JP2647242B2 - Method for producing gamma-methacryloxypropylsilane compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a γ-methacryloxypropylsilane compound, and more particularly, to a reaction between allyl methacrylate and a hydrosilane compound in one step, in a reaction system and in distillation. The present invention relates to a method for producing a γ-methacryloxypropylsilane compound with high yield without causing gelation during purification.

TECHNICAL BACKGROUND OF THE INVENTION γ-methacryloxypropyltrimethoxysilane, γ
-Γ such as methacryloxypropyltriethoxysilane
The methacryloxypropylsilane compound has a methacryloxy group which is an organic functional group together with a hydrolyzable group which reacts with an inorganic substance, and is frequently used as a silane coupling agent.

As a method for producing such a γ-methacryloxypropylsilane compound, for example, an allyl methacrylate is reacted with trichlorosilane in the presence of a platinum catalyst, and the obtained reaction product is treated with an alcohol to obtain γ-methacryloxypropyl. Methods for isolating trialkoxysilanes are known.

However, in such a method, since corrosive hydrogen chloride is generated during the synthesis of γ-methacryloxypropyl trialkoxysilane, the step of removing the hydrogen chloride becomes indispensable, and the chlorine content in the product increases. There was a problem.

As a method that does not require a hydrogen chloride removal step and does not increase the chlorine content in the product, allyl methacrylate and a hydrosilane compound such as trialkoxysilane are reacted in a single step in the presence of a platinum catalyst. (Hydrosilylation reaction), and a method of purifying the reaction product by distillation is known.

However, in such a method, during the reaction between the allyl methacrylate and the hydrosilane compound, or during the purification of the reaction product, the allyl methacrylate as the raw material or the γ-methacryloxypropyl silane compound as the reaction product is polymerized to form a gel. There was a problem of becoming. The gelation occurs in the reaction system and during the purification, in addition to lowering the production rate of the γ-methacryloxypropylsilane compound, and it is difficult to remove the generated gel because it is difficult to dissolve in the solvent, and the γ-methacryloxypropylsilane compound It is difficult to efficiently isolate by distillation.

Therefore, in order to prevent the formation of this gel, a toluene solution containing 2,5-di-t-butylhydroquinone as a polymerization inhibitor and a chloroplatinic acid solution as a catalyst,
A method of simultaneously introducing a hydrosilane compound and allyl methacrylate has been proposed (US Pat. No. 3,258,477).
No.). However, this method has a problem that it is economically disadvantageous because a large amount of toluene is used as a solvent.

Furthermore, a method using a conventional polymerization inhibitor such as a phenol compound such as hindered phenol, an aromatic amine compound such as diphenylenediamine, or an aromatic sulfur compound such as phenothiazine (Japanese Patent Laid-Open No. 62-2839)
No. 83 and JP-A-63-188689) have been proposed, but the formation of a gel in the reaction system and during the purification by distillation has not yet been sufficiently prevented. There is a need for a way to prevent it.

An object of the present invention is to solve such problems associated with the prior art, and when reacting allyl methacrylate and a hydrosilane compound in one step in the presence of a platinum catalyst, the reaction system and distillation An object of the present invention is to provide a method for producing a γ-methacryloxypropylsilane compound which can effectively prevent gelation during purification, is inexpensive and has a good yield.

SUMMARY OF THE INVENTION A method for producing a γ-methacryloxypropylsilane compound according to the present invention comprises reacting an allyl methacrylate with a hydrosilane compound in the presence of a platinum catalyst, at least one of a hindered phenol compound and an aromatic amine compound. And an amide compound.

According to the method for producing a γ-methacryloxypropylsilane compound according to the present invention, when reacting allyl methacrylate and a hydrosilane compound in the presence of a platinum catalyst, at least one of a hindered phenol compound and an aromatic amine compound And the amide compound coexist, gel formation in the reaction system and during distillation purification can be effectively prevented, and the γ-methacryloxypropylsilane compound can be produced with a high yield.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing a γ-methacryloxypropylsilane compound according to the present invention will be specifically described.

In the method for producing a γ-methacryloxypropylsilane compound according to the present invention, the reaction between the allyl methacrylate and the hydrosilane compound is carried out in the presence of a platinum catalyst in the presence of a specific polymerization inhibitor.

The hydrosilane compound used in the present invention is Si-H
A compound having at least one bond, for example, a compound represented by the following formula [I], [II] or [III].

