JPH1129583A - Production of acryloxy or methacryloxy group-containing chlorosilane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing acryloxy or methacryloxy group- containing chlorosilanes, achieving extremely excellent polymerization-inhibiting effects in the presence of a specific compound as a catalyst without inhibiting hydroxylation at all. SOLUTION: This method comprises subjecting a hydrochlorosilane expressed by the formula: HSiCln R<2> 3-n and an allylacrylate or allylmethacrylate to hydroxylation in the presence of a plastinum group catalyst and 2,2-thio- diethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate to produce acryloxy or methacryloxy group-containing chlorosilane expressed by the formula: CH2 = CR<1> COOCH2 CH2 CH2 SiCln R<2> 3-n [R<2> is H or methyl; R is a 1-6C univalent hydrocarbon; (n) is an integer of 1-3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an acryloxy or methacryloxy group-containing alkoxysilane which is widely used in industry as a silane coupling agent or a polymerizable monomer for obtaining a silicon-containing polymer. The present invention relates to a method for producing a methacryloxy group-containing chlorosilane.

[0002]

2. Description of the Related Art An acryloxy or methacryloxy group-containing chlorosilane represented by the following general formula (I) is characterized by having an acryloxy or methacryloxy group of a polymerizable functional group in its structure. It is useful as a raw material for an acryloxy or methacryloxy group-containing alkoxysilane, which is widely used in industry as a silane coupling agent or a polymerizable monomer for obtaining a silicon-containing polymer.

[0003]

Embedded image (Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is
6 represents a monovalent hydrocarbon group, and n is an integer of 1 to 3. )

[0004] However, the acryloxy or methacryloxy group-containing chlorosilane has a polymerizable functional group, which is a characteristic feature thereof, so that it is very easily self-polymerized by heat during its production process, which causes many problems. For example, when reacting and synthesizing on an industrial scale, because it is exposed to high temperature conditions for a long time, the polymerization heat spontaneously occurs due to the heat of the process, causing gelation in the reactor or blocking the piping. , With great damage to the manufacturing process,
The repairs are labor intensive and labor intensive. For these reasons, development of a method for producing a chlorosilane containing an acryloxy group or a methacryloxy group that does not cause a spontaneous polymerization reaction is extremely important for facilitating production on an industrial scale, and has been rushed.

Conventionally, chlorosilanes of the above formula (I)
Generally, the following general formula (II) H SiCl_nR^Two _3-n (II) (wherein R^TwoAnd n have the same meaning as described above. )
Hydrochlorosilane and allyl acrylate or alcohol
Ryl methacrylate is converted to a hydrate in the presence of a platinum group catalyst
It is synthesized by the reaction of lossylation.
To prevent spontaneous polymerization in this process
Although various attempts have been proposed,
Results are inadequate or contain various problems.
No satisfactory solution was known.

[0006] That is, as one of the polymerization reaction preventing techniques, it is known to add phenolic compounds such as hydroquinone and hydroquinone monomethyl ether. In this method, these compounds gradually react with chlorosilane to form a system. The effect of inhibiting polymerization was poor because it disappeared in the reactor. Also, quinone-based benzoquinone, 2,5-
It is also known to add t-butylbenzoquinone, quinone dioximes, etc., but these compounds are problematic in that they have strong irritation and have problems in handling properties, and have high coloring properties. was there.

Further, addition of phenothiazine generally known in Japanese Patent Publication No. 6-51707, Japanese Patent No. 2539505, etc., has insufficient polymerization inhibiting effect.

[0008] Further, addition of various hindered phenol compounds is also known, and those proposed so far (2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-m-cresol), 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, etc.), the polymerization inhibition effect was generally insufficient. Although it is effective in preventing self-polymerization to some extent, it has been found that various problems are caused in recent years, since the boiling point is almost the same as that of the target product, so that it is entrained in the product during distillation and is mixed into the product. Some are considered problematic. For example, 2,6-di-t-butyl-4-methylphenol is a substance (quinone methide, stilbene quinone, etc.) that causes yellowing and coloring as shown in the following formula under the influence of nitrogen oxides in the air. It has recently been found to change and has problems in use as polymerization inhibitors (KS Smeltz, Textile Che).
m, Color. , 15, [4], 52 (1983) and Shinichi Yago; Plastics Age Encyclopedia
pedia, Progress, 1995, p131-138 (1
994) and Kenji Kimura; JETI, Vol. 44, N
o. 5, p92-97 (1996)). Furthermore, in applications where the final target product is used as a polymerizable monomer, if a polymerization inhibitor is mixed, the polymerization reaction will be inhibited and the desired operation will be hindered. If this is the case, the polymerization inhibiting effect will be insufficient. In addition, there is also a substance which is converted into 2,6-di-t-butyl-4-methylphenol or a substance which causes the above-mentioned yellowing and coloring in the reaction system. Specifically, bis (3,5 -Di-t-
Butyl-4-hydroxybenzyl) sulfide and 2,6-di-t-butyl-4-dimethylaminomethylenephenol described in JP-A-5-186478;
2,6-di-t-butyl- in JP-A-25-25907
4-hydroxymethylphenol and 4,4′-methylenebis (2,6-di-t-butylphenol), which are substances which cause the above-mentioned yellowing and coloring due to changes over time after addition. It has been confirmed that it is converted to 2,6-di-t-butyl-4-methylphenol, quinone methide, and stilbenequinone, and there is a problem in using it as a polymerization inhibitor.

