JP2667566B2 - 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 the step of removing hydrogen chloride and there is no fear that the chlorine content in the product will become the base, react allyl methacrylate with a hydrosilane compound such as trialkoxysilane 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. Since gelation occurs in the reaction system and during purification, the production rate of the γ-methacryloxypropylsilane compound is reduced, and a pure γ-methacryloxypropylsilane compound can be isolated in a high yield. It will be difficult.

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.

However, when the reaction products obtained by these methods are produced by distillation, it is difficult to isolate the γ-methacryloxypropylsilane compound due to the gel produced in the reaction system and the gel produced during distillation purification. Therefore, there is a demand for the development of a method for producing a γ-methacryloxypropylsilane compound that can efficiently purify a γ-methacryloxypropylsilane compound from the obtained reaction product by distillation.

OBJECT OF THE INVENTION The present invention is intended to solve the above problems associated with the prior art, and comprises a reaction product obtained by reacting allyl methacrylate with a hydrosilane compound in one step in the presence of a platinum catalyst. Low cost and good yield of γ-
An object of the present invention is to provide a method for producing a methacryloxypropylsilane compound.

SUMMARY OF THE INVENTION A first 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 to obtain at least a hindered phenol compound and an aromatic amine compound. It is characterized in that either one of them is allowed to coexist, an aliphatic hydrocarbon solvent is added to the obtained reaction product to precipitate and remove a high molecular weight polymer, and then the product is distilled and purified.

A second method for producing a γ-methacryloxypropylsilane compound according to the present invention is that at least one of a hindered phenol compound and an aromatic amine compound is reacted with an allyl methacrylate and a hydrosilane compound in the presence of a platinum catalyst. And an aliphatic hydrocarbon solvent, and the resulting reaction product is cooled to precipitate and remove a high molecular weight polymer, followed by distillation and purification.

According to the first and second methods for producing a γ-methacryloxypropylsilane compound according to the present invention, the reaction between an allyl methacrylate and a hydrosilane compound is carried out in the presence of a platinum catalyst to obtain a hindered phenol compound and an aromatic amine compound. At least one of them is allowed to coexist, and an aliphatic hydrocarbon solvent is added to the obtained reaction product to precipitate and remove a high molecular weight polymer, or an aliphatic hydrocarbon solvent is further allowed to coexist in the reaction system. The resulting reaction product is cooled to precipitate a high molecular weight polymer and then purified by distillation, so the gel generated in the reaction system can be removed efficiently, and gel formation during purification can be effectively prevented. Γ-methacryloxypropylsilane compound can be produced in good 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 first and second methods 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. I have.

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, and at least one of R ⁴ is hydrogen. (In the formula, m is an integer of 3 to 10.) Specific examples of the hydrosilane compound represented by the above formula [I], [II] or [III] include triethoxysilane, trimethoxysilane and trimethylsilane. , Triethylsilane, tripropoxysilane, tributoxysilane, methyldimethoxysilane, ethyldimethoxysilane, methyldiethoxysilane, dimethylmethoxysilane, trioctyloxysilane, methyldioctyloxysilane, dimethyloctyloxysilane, 1,1,3 , 3-tetramethyldisiloxane, pentamethyldisiloxane, 1,3,
5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9
-Pentamethylcyclopentasiloxane and the like.

In the first and second methods for producing a γ-methacryloxypropylsilane compound according to the present invention, such an allyl methacrylate and a hydrosila compound have a molar ratio (allyl methacrylate / hydrosilyl group of a hydrosilane compound) of usually 0.66 / It is used in an amount of 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 first and second methods for producing a γ-methacryloxypropylsilane compound according to the present invention, when a hydrosilane compound as described above and an allyl methacrylate are reacted in the presence of the platinum catalyst, a hindered phenol compound is used. And at least one of the aromatic amine compounds is used as a polymerization inhibitor.

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
Cyl-4'-hydroxyphenyl) -propione (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
(Phenol) (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-methylphen
Nyl acrylate (trade 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, the γ-methacryloxypropylsilane compound is produced using the above-mentioned raw materials, catalysts, polymerization inhibitors and the like.

In the method of the present invention, the reaction temperature in producing the γ-methacryloxypropylsilane compound is 40 to 130 ° C., preferably 60 to 120 ° C., and the addition order of the raw material, the catalyst, the polymerization inhibitor and the like is not particularly limited. Not done. Further, in the method of the present invention, the allyl methacrylate and the hydrosilane compound may be reacted under either an oxygen atmosphere or a nitrogen atmosphere.

Further, in the first method for producing a γ-methacryloxypropylsilane compound according to the present invention, a reaction solvent may or may not be used. However, when the reaction is carried out at a temperature of 70 ° C. or higher, a gel is likely to be generated during the reaction.