(In the formula, R ¹ , R ² and R ³ may be the same or different and each is an alkyl group or an alkoxy group.) (Wherein, R ⁴ is hydrogen or a methyl group, at least one of R ⁴ is hydrogen, and n is an integer of 0 to 300.) (In the formula, m is an integer of 3 to 10.) As the hydrosilane compound represented by the above formula [I], [II] or [III], specifically, triethoxysilane, trimethoxysilane, trimethylsilane Silane, triethylsilane, tripropoxysilane, tributoxysilane, methyldimethoxysilane, ethyldimethoxysilane, methyldiethoxysilane, dimethylmethoxysilane, trioctyloxysilane, methyldioctyloxysilane, dimethyloctyloxysilane, 1,1, 3,3-tetramethyldisiloxane, pentamethyldisiloxane, α-
ω-dihydropolysiloxane, polysiloxane having a Si-H bond in the middle of the molecular chain, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, etc. Can be mentioned.

In the method for producing a γ-methacryloxypropylsilane compound according to the present invention, such an allyl methacrylate and hydrosilane compound are usually contained in a molar ratio (allyl methacrylate / hydrosilyl group of hydrosilane compound) of 0.1.
It is used in an amount of 66 / 1.5, preferably 0.83 / 1.2.

In the present invention, any platinum catalyst conventionally used in hydrosilylation reactions may be used as the platinum catalyst. Specifically, chloroplatinic acid, dichlorobis (acetonitrile) platinum (II), dichlorodiethylene Platinum (II), dichloro (1,5-cyclooctadiene) platinum (I
I), platinum-vinylsiloxane complex and platinum carried on platinum activated carbon, platinum-alumina and the like can be used.

Such a platinum catalyst is generally used in an amount of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, based on allyl methacrylate.
It is used in an amount of 1 × 10 ^-4 mol.

In the method for producing a γ-methacryloxypropyl silane compound according to the present invention, when the above-mentioned hydrosilane compound and allyl methacrylate are reacted in the presence of the platinum catalyst, a hindered phenol compound and an aromatic amine compound are used. At least one of them and a specific amide compound coexist.

Hindered phenol compound used in the present invention,
It is a compound in which at least one substituent which gives steric hindrance near the hydroxyl group in the aromatic ring is bonded, and any of hindered phenol compounds conventionally used as a polymerization inhibitor in a hydrosilylation reaction may be used. .

 Such hindered phenol compounds include
Physically, (1) 2,6-di-t-butyl-p-cresol (BHT)(2) 2,6-di-t-butylphenol(3) 2-methyl-6-t-butyl-P-cresol
(MBPC)(4) 2-t-butyl-4-methoxyphenol(5) 2,5-di-t-butylhydroquinone (trade name; DBH, manufactured by Kawaguchi Chemical Co.)(6) n-octadecyl-3- (3 ', 5'-di-t-butyl
Tyl-4'-hydroxyphenyl) -propionate (trade name: Irganox 1076, made by Ciba Geigy)(7) 4,4'-methylene-bis (2,6-di-tert-butyl
Enol) (Product name Ethanox 702, manufactured by Ethyl Corporation)(8) 2,2'-methylene-bis- (4-methyl-6-t
-Butylphenol)(9) 2,2'-ethylidene-bis- (4,6-di-t-butyl
Lephenol) (Product name: Isonox 129, Schenectady)(10) 2,2'-butylidene-bis- (6-t-butyl-
4-Methylphenol) (Product name: Sumilizer BBP, manufactured by Sumitomo Chemical Co., Ltd.)(11) 4,4'-butylidene-bis- (2-t-butyl-
5-methylphenol)(12) 2-tert-butyl-6- (3'-tert-butyl-5 '
-Methyl-2'-hydroxybenzyl) -4-methylph
Phenyl acrylate (Product name: Sumilizer GM, manufactured by Sumitomo Chemical Industries)(13) Tetrakis methylene-3- (3 ', 5'-di-t
-Butyl-4'-hydroxyphenyl) propione
Tomethane (Product name: Irganox 1010, Ciba-Geigy)(14) (mono, di, tri) α-methylbenzyl phenol
LeAnd the like. Where tBu
Is -C (CH_Three)₃Is shown.

Such a hindered phenol compound is used in an amount of 1 ppm to 20% by weight, preferably 10% by weight, based on allyl methacrylate.
Used in amounts from ppm to 5% by weight.

Specific examples of the aromatic amine compound used in the present invention include the following compounds.

(1) N, N'-diphenyl-p-phenylenediamine(2) N-phenyl-β-naphthylamine (trade name: Antage C , Manufactured by Kawaguchi Chemical Co., Ltd.)(3) 4,4'-dioctyl-diphenylamine(4) Phenothiazine Such aromatic amine compounds are allyl methacrylate
1 ppm to 20% by weight, preferably 10 ppm to 5%
It is used in amounts by weight.

In the method for producing a γ-methacryloxypropylsilane compound according to the present invention, an amide compound is used together with at least one of the above-mentioned hindered phenol compound and aromatic amine compound.