[0009]

Embedded image

On the other hand, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4- known in JP-A-4-356442 and JP-A-4-128294. Acrylic esters such as methylphenyl acrylate are not suitable because if added to the hydrosilylation reaction, hydrochlorosilane will be added to the acrylic groups of the compound, thereby impairing the polymerization inhibiting effect.

Further, a means for blowing oxygen at the time of the addition reaction is also known as disclosed in Japanese Patent No. 2539505 and Japanese Patent Application Laid-Open No. 4-128293, but the effect of inhibiting polymerization is insufficient and the oxygen concentration is reduced. It is difficult to control (a large oxygen concentration promotes radical polymerizability). Furthermore, Japanese Patent Publication No. Hei 3-12075,
Acetylacetone and benzoylacetone, which are known from JP-A-81, also have insufficient polymerization inhibiting effects.

JP-B-7-316164, JP-A-5-316164
No. 271248 discloses cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, an inorganic copper compound such as copper sulfate, and a copper complex such as copper dimethyldithiocarbamate conventionally known. Cannot inhibit the hydrosilylation reaction in the presence of a platinum group catalyst and hinder the production of the desired product.

Further, a phosphorus-containing compound system (Japanese Patent Laid-Open No.
P (C ₆ H ₅ ) ₃ , P (OC ₆
H _5), such as _{3, O = P (C 6} H 5) 3), sulfur-containing compound-based (butyl sulfide according etc. JP-A 4-117390 and JP-2,4-bis [(octylthio) methyl]
Polymerization inhibitors such as -o-cresol, tetramethylthiuram disulfide and the like generally cannot be used because they also interfere with the hydrosilylation reaction. Further, amine-based compound compounds and some sulfur-containing compound-based polymerization inhibitors may cause odor and coloring quality problems in products.

An acryloxy group or methacryloxy group
As another method of producing the group-containing alkoxysilane,
Acryloxy or methacryloxy group-containing chlorosilanes
Without passing through the following general formula (III) H Si (OR^Three)_mR^Four _3-m (III) (wherein, R^Three, R^FourRepresents a monovalent hydrocarbon group having 1 to 6 carbon atoms.
And m is an integer of 1 to 3. )
Coxysilane and allyl acrylate or allyl methacrylate
Rate in the presence of a platinum group catalyst and various polymerization inhibitors
A method for causing a hydrosilylation reaction is disclosed in
No. 188689, Japanese Patent Publication No. 3-12075, etc.
However, this method includes addition isomers and various
Problems such as formation of organisms and hydrolysis of end products
There are quality problems such as unstable behavior,
The solution has not been solved and is still established as an industrial production method
It is not at present. Also, halopropylsilane
Compound and alkali metal salt of acrylic acid or methacrylic acid
For the synthesis by reacting with a phase transfer catalyst in the presence of
It is also known that the yield per unit volume is low.
It takes a lot of time to remove a large amount of by-product salt
There is a problem. For this reason, the industry still does not
Obtain alkoxy silane containing silane or methacryloxy group
As a method, the hydrid represented by the general formula (II) is used.
Rochlorosilane and allyl acrylate or allyl methax
And a hydrosilylation reaction in the presence of a platinum group catalyst.
Having the general formula (I)
Acryloxy or methacryloxy group-containing chlorosila
Raw material and then continuously or with a hydrochloric acid catcher
Reaction with alcohol in the presence of a base as a batch
The production method is the mainstream, and therefore the
Of spontaneous self-polymerization in the production of product (I)
Can be sufficiently avoided and quality problems may be caused to the final product.
Proposal of an irreversible solution is very much desired in the industry
It had been.

The present invention is intended to solve the problems associated with the prior art, and can sufficiently avoid the problem of spontaneous self-polymerization and give a quality problem to the final product. It is an object of the present invention to provide a method for producing an acryloxy group- or methacryloxy group-containing chlorosilane represented by the above formula (I) without chlorosilane.