Examples of the reaction solvent used in the first method for producing a γ-methacryloxypropylsilane compound of the present invention include aromatic compounds such as benzene, toluene, xylene, aliphatic compounds such as hexane and heptane, and ether compounds such as tetrahydrofuran. It can be illustrated.

In the first method for producing a γ-methacryloxypropylsilane compound according to the present invention, an aliphatic hydrocarbon solvent is added to the reaction product obtained by reacting the allyl methacrylate and the hydrosilane compound in this manner to obtain a high-concentration compound. A molecular weight polymer is precipitated, and after removing this, distillation purification is performed.

As the aliphatic hydrocarbon solvent, specifically, the boiling point is 30
Examples thereof include a high-boiling aliphatic hydrocarbon having a temperature of 0 ° C. or higher, petroleum ether, pentane, hexane, heptane, octane, decane, dodecane, and the like.

In the present invention, the use amount of such an aliphatic hydrocarbon solvent is not particularly limited, but based on the obtained reaction product,
Usually 0.5 to 5 times (volume), preferably 1 to 3 times (volume)
Used in amounts.

In the second method for producing a γ-methacryloxypropylsilane compound according to the present invention, an aliphatic hydrocarbon solvent is used as a reaction solvent.

As such an aliphatic hydrocarbon solvent, the aliphatic hydrocarbon used in the first method of the present invention can be exemplified.

In the present invention, the amount of the aliphatic hydrocarbon solvent used is not particularly limited, but is usually 0.5 to 5 times (by volume) with respect to the allyl methacrylate and the hydrosilane compound.
It is preferably used in an amount of 1 to 3 times (volume).

In the second method for producing a γ-methacryloxypropylsilane compound according to the present invention, the reaction product thus obtained by reacting the allyl methacrylate and the hydrosilane compound is cooled to precipitate a high molecular weight polymer, After removing this, distillation purification is performed.

The high molecular weight polymer precipitated by the first and second methods of the present invention can be easily removed by filtration or decantation.

Effects of the Invention According to the first and second methods for producing a γ-methacryloxypropylsilane compound according to the present invention, the reaction between an allyl methacrylate and a hydrosilane compound is carried out in the presence of a platinum catalyst, a hindered phenol compound and an aromatic compound. At least one of the amine compounds is allowed to coexist and an aliphatic hydrocarbon solvent is added to the obtained reaction product to precipitate and remove a high molecular weight polymer, or an aliphatic hydrocarbon is further added to the reaction system. The solvent is allowed to coexist, the obtained reaction product is cooled to precipitate a high-molecular weight polymer, and then purified by distillation, so that the gel formed in the reaction system can be efficiently removed, and further gel formation during purification can be prevented. It can be effectively prevented, and a γ-methacryloxypropylsilane compound can be produced with a high yield.

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
4,4'-methylene-bis (2,6-di-t-butyl)
Phenol (Product name: Ethanox 702, Ethyl) 3.0
g was introduced.

Next, this flask was heated to 60 to 65 ° C. in an oil heating tank, and then 122 g of trimethoxysilane was added dropwise from the dropping funnel over 90 minutes while adjusting the temperature so as not to exceed 65 ° C. Thereafter, heating was continued at 60 to 65 ° C. for 6 hours.

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 80% was obtained. GPC analysis of the reaction product revealed that polymers having a molecular weight of 2,000 or more were found to be 4.
It turned out that 3% was produced.

Next, 600 ml of n-hexane was added to the obtained reaction product, and the precipitated gel (high molecular weight polymer) was removed by filtration. The removed polymer was 13 g.

When the target product was isolated by subjecting the obtained product to filtration distillation, γ-methacryloxypropyltrimethoxysilane could be isolated in a yield of 74% without gelation.

Comparative Example 1 The reaction product obtained in the same manner as in Example 1 was distilled as it was without adding n-hexane. When 60% of the product was distilled, gelation occurred and further product was obtained. Couldn't distill.

Example 2 A reaction product was obtained in the same manner as in Example 1 except that 700 ml of n-hexane was used as a reaction solvent and the reaction was carried out while maintaining the reaction temperature at 75 to 80 ° C.

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 83% was obtained.

The resulting reaction product was cooled to room temperature to precipitate a high molecular weight polymer, which was removed by decantation.
The removed polymer was 7 g.

Subsequently, distillation was performed to isolate the target product. As a result, gelation did not occur, and γ-methacryloxypropyltrimethoxysilane could be isolated with a yield of 78%.

Example 3 A gel (high molecular weight polymer) precipitated by adding 500 ml of n-heptane to the reaction product obtained in the same manner as in Example 1.
Was removed by decantation. The removed polymer was 15 g.

Next, distillation was performed to isolate the target product. As a result, gelation did not occur, and γ-methacryloxypropyltrimethoxysilane was isolated with a yield of 73%.