As such an amide compound, specifically, N, N
-Dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methylacetamide, N-methylformamide and the like, and the following compounds may be mentioned. it can.

(1) Nt-butylacetoacetamide(2) N, N'-bis-3- (3 ', 5'-di-t-butyl
4'-hydroxyphenyl) propionylhexamethyl
Rangeamine (Product name: Irganox 1098, Ciba-Geigy)(3) Tris [2- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenylcinnamyloxy) ethyl] iso
Cyanurate (Product name: Irganox 3125, Ciba-Geigy)(In the above formula [A], R is represented by the following formula)(4) Tris (3,5-di-t-butyl-4'-hydroxy
Sibenzyl) isocyanurate (Product name: Irganox 3114, manufactured by Ciba-Geigy) (In the above formula [A], R is represented by the following formula)(5) Tris (4-t-butyl-2,6-dimethyl-3-
(Hydroxybenzyl) isocyanurate) (Product name: Cyanox 1790, manufactured by ACC) (In the above formula [A], R is represented by the following formula) The amide compound used in the present invention may be used alone.
Two or more kinds may be used in combination, and the total amount
It is effective with more than 1 equivalent of platinum catalyst.
More preferably, it is used in an amount of 1 to 10 equivalents.

In the method for producing a γ-methacryloxypropylsilane compound according to the present invention, a γ-methacryloxypropylsilane compound is produced using the above-described raw materials, a catalyst, a polymerization inhibitor, and the like. May not be used.

Examples of the reaction solvent used in the present invention include aromatic compounds such as benzene, toluene, and xylene, aliphatic compounds such as hexane and heptane, and ether compounds such as tetrahydrofuran.

In the method of the present invention, the reaction temperature for producing the γ-methacryloxypropylsilane compound is 40 to 130.
° C, preferably 60 to 120 ° C, and the order of addition of the raw materials, catalyst, polymerization inhibitor and the like is not particularly limited. further,
According to the method of the present invention, a γ-methacryloxypropylsilane compound can be produced not only in an oxygen atmosphere but also in a nitrogen atmosphere.

In the present invention, the γ-methacryloxypropyl silane compound is isolated by distillation and purification from the reaction product obtained by reacting the allyl methacrylate and the hydrosilane compound in this manner. By adding the compound to the reaction product, the generation of a gel can be more effectively suppressed. The amide compound added at the time of distillation generation may be the same as or different from the amide compound coexisting during the reaction of the allyl methacrylate and the hydrosilane compound.

The total amount of the amide compound added to the reaction product during the purification by distillation is usually 1 equivalent to 500 equivalents, preferably 10 equivalents to 100 equivalents, relative to the platinum catalyst.

Effects of the Invention According to the method for producing a γ-methacryloxypropylsilane compound according to the present invention, when reacting allyl methacrylate and a hydrosilane compound in the presence of a platinum catalyst, at least one of a hindered phenol compound and an aromatic amine compound Since either one of them and the amide compound coexist, gel formation in the reaction system and during distillation purification can be effectively prevented, and the γ-methacryloxypropylsilane compound can be produced with high yield. Also, during distillation purification,
By further adding an amide compound to the reaction product,
It is possible to more effectively prevent gel formation.

Hereinafter, the method for producing the γ-methacryloxypropylsilane compound according to the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Also,
The percentages in the examples are mol% based on allyl methacrylate.

Example 1 A reflux condenser, a stirrer, a thermometer and a dropping funnel were provided.
Allyl methacrylate in a four-necked flask purged with nitrogen
126g, isopropanol solution of chloroplatinic (IV) acid 0.1m
l (10 as platinum^-Fivemol), radical polymerization prevention
2,2'-ethylidene-bis- (4,6-di-t
-Butylphenol) (trade name: Isonox 129, Schenect
ady) (2.8 g) was introduced.

Next, 17.4 mg of N, N-dimethylacetamide was added to the mixture in this flask, and after heating to 80 ° C. in an oil heating tank,
122 g of trimethoxysilane was dropped from the dropping funnel over 1 hour. Thereafter, heating was continued at 80 ° C. for 5 hours.

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 83% was obtained. When the reaction product was analyzed by GPC, the amount of the polymer having a molecular weight of 2,000 or more was found to be 0.
Only 3% was present.

Then, the reaction product was distilled to isolate the target product, and no gelation occurred. Table 2 shows the obtained results.

Example 2 17.4 mg of N, N-dimethylacetamide of Example 1 was added to N
Example 1 except that 21.9 mg of -methylacetamide was used.
The reaction was carried out in the same manner as described above, and the desired product was isolated.