[0016]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, as a novel polymerization inhibitor, 2,2 of the chemical formula (1)
-Hydrochlorosilane represented by the general formula (II) and allyl acrylate or allyl methacrylate in the presence of -thio-diethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Is subjected to a hydrosilylation reaction in the presence of a platinum group catalyst to produce an acryloxy or methacryloxy group-containing chlorosilane represented by the general formula (I). Without inhibiting the reaction at all, it has a very excellent polymerization inhibiting effect, and has found the effectiveness of not giving any quality problem to the final target acryloxy group or methacryloxy group-containing alkoxysilane, and found the present invention. I've reached the point.

Accordingly, the present invention provides a compound represented by the following general formula (II): SiCl_nR^Two _3-n (II) (wherein R^TwoRepresents a monovalent hydrocarbon group having 1 to 6 carbon atoms,
n is an integer of 1 to 3. )
Orchid with allyl acrylate or allyl methacrylate
With a platinum group catalyst and 2,2 represented by the following chemical formula (1).
-Thio-diethylene-bis [3- (3,5-di-t-butyl)
Tyl-4-hydroxyphenyl) propionate]
Characterized by a hydrosilylation reaction in the presence of
An acryloxy group or methacrylic group represented by the general formula (I)
Provided is a method for producing a roxy group-containing chlorosilane.

[0018]

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and n
Has the same meaning as above. )

Hereinafter, the present invention will be described in more detail.
The acryloxy group represented by the above general formula (I) of the present invention or
The method for producing methacryloxy group-containing chlorosilanes is as follows.
The general formula (II) H SiCl_nR^Two _3-n (II) hydrochlorosilane and allyl acrylate or
Causes hydrosilylation reaction with allyl methacrylate
Things.

Here, in the formula (II), R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. And the like, and a methyl group is particularly preferable. Note that n is 1, 2 or 3, and specific examples of the hydrochlorosilane include trichlorosilane, methyldichlorosilane, and dimethylchlorosilane.

The acryloxy or methacryloxy group-containing chlorosilane obtained by subjecting such hydrochlorosilane to a hydrosilylation reaction with allyl acrylate or allyl methacrylate is represented by the general formula (I). Is 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, 3-methacryloxypropyldimethylchlorosilane, 3-acryloxypropyltrichlorosilane, 3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyldimethylchlorosilane Etc. can be exemplified.

In the method for producing an acryloxy or methacryloxy group-containing chlorosilane according to the present invention, the hydrochlorosilane and allyl acrylate or allyl methacrylate have a molar ratio of 0.5 to 2.0, preferably 0.8 to 1 in terms of molar ratio. .2.

In the present invention, the hydrosilylation reaction between the above hydrochlorosilane and allyl acrylate or allyl methacrylate is carried out by a platinum group catalyst and the above-mentioned chemical formula (1).
In the presence of a polymerization inhibitor.

In this case, in the present invention, any of those conventionally known in the hydrosilylation reaction may be used as the platinum group catalyst, and specific examples thereof include the following. That is, chloroplatinic acid, chloroplatinic acid hexahydrate, Spei
er platinum catalyst (i.e., an alcohol solution of chloroplatinic acid), Karstedt platinum catalyst (i.e., a complex of chloroplatinic acid and sym-divinyltetramethyldisiloxane), a THF solution of chloroplatinic acid, and a supported platinum catalyst (Platinum activated carbon, platinum alumina, etc.), dichloro (1,5
-Cyclooctadiene) platinum (II), dichlorodiethyleneplatinum (II), dichlorobis (acetonitrile) platinum (II), dicarbonyldichloroplatinum (II), platinum oxide and the like can be used.

Such a platinum group catalyst is generally used as a platinum group metal in an amount of 1 × 10 ^-7 to 1 × 10 ^-3 mol, preferably 1 × 10 ^-6 to 1 × 10 ³ mol per mol of allyl acrylate or allyl methacrylate. Used in an amount of ^-4 mol.

On the other hand, 2,2-thio-diethylene-ethylene of the formula (1) is added as a polymerization inhibitor to the production method of the present invention.
Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is easily available industrially,
It is an inexpensive compound that can be safely handled. The 2,2-thio-diethylene-bis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] is added in an amount of 0.01 to 1 mol per 1 mol of the acryloxy or methacryloxy group-containing chlorosilane represented by the general formula (I). It is used in an amount of 10% by weight, preferably 0.1-1% by weight.

In the present invention, a reaction solvent may or may not be used. When a reaction solvent is used, the reaction solvent may be an aromatic compound such as benzene, toluene, xylene, mesitylene, tetralin, hexane, isooctane, decane. And aliphatic compounds such as heptane, and ether compounds such as THF.

In the present invention, 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate of the formula (1) is added as a novel polymerization inhibitor. In addition, as long as it does not inhibit the hydrosilylation reaction and does not cause a quality problem to the final target acryloxy group or methacryloxy group-containing alkoxysilane, a conventionally known polymerization inhibitor may be present together. I don't care.