Example 4 As a radical polymerization inhibitor, tetrakisdimethylene-
3- (3 ', 5'-di-tert-butyl-4'-hydroxyf
Enyl) propionate @ methane (trade name: Irganox Ten
Example 1 except that 2.8 g was used.
A reaction product was obtained in the same manner as described above.

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 78% was obtained. GPC analysis of the reaction product revealed that 7.2% of a high molecular weight polymer was produced.

500 ml of n-hexane was added to the obtained reaction product,
After removing the precipitated gel (high molecular weight polymer), distillation was carried out to isolate the desired product. No gelation occurred, and γ-methacryloxypropyltrimethoxysilane was isolated in 71% yield. I was able to separate.

Example 5 After the reaction and the removal of high molecular weight polymer were performed in the same manner as in Example 2 except that 3.2 g of N, N-diphenylethylenediamine was used as the radical polymerization inhibitor, the target product was distilled. Upon isolation, gelation did not occur during distillation, and γ-methacryloxypropyltrimethoxysilane was isolated with a yield of 70%.

Example 6 122 g of trimethoxysilane and 164 g of triethoxysilane
After the reaction and the removal of the high molecular weight polymer were carried out in the same manner as in Example 4 except that the above was replaced with, the target product was isolated by distillation.
-Methacryloxypropyltriethoxysilane could be isolated with a yield of 73%.

Example 7 122 g of trimethoxysilane was added to dimethylmethoxysilane
A reaction product was obtained in the same manner as in Example 1 except that the amount was changed to 90 g.

Analysis of the reaction product by gas chromatography showed that γ-methacryloxypropyldimethylmethoxysilane was obtained in a yield of 76%. GPC analysis of the reaction product revealed that 8% of a high molecular weight polymer was produced.

Next, 600 ml of petroleum ether was added to the obtained reaction product, the precipitated gel (high molecular weight polymer) was removed, and the target product was isolated by distillation.
No gelling occurred, and γ-methacryloxypropyldimethylmethoxysilane was isolated with a yield of 70%.

Example 8 2,2'-Ethylidene-bis as radical polymerization inhibitor
-(4,6-di-t-butylphenol) (trade name: Isonox
129, Schenectady) 2.5g, hydrosilation
Use 67 g of 1,1,3,3-tetramethyldisiloxane as compound
A reaction product was obtained in the same manner as in Example 2 except for the above.

Analysis of the reaction product by gas chromatography showed that 1,3-γ-methacryloxypropyltetramethyldisiloxane was obtained in a yield of 80%. GPC analysis of the reaction product revealed that 2% of a high molecular weight polymer was produced.

Then, the obtained reaction product was cooled, and after removing 0.5 g of the precipitated gel (high molecular weight polymer), distillation was carried out to isolate the desired product, and gelation did not occur,
It could be isolated with a yield of 73%.

Example 9 0.1 ml of a solution of chloroplatinic (IV) acid in isopropanol was
Reaction and removal of high molecular weight polymer were carried out in the same manner as in Example 1 except that 0.1 ml of a toluene solution of 1,3-divinyltetramethylsiloxane platinum complex (corresponding to 10 ^-5 mol of platinum) was used. The reaction product was purified by distillation. As a result, gelation did not occur, and γ-methacryloxypropyltrimethoxysilane could be isolated with a yield of 81%.

Example 10 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 1 except that

When the reaction product was analyzed by gas chromatography, γ-methacryloxypropyltrimethoxysilane was found.
It was found that a yield of 79% was obtained. GPC analysis of the reaction product revealed that 5.2% of a high molecular weight polymer was produced.

Next, 600 ml of white oil having a boiling point of 300 to 350 ° C. was added to the obtained reaction product to remove the precipitated gel (high molecular weight polymer), followed by distillation to isolate the desired product. Could be isolated with a yield of 72%. The distillation residue was a free flowing liquid.

 ───────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideaki Ogawa 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. 1-3-1 Kaoka, Tonen Co., Ltd. (72) Inventor Yoshiharu Okumura 1-3-1, Nishi Tsurugaoka, Oi-machi, Iruma-gun, Saitama

Claims (2)

(57) [Claims] 1. A reaction between an allyl methacrylate and a hydrosilane compound is carried out in the presence of at least one of a hindered phenol compound and an aromatic amine compound in the presence of a platinum catalyst, and the obtained reaction product is aliphatic. A method for producing a γ-methacryloxypropylsilane compound, comprising adding a hydrocarbon solvent, precipitating and removing a high molecular weight polymer, and then purifying by distillation. 2. A reaction between an allyl methacrylate and a hydrosilane compound is carried out in the presence of a platinum catalyst in the presence of at least one of a hindered phenol compound and an aromatic amine compound and an aliphatic hydrocarbon solvent.
A method for producing a γ-methacryloxypropyl silane compound, comprising cooling the obtained reaction product to precipitate and remove a high molecular weight polymer, and then purifying it by distillation.