Gas chromatography analysis and GPC of reaction products
The results of the analysis are shown in Table 1, and the results of distillation and purification of the reaction product are shown in Table 2.

Examples 3 to 10 The reaction was carried out in the same manner as in Example 1 except that the radical polymerization inhibitor, hydrosilane compound and amide compound shown in Table 1 were used and the reaction was carried out at the temperature shown in Table 1. Was isolated.

Gas chromatography analysis and GPC of reaction products
Table 1 shows the results of the analysis, and Table 2 shows the results of distillation of the reaction product.
Shown in

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 17.4 mg of N, N-dimethylacetamide was not added.

When about 1/3 of the trimethoxysilane was dropped, the reaction mixture in the flask completely gelled.

Example 11 0.1 ml of a solution of chloroplatinic (IV) acid in isopropanol was
The reaction was carried out in the same manner as in Example 1, except that 0.2 ml of a toluene solution of 1,3-divinyltetramethylsiloxane platinum complex was used (corresponding to 10 ^-5 mol as platinum).

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 84% was obtained. GPC analysis of the reaction product revealed that no polymer having a molecular weight of 2,000 or more was present.

Then, the reaction product was distilled to isolate the target product. As a result, gelation did not occur and the target product could be isolated with a yield of 79%.

Example 12 0.1 ml of a solution of chloroplatinic (IV) acid in isopropanol was
3.7 mg of dichloro (1,5-cyclooctadiene) platinum (II)
The reaction was carried out in the same manner as in Example 2 except that

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 86% was obtained. GPC analysis of the reaction product revealed that no polymer having a molecular weight of 2,000 or more was present.

Then, the reaction product was distilled to isolate the target product. As a result, gelation did not occur and the target product could be isolated with a yield of 80%.

Example 13 As a hydrosilane compound, a polymethyl hydrogen siloxane represented by the following formula (100 cSt, having an SiH group content of 10
%) The reaction was carried out in the same manner as in Example 1 except that 500 g was used.

Analysis of the reaction product by gas chromatography showed that the conversion of allyl methacrylate was 90%. GPC analysis of the reaction product revealed that no high molecular weight polymer was present.

Example 14 A reaction was carried out in the same manner as in Example 1, except that 100 ml of toluene was used as a reaction solvent. Analysis of the reaction product by gas chromatography showed that γ-methacryloxypropyltrimethoxysilane was obtained in a yield of 87%. GPC analysis of the reaction product revealed that no polymer having a molecular weight of 2,000 or more was present.

Then, the reaction product was distilled to isolate the target product. As a result, gelation did not occur and isolation was achieved at a yield of 81%. The polymer in the distillation residue was 1.5%.

Example 15 A reaction was carried out in the same manner as in Example 1, except that 100 ml of n-hexane was used as a reaction solvent.

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 88% was obtained. GPC analysis of the reaction product revealed that no polymer having a molecular weight of 2,000 or more was present.

Then, the reaction product was distilled to isolate the target product. As a result, gelation did not occur and isolation was achieved at a yield of 81%. The polymer in the distillation residue was 1.0%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 14, except that 17.4 mg of N, N-dimethylacetamide was not added.

When the reaction product was analyzed by gas chromatography, no gelation occurred, but a viscous solution was obtained. Further, γ-methacryloxypropyltrimethoxysilane was obtained in a yield of 65%.

Then, the reaction product was distilled to isolate the target product. As a result, a gel was formed at the bottom of the distillation, and only a 40% yield could be isolated.

Example 16 To the reaction product obtained in Example 1 was added 87.1 mg of N, N-dimethylacetamide, followed by distillation to isolate the desired product. As a result, gelation did not occur and γ-methacryloxypropyl Methoxysilane could be isolated with a yield of 79%, and the polymer in the distillation residue could be reduced to 0.4%.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // C07B 61/00 300 C07B 61/00 300 (72) Inventor Akihito Shinohara Oimachi, Iruma-gun, Saitama 1-3-1, Nishitsurugaoka, Tonen Co., Ltd. Research Institute (72) Inventor Koji Shiozawa 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (72) Inventor Yoshiharu Okumura 1-3-1 Nishi-Tsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Inside the Tonen Research Laboratory (56) References JP-A-62-283983 (JP, A) JP-A-63-188689 (JP, A)

Claims (2)

(57) [Claims] An allyl methacrylate and a hydrosilane compound are reacted in the presence of a hindered phenol compound and an aromatic amine compound with an amide compound in the presence of a platinum catalyst to obtain a reaction product. A method for producing a γ-methacryloxypropylsilane compound, characterized in that: 2. The method for producing a γ-methacryloxypropyl silane compound according to claim 1, wherein an amide compound is further added to the reaction product, followed by purification by distillation.