Specifically, phenolic compounds such as hydroquinone and hydroquinone monomethyl ether;
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-
6-t-butylphenol), 4,4′-butylidenebis (6-t-butyl-m-cresol), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Hindered phenol compounds such as isocyanurate and the like can be mentioned. The amount of these additives is not particularly limited, and may be used alone or in combination of two or more in the range of 1 ppm to 10% by weight based on the weight of the compound represented by formula (I). it can.

In the present invention, the reaction temperature of the hydrosilylation reaction is from 20 to 150 ° C., preferably from 40 to 120 ° C. The pressure is not limited and may be normal pressure or pressurized. The atmosphere may be a nitrogen atmosphere or a condition in which oxygen (air) is blown.

In the present invention, the mode for carrying out the hydrosilylation reaction is not particularly limited, and the reaction can be carried out as a batch reaction, a semi-continuous reaction, or a continuous reaction. In the present invention, the order of addition of the reaction raw material, the platinum group catalyst, and the polymerization inhibitor is not particularly limited, and allyl acrylate or allyl methacrylate and hydrochlorosilane are simultaneously introduced into the platinum group catalyst and the polymerization inhibitor. However, if synthesized by the batch method,
More preferably, it is recommended to add in the order of polymerization inhibitor → reaction raw material (allyl acrylate or allyl methacrylate) → platinum group catalyst → reaction raw material (hydrochlorosilane).

The novel polymerization inhibitor used in the production method of the present invention, 2,2-thio-diethylene-
Although it is not desired to be bound by any particular theory as to how the polymerization inhibiting effect of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is exhibited, radical scavenging is not required. Phenolic hydroxyl group (stopping the radical chain reaction) and S atom (suppression of radical generation) having a peroxide decomposition effect have the same structure, so that they have unexpected synergistic effects. It seems that it exerts an excellent polymerization inhibition effect. In addition, although it generally contains an S atom in the molecule that inhibits the hydrosilylation reaction in the presence of a platinum group catalyst, it has the characteristic of not causing any reaction inhibition. It is considered to be a characteristic characteristic of the possible chemical structure of the compound. For this reason, among the various polymerization inhibitors, the 2,2-
Thio-diethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] having desirable properties (having excellent polymerization inhibiting ability and non-reaction inhibiting property) it is conceivable that.

The compound represented by the general formula (I) obtained in the present invention is then reacted with an alcohol in a continuous manner or in a batch manner in the presence of a base as a catcher of hydrochloric acid to give an acryloxy or methacryloxy group-containing compound. It is converted into an alkoxysilane and further purified by distillation to provide the final target acryloxy or methacryloxy group-containing alkoxysilane. In addition, in the case of reaction with alcohol or purification by distillation, 2,2 of chemical formula (1) is further added.
-Thio-diethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] may be added, and the amount of addition is not particularly limited. It may be added in an amount of 0.01 to 10% by weight, preferably 0.1 to 1% by weight, per mole of the acryloxy or methacryloxy group-containing chlorosilane represented by the formula (I). If the acryloxy group or methacryloxy group-containing alkoxysilane of the final target does not cause a quality problem, a conventionally known polymerization inhibitor may be arbitrarily selected and added to the above step at the same time. Specifically, the above-mentioned phenolic compounds and hindered phenol compounds, phenothiazine, copper compounds such as cuprous chloride, cupric chloride, cuprous oxide, cupric oxide, copper sulfate, and copper dimethyldithiocarbamate; Phosphorus or selected sulfur-containing compounds.

[0034]

According to the present invention, the hydrochlorosilane represented by the general formula (II) and the allyl acrylate or allyl methacrylate are subjected to a hydrosilylation reaction in the presence of a platinum group catalyst to give a compound represented by the general formula (I) When producing an acryloxy or methacryloxy group-containing chlorosilane, a novel polymerization inhibitor such as 2,2 of the formula (1) is used.
In the presence of -thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], a very excellent polymerization inhibiting effect can be obtained without any inhibition of the hydrosilylation reaction. By exerting such an effect, a spontaneous self-polymerization reaction can be sufficiently prevented, and the effect that no quality problem occurs in the final target acryloxy or methacryloxy group-containing alkoxysilane is obtained.

[0035]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited to the following Examples.

