in a reaction with an inorganic material, an alkoxy group bonded to a silicon atom is used. It undergoes hydrolysis with water to form silanol groups, which undergo condensation reactions with hydroxyl groups on the surface of the inorganic material to form strong covalent bonds, and in the reaction with various resins, acid anhydride groups and double bonds. The bond reacts with various resins to form a strong covalent bond, and thus the acid anhydride group-containing silane compound is a raw material such as a silicon-containing polyimide resin, a silicon-containing polyamide resin, a silicon-containing polyester resin, or a silane coupling agent, Further, it is useful for various uses such as a plasticizer for a vinyl chloride resin and a curing agent for an epoxy resin. Especially effective as a raw material of polyimide resin or a silane coupling agent for polyimide resin, polyimide resin using the above acid anhydride group-containing silane compound as a part of the raw material has significant adhesion to metals such as copper and silicon and glass. It is possible to improve many basic physical properties, such as improved moldability and processability because the glass transition point is further lowered, and moreover, when a silicon skeleton is generally introduced into a polyimide resin as described above. Although the preferred properties are obtained, the mechanical properties are reduced, but the polyimide resin obtained by using the present compound has an intermolecular condensation at a silicon-alkoxy bond after firing, so that it has three-dimensional cross-linking. As a result, practically sufficient hardness and strength are given.

Accordingly, the present invention provides a method of reacting an acid anhydride group-containing silane compound represented by the formula (I) and a cyclopentadienylalkyl group-containing silane represented by the formula (II) with maleic anhydride. The present invention provides a method for producing an acid anhydride group-containing silane compound represented by the formula (1).

 Hereinafter, the present invention will be described in more detail.

The acid anhydride group-containing silane compound of the present invention has the following formula (I) (Wherein, R and R 'are the same or different monovalent hydrocarbon groups, m is an integer of 1 to 3, and n is 0.1, or 2). Substitution-5
-Norbornene-2,3-dicarboxylic anhydride.

Here, examples of the monovalent hydrocarbon group of R and R 'include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group having 5 to 6 carbon atoms, and a phenyl group. No. Specific examples of the acid anhydride group-containing silane compound represented by the formula (I) include trimethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride, methyldimethoxysilylmethyl-5-norbornene-2, 3-dicarboxylic anhydride, dimethylmethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride, trimethoxysilylpropyl-5-norbornene-
2,3-dicarboxylic anhydride, methyldimethoxysilylpropyl-5-norbornene-2,3-dicarboxylic anhydride, dimethylmethoxysilylpropyl-5-norbornene-2,3-dicarboxylic anhydride, triethoxysilylmethyl- 5-norbornene-2,3-dicarboxylic anhydride,
Triethoxysilylpropyl-5-norbornene-2,3
-Dicarboxylic anhydrides and the like.

The acid anhydride group-containing silane compound represented by the above formula (I) is represented by the following general formula (II) (Wherein, R, R ', m and n have the same meanings as described above). A cyclopentadienylalkyl group-containing silane represented by It can be easily synthesized by Alder reaction.

Here, the cyclopentadienylalkyl group-containing silane represented by the above formula (II) is a known compound, and can be generally obtained by a method such as reacting cyclopentadienyl sodium with a haloalkyl group-containing silane.

The Diels-Alder reaction proceeds sufficiently without a solvent, but if necessary, using a solvent such as benzene, toluene, o-xylene, m-xylene, mixed xylene, cyclohexene, ethyl ether, and tetrahydrofuran. Is also good. This reaction proceeds at room temperature, but may be carried out at the reflux temperature of the solvent, if necessary. The reaction time depends on the type of the substrate which reacts with maleic anhydride, that is, the compound represented by the above general formula (II), and can be freely selected from about 30 minutes to several tens hours or more. Is possible. In the reaction, a catalyst such as AlCl ₃ , BF ₃ or SnCl ₂ may be used.

In the above reaction, the amount of the maleic anhydride used may be any amount as long as it is at least equimolar to the cyclopentadienylalkyl group-containing silane represented by the general formula (II). From an economical viewpoint, the molar ratio is preferably 1 to 1.2 times.

The thus obtained acid anhydride group-containing silane compound represented by the formula (I) of the present invention can be purified by distillation and can be highly purified by distillation.