Example 1 A 300 ml four-necked flask equipped with a dropping funnel, a Dimroth water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Next, 126.2 g (1 mol) of allyl methacrylate, 0.1 g of a solution of chloroplatinic (VI) acid in 2-ethylhexanol (Pt10 ⁻⁵ mo)
1) and 2,2-thio-diethylene-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] was charged to 0.79 g (corresponding to 0.3% by weight per 1 mol of 3-methacryloxypropyltrichlorosilane (261.7 g)), and the contents of the flask were cooled to 110 ° C. while passing nitrogen gas through the vent of the condenser. The thing was heated. Then, 135.5 g of trichlorosilane (1 mo)
l) was fed into the liquid. Immediately after the start of the dropwise addition, a sharp exotherm was observed, and it was confirmed that the hydrosilylation reaction started smoothly. Thereafter, the reaction temperature is raised to 100 to 11
The whole amount was dropped over 3 to 4 hours while adjusting the dropping speed and the heating medium so as to maintain the temperature at 0 ° C. After dropping,
The mixture was aged at 100-110 ° C for 3 hours. afterwards,
After cooling to room temperature and examining the composition by gas chromatography, it was found that 3-methacryloxypropyltrichlorosilane was obtained in a yield of 96.5%. Also,
No impurities related to the polymerization inhibitor were detected near the target.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Example 2 The amount of a solution of chloroplatinic (VI) acid in 2-ethylhexanol was 0.05 g (Pt 5 × 10
^-6 mol), and the reaction was carried out in the same manner as in Example 1. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 96.4%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was fully purged with nitrogen.
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Example 3 2,2-thio-diethylene-
The amount of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] added was 0.52 g (1 mol based on 3-methacryloxypropyltrichlorosilane).
(Equivalent to 0.2% by weight per 261.7 g). Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography.
Methacryloxypropyltrichlorosilane yield 9
It turned out that it was obtained by 6.5%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Example 4 2,2-thio-diethylene-
The amount of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] added was 1.58 g (to 1 mol of 3-methacryloxypropyltrichlorosilane).
(Equivalent to 0.6% by weight per (261.7 g)). Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography.
Methacryloxypropyltrichlorosilane yield 9
It turned out that it was obtained at 6.6%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Comparative Example 1 2,2-thio-diethylene-
Instead of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-
The same operation as in Example 2 was performed except that t-butyl-4-hydroxy-benzylphosphonate-diethyl ester was used. However, no exotherm was observed even when the dropping was started, and when 50 g of trichlorosilane was dropped,
When the reflux became too violent, cooling was stopped by further dropping, and the composition of the contents was examined by gas chromatography.The hydrosilylation reaction did not occur at all, and only the raw material was recovered. .

Comparative Example 2 The 3,5-di-t- of Comparative Example 1
Butyl-4-hydroxy-benzylphosphonate-
A similar method was carried out except that the diethyl ester was changed to AO-23 (trade name of Asahi Denka Kogyo KK) shown below, but no exotherm was observed even when the dropping was started, and the reflux of trichlorosilane was carried out. When the reaction became violent, the dropwise addition was stopped and the mixture was cooled, and the composition of the content was examined by gas chromatography. As a result, no hydrosilylation reaction had occurred, and only the raw material was recovered.

[0046]

Embedded image

Comparative Example 3 The 3,5-di-t- of Comparative Example 1
Butyl-4-hydroxy-benzylphosphonate-
A similar method was carried out except that the diethyl ester was replaced with HP-10 (trade name of Asahi Denka Kogyo KK) shown below, but no exotherm was observed even when the dropping was started, and the reflux of trichlorosilane was carried out. When the reaction became violent, the dropwise addition was stopped and the mixture was cooled, and the composition of the content was examined by gas chromatography. As a result, no hydrosilylation reaction had occurred, and only the raw material was recovered.

[0048]

Embedded image

Comparative Example 4 The 3,5-di-t- of Comparative Example 1
Butyl-4-hydroxy-benzylphosphonate-
The diethyl ester is converted to bis (3,5-di-t-butyl-
The same procedure was performed, except that 4-hydroxybenzyl) sulfide was used. However, even when the dropping was started, no sharp exotherm was observed, and the reflux became vigorous as the dropping of trichlorosilane proceeded. After the dropping was completed over 5 to 6 hours, the mixture was heated to 90 to 100 ° C (for refluxing, (The temperature could not be raised any more.), And the mixture was further aged for 6 hours. However, trichlorosilane remained in the contents, and only about 80% of 3-methacryloxypropyltrichlorosilane was produced.

Comparative Example 5 3,5-di-t- of Comparative Example 1
Butyl-4-hydroxy-benzylphosphonate-
A similar method except that the diethyl ester was replaced by 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine. Carried out. However, no exotherm was observed even when the dropping was started. When 30 g of trichlorosilane was dropped, the reflux was so intense that the dropping was stopped and the content was cooled by gas chromatography. According to the graph, 3-methacryloxypropyltrichlorosilane was produced only in a few%,
The hydrosilylation reaction was deactivated halfway, and almost only the raw material was recovered.

Example 5 A 5000 ml four-necked flask equipped with a dropping funnel, a Dimroth type water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Then, 1891.5 g (15 mol) of allyl methacrylate, platinum chloride (V
I) 1.47 g of a solution of acid in 2-ethylhexanol (Pt
10 × 10 ⁻⁶ mol) and 11.8 g of 2,2-thio-diethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (versus 3-
1 mol of methacryloxypropyltrichlorosilane (2
61.7 g), and the contents of the flask were heated to 100 ° C. while venting nitrogen through the vent of the condenser. Then, trichlorosilane 20
31.0 g was fed into the liquid. Immediately after the start of the dropwise addition, a sharp exotherm was observed, and it was confirmed that the hydrosilylation reaction started smoothly. Thereafter, the reaction temperature is raised to 90-
The whole amount was dropped over 5 to 6 hours while adjusting the dropping speed and the heating medium so as to maintain the temperature at 100 ° C. After completion of the dropwise addition, the mixture was aged at 90 to 100 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.6%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was fully purged with nitrogen.
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Reference Example 1 2,2-thio-diethylene-
The reaction was carried out in the same manner as in Example 5, except that bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was not added. However, after completion of dropping, the mixture was aged at 80 to 90 ° C. for 2 hours, and the viscosity increased.

10 g of the thickened mixture was put into a 20 ml test tube with a screw mouth sufficiently purged with nitrogen, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C. to obtain a hard gel within 30 minutes. It became a state.

Comparative Example 6 2,2-thio-diethylene-
11.8 g of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261.
2,2 ′ instead of 0.3% by weight per 7 g)
10.5 g of methylene-bis- (4-ethyl-6-t-butylphenol) (0.5 / mol (261.7 g) of 3-methacryloxypropyltrichlorosilane)
The reaction was carried out in the same manner as in Example 5 except that (equivalent to% by weight) was used. However, after the end of the dropping, the mixture was added to the mixture at 90 to 10
After aging for 3 hours at 0 ° C., the viscosity increased.

10 g of this thickened mixture was put into a 20 ml screw-mouth test tube which had been sufficiently purged with nitrogen, sealed again after purging with nitrogen, and left in an oil bath at 150 ° C. to form a hard gel in 2 hours. Became.

Comparative Example 7 2,2-thio-diethylene-
11.8 g of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261.
2,2 ′ instead of 0.3% by weight per 7 g)
0.5 parts per 19.6 g of methylene-bis- (4-methyl-6-t-butylphenol) (based on 1 mol (261.7 g) of 3-methacryloxypropyltrichlorosilane).
The reaction was carried out in the same manner as in Example 5 except that (equivalent to% by weight) was used. However, after the end of the dropping, the mixture was added to the mixture at 90 to 10
When ripening at 0 ° C., the contents thickened in about 2 hours, and eventually gelled.

Comparative Example 8 2,2-thio-diethylene-
11.8 g of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261.
2,6-) instead of 2,6-
0.39 g of di-t-butyl-4-methylphenol (to 1 mol of 3-methacryloxypropyltrichlorosilane)
(Equivalent to 0.01% by weight per 261.7 g), and the reaction was carried out in the same manner as in Example 5. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.3%.

10 g of this mixture was fully purged with nitrogen.
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., whereupon it became a hard gel in 2 hours.

Comparative Example 9 2,2-thio-diethylene-
11.8 g of bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261.
2,6-) instead of 2,6-
0.39 g of di-t-butyl-4-methylphenol (to 1 mol of 3-methacryloxypropyltrichlorosilane)
(Equivalent to 0.01% by weight per (261.7 g)) and 19.6 g of 2,2′-methylene-bis- (4-ethyl-6-t-butylphenol) (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261 mol) The reaction was carried out in the same manner as in Example 5 except that 0.5% by weight per 0.7 g) was used. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.4%.

10 g of this mixture was fully purged with nitrogen.
After placing in a test tube with a 0 ml screw hole, replacing the atmosphere with nitrogen again, and sealing the mixture, it was left in an oil bath at 150 ° C.
It turned into a hard gel in 3 hours.

Comparative Example 10 A reaction was carried out in the same manner as in Comparative Example 9 except that dry air was bubbled into the reaction system through an ultrafine glass tube at 37.5 ml / min. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.4%.

10 g of this mixture was replaced with 2
After placing in a test tube with a screw cap of 0 ml, replacing with nitrogen again and sealing, and leaving it in an oil bath at 150 ° C.,
It became a hard gel in 5 hours.

[Comparative Example 11] 2,6-di-t-butyl-
0.39 g of 4-methylphenol (based on 1 mol (261.7 g) of 3-methacryloxypropyltrichlorosilane)
Per weight) and 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol) 1
Instead of 9.6 g (corresponding to 0.5% by weight per mol of 3-methacryloxypropyltrichlorosilane (261.7 g)), 1.96 g of 2,6-di-tert-butyl-4-methylphenol (vs. 3) 0.0 per mol of methacryloxypropyltrichlorosilane (261.7 g)
5% by weight) and 2,2′-methylene-bis- (4
3.93 g (to 1-mol of 3-methacryloxypropyltrichlorosilane)
The reaction was carried out in the same manner as in Comparative Example 10 except that (equivalent to 0.1% by weight per 261.7 g) was used. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.6%.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but it became a hard gel in 5 hours.