〔The invention's effect〕

As explained above, the acid anhydride group-containing silane compound represented by the formula (I) of the present invention has an acid anhydride group, a double bond and a hydrolyzable alkoxy group in the molecule, and contains a silicon-containing polyimide. It is useful as a raw material for resins, silicon-containing polyamide resins, silicon-containing polyester resins, etc., silane coupling agents, plasticizers for vinyl chloride resins, etc., and curing agents for epoxy resins. In particular, the use of the substance of the present invention makes it possible to obtain a polyimide resin having excellent adhesiveness to a substrate, moldability, workability, and sufficient hardness and strength, and is also very effective as a silane coupling agent. . Further, according to the production method of the present invention, an acid anhydride group-containing silane compound represented by the formula (I) can be produced reliably in a simple process using inexpensive maleic anhydride as a raw material.

Hereinafter, the present invention will be described in detail with reference to Examples,
The present invention is not limited to the following examples.

[Example 1] 100 ml equipped with a thermometer, a stirrer, and a Dimroth condenser
Was charged with 10.8 g (0.11 mol) of maleic anhydride and 50 ml of toluene and stirred at 30 ° C. After the maleic anhydride was completely dissolved, 20.0 g (0.1 mol) of (cyclopentadienylmethyl) trimethoxysilane was gradually introduced into the reactor using a dropping funnel. As the temperature gradually increased to 40 to 50 ° C., the color of the reaction solution turned dark brown. After the dropping of (cyclopentadienylmethyl) trimethoxysilane was completed, the mixture was heated and aged for about 2 hours while maintaining 90 ° C. Next, after stripping the toluene, the following formula (I-a) of a pale yellow oil was obtained in a single distillation apparatus. The trimethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride represented by was isolated. It had a boiling point of 155 to 158 ° C (1 mmHg) and a yield of 83%. The structure of the obtained trimethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride was determined by nuclear magnetic resonance ( ¹
H-NMR) and infrared absorption (IR). The results are shown below. ¹ H-NMR (CCl ₄ ): δ (ppm) 1.43 to 2.13 (4H, m), 3.19
3.63.63 (4H, m), 3.70 (9H, s), 5.86 (1H, m) IR: (cm ⁻¹ ) 933, 1097, 1214, 1236, 1795 (C =
O), 1874, 2855, 2960 Example 2 The same operation as in Example 1 was carried out except that (cyclopentadienylmethyl) methyldimethoxysilane was used instead of (cyclopentadienylmethyl) trimethoxysilane. And the following formula (Ib) The methyl dimethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride represented by was obtained. It had a boiling point of 147 to 149 ° C (1 mmHg) and a yield of 59%.

The structure of the obtained methyldimethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride was confirmed by nuclear magnetic resonance ( ¹ H-NMR) and infrared absorption (IR). The results are shown below. ¹ H-NMR (CCl ₄ ): δ (ppm) 0.17 (3H, s), 1.49 to 1.91
(4H, m), 3.03-3.43 (4H, m), 3.47 (6H, s), 5.67
(1H, m) IR: (cm ^-1 ) 903, 1062, 1216, 1782 (C = O), 186
8, 2840, 2950 Example 3 The following formula was prepared by the same operation as in Example 1 except that (cyclopentadienylmethyl) dimethylmethoxysilane was used instead of (cyclopentadienylmethyl) trimethoxysilane. (Ic) And dimethylmethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride was obtained. It had a boiling point of 140-142 ° C (2 mmHg) and a yield of 61%.

The structure of the obtained dimethylmethoxysilylmethyl-5-norbornene-2,3-dicarboxylic anhydride was confirmed by nuclear magnetic resonance ( ¹ H-NMR) and infrared absorption (IR). The results are shown below. ¹ H-NMR (CCl ₄ ): δ (ppm) 0.01 to 0.03 (6H, d), 1.17
~ 1.85 (4H, m), 2.88 ~ 3.88 (4H, m), 3.88 (3H, s),
5.50 (1H, m) IR: (cm ^-1 ) 923, 1088, 1229, 1788 (C = O), 186
5, 2960

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toru Kubota 28-1, Nishifukushima, Oaza, Kushiro-mura, Nakakushiro-gun, Niigata Prefecture Inside the Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28, Nishifukushima, Oita 1 Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (56) Reference JP-A-63-316790 (JP, A) JP-A-61-56189 (JP, A) JP-A 49-114463 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/18 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein R and R 'are the same or different monovalent hydrocarbon groups, m is an integer of 1 to 3, and n is 0.1, or 2). . 2. The following general formula (II) (Wherein, R and R ′ are the same or different monovalent hydrocarbon groups, m is an integer of 1 to 3, and n is 0.1, or 2). The method for producing an acid anhydride group-containing silane compound according to claim 1, wherein the silane is reacted with maleic anhydride.