Comparative Example 12 Example 5 was repeated except that phenothiazine was used instead of 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. The reaction was carried out in the same manner as described above. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 95.4%.

10 g of this mixture was replaced with 2
After placing in a test tube with a screw cap of 0 ml, replacing with nitrogen again and sealing, and leaving it in an oil bath at 150 ° C.,
A hard gel was formed in 6 hours.

Comparative Example 13 0.79 g of 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (vs. 3-methacryloxypropyltrichlorosilane) 1 mol (26
Instead of 0.26 g of hydroquinone monomethyl ether (based on 1 mol of 3-methacryloxypropyltrichlorosilane (26 g / 1.7 g)).
(Equivalent to 0.1% by weight per 1.7 g)), and the reaction was carried out in the same manner as in Example 1 except that 112.2 g of toluene was further used as a reaction solvent. However, after dripping,
When the mixture was aged at 100 to 110 ° C., the content thickened after about 1 hour, so the aging was stopped and the mixture was cooled.

Comparative Example 14 0.79 g of 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (vs. 3-methacryloxypropyltrichlorosilane) 1 mol (26
1.7 g) equivalent to 0.3% by weight) instead of 2,
0.26 g of 2'-methylene-bis- (4-ethyl-6-t-butylphenol) (corresponding to 0.1% by weight per 1 mol (261.7 g) of 3-methacryloxypropyltrichlorosilane) and 1,3,3 5-trimethyl-
0.26 g of 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (based on 1 mol of 3-methacryloxypropyltrichlorosilane (261.
The reaction was carried out in the same manner as in Example 1 except that 0.1% by weight per 7 g) was used. However, after dripping,
The mixture was aged at 100 to 110 ° C. for 3 hours, and was cooled to room temperature and allowed to stand. After several days, the content became thick.

Example 6 A 5000 ml four-necked flask equipped with a dropping funnel, a Dimroth water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Then, 1891.5 g (15 mol) of allyl methacrylate, platinum chloride (V
I) 0.74 g of a solution of acid in 2-ethylhexanol (Pt
5 × 10 ⁻⁶ mol) and 11.8 g of 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (vs. 3-methacryloxypropyl) 1 mol of trichlorosilane (26
The content of the flask was heated to 100 ° C. while passing nitrogen gas through the vent of the condenser. Next, trichlorosilane 203
1.0 g (15 mol) was fed into the liquid. Immediately after the start of the dropwise addition, a sharp exotherm was observed, and it was confirmed that the hydrosilylation reaction started smoothly. Thereafter, the entire amount was dropped over 5 to 6 hours while adjusting the dropping speed and the heating medium so as to maintain the reaction temperature at 100 to 110 ° C. After completion of the dropwise addition, the mixture is heated at 100 to 110 ° C for 1 to 2
Aged for hours. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 96.2%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Example 7 A 300 ml four-necked flask equipped with a dropping funnel, a Dimroth water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Then, 112.2 g (1 mol) of allyl acrylate and 2 parts of chloroplatinic (VI) acid were added.
0.1 g of ethylhexanol solution (Pt10 ^-5 mol
And 2,2-thio-diethylene-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] 0.74 g (corresponding to 0.3% by weight per 1 mol (247.7 g) of 3-acryloxypropyltrichlorosilane) was charged, and the contents of the flask were cooled to 80 ° C. while passing nitrogen gas through the vent of the condenser. The thing was heated. Then, 135.5 g of trichlorosilane (1 mo)
l) was fed into the liquid. An exotherm was observed immediately after the start of the dropwise addition, confirming that the hydrosilylation reaction had started. Thereafter, the entire amount was dropped over 3 to 4 hours while adjusting the dropping speed and the heating medium so as to maintain the reaction temperature at 80 to 90 ° C. After completion of the dropwise addition, the mixture is heated to 80 to 90 ° C.
For 3 hours. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-acryloxypropyltrichlorosilane was obtained at a yield of 83.5%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was replaced with 2
It was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C. No viscosity was observed even after 15 hours.

Example 8 A 300 ml four-necked flask equipped with a dropping funnel, a Dimroth water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Then, 126.2 g (1 mol) of allyl methacrylate, 0.1 g (including 10 ^-5 mol of Pt) of a complex xylene solution of sym-divinyltetramethyldisiloxane and chloroplatinic acid, and 2,2-thio-diethylene-bis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] 0.79 g
(Vs 3-methacryloxypropyltrichlorosilane 1m
ol (equivalent to 0.3% by weight per 261.7 g), and the contents of the flask were heated to 110 ° C. while passing nitrogen through the vent of the condenser. Next, 135.5 g (1 mol) of trichlorosilane was fed into the liquid.
Immediately after the start of the dropwise addition, a sharp exotherm was observed, and it was confirmed that the hydrosilylation reaction started smoothly. Thereafter, the whole amount was dropped over 4 hours while adjusting the dropping speed and the heating medium so as to maintain the reaction temperature at 100 to 110 ° C. After completion of the dropwise addition, the mixture was heated at 100 to 110 ° C for 2 hours.
Aged for ~ 3 hours. Thereafter, the mixture was cooled to room temperature, and the composition was examined by gas chromatography. As a result, it was found that 3-methacryloxypropyltrichlorosilane was obtained at a yield of 96.4%. In addition, impurities related to the polymerization inhibitor were not detected near the target.

10 g of this mixture was replaced with 2
The mixture was placed in a test tube with a 0 ml screw opening, replaced with nitrogen, sealed, and left in an oil bath at 150 ° C., but no viscosity was observed even after 20 hours.

Comparative Example 15 A 300 ml four-necked flask equipped with a dropping funnel, a Dimroth water-cooled condenser, a stirrer, and a thermometer was sufficiently purged with nitrogen. Next, 126.2 g (1 mol) of allyl methacrylate and 0.05 g of a 2-ethylhexanol solution of chloroplatinic (VI) acid (Pt5 × 1
0 ^-6 including mol) and cupric 0.79 g (vs. chloride 3-
1 mol of methacryloxypropyltrichlorosilane (2
61.7 g), and the content of the flask was heated to 110 ° C. while passing nitrogen gas through the vent of the condenser. Then, trichlorosilane 13
5.5 g (1 mol) was fed into the liquid. However, no exotherm was observed even when the dropping was started, and at the time when 40 g of trichlorosilane was dropped, the reflux was so intense that the dropping was stopped and cooling was continued.
When the composition of the contents was examined by gas chromatography, no hydrosilylation reaction occurred, and only the raw material was recovered.

Reference Example 2 The following polymerization inhibitor was added to 3-methacryloxypropyltrichlorosilane in an amount of 5% by weight, and after standing for 3 days, the composition of the contents (focusing on the vicinity of the target substance) was examined by gas chromatography. Was. (Polymerization inhibitor) 1: 2,2-thio-diethylene-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] No. 2: AO-23 No. 3: bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide No. 3: 4: 2,6-di-t-butyl-4-methylphenol No. 4: 5: di-t-butyl-4-dimethylaminomethylenephenol No. 5 6: 2,6-di-t-butyl-4-hydroxymethylphenol (Results) 1: No impurities derived from the polymerization inhibitor were detected near the target. No. 2: Many impurities were detected near the target. No. 3: Quinone methide was detected near the target. No. 4: 2,6-di-tert-butyl-4-near the target
Methyl phenol itself was detected. No. 5: Di-t-butyl-4-dimethylaminomethylenephenol itself and quinone methide were detected near the target. No. 6: Quinone methide and 2,6-di-in the vicinity of the target
t-Butyl-4-methylphenol was detected.

Reference Example 3 The same method (2,
2-thio-diethylene-bis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] to 3-methacryloxypropyltrichlorosilane 1mo
using an amount equivalent to 0.3% by weight per 1 (261.7 g)) and continuously reacting with methanol by a known conventional method using the crude 3-methacryloxypropyltrichlorosilane. To synthesize 3-methacryloxypropyltrimethoxysilane. Next, 0.1 wt% of hydroquinone monomethyl ether and 0.3 wt% of copper dimethyltyldithiocarbamate were added to the crude product, and purified by distillation. Methoxysilane was obtained. Next, the composition of the product (focusing on the vicinity of the target substance) was examined by gas chromatography. As a result, no impurity derived from the polymerization inhibitor was detected near the target product. It was colorless and transparent without coloring, and had no off-flavor.

Claims (2)

[Claims] 1. A compound represented by the following general formula (II): SiCl_nR^Two _3-n (II) (wherein R^TwoRepresents a monovalent hydrocarbon group having 1 to 6 carbon atoms,
n is an integer of 1 to 3. )
Orchid with allyl acrylate or allyl methacrylate
With a platinum group catalyst and the following chemical formula (1):2,2-thio-diethylene-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Hydrosilylation reaction in the presence of [propionate]
Having the following general formula (I):(Where R¹Represents a hydrogen atom or a methyl group;^TwoAnd n
Has the same meaning as above. Acryloxy group represented by)
Alternatively, a method for producing a methacryloxy group-containing chlorosilane. 2. The method according to claim 1, wherein R ² is a methyl group.