JPH07206877A - Production of organosilicon compound containing unsaturated double bond - Google Patents

Abstract

PURPOSE:To continuously obtain an organosilicon compound in good yield without causing polymerization thereof by adding a specific polymerization inhibitor to an organosilicon compound containing a polymerizable unsaturated double bond. CONSTITUTION:This method for producing the objective substance is to react an organosilicon compound having at least one polymerizable unsaturated double bond in the molecule, especially a functional silane, containing (meth)acrylic group and expressed by the formula [R<1> is H or methyl; R<2> is a 1-11C bivalent hydrocarbon; X is Cl, OCH3, OC2H5 or OSi(CH3)3; m is 1-3] with at least one polymerization inhibitor selected from (i) 2,2-diphenyl-1-picryl-hydrazyl, (ii) galvinoxyl and (iii) 1,3,5-triphenyl-verdazyl. The polymerization inhibitor is added in an amount of 1-30000ppm based on the organosilicon compound thereto. The polymerization inhibitor has excellent inhibiting effects on the polymerization and the reaction can stably and continuously be carried out without polymerizing the organosilicon compound even when keeping thereof at a high temperature for a long time. Thereby, the maintenance of the interior of a reactional vessel and a distillation apparatus can readily be performed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an unsaturated double bond-containing organosilicon compound, and more particularly to an organosilicon compound containing a group having high polymerizability such as (meth) acryloxy group, styryl group and butadienyl group. The present invention relates to a method for preventing polymerization during compound synthesis or distillation purification.

[0002]

2. Description of the Related Art Organosilicon compounds containing a polymerizable unsaturated double bond in the molecule, for example, a (meth) acryloxy group, a styryl group, a butadienyl group, etc., can be synthesized at the time of synthesis or distillation purification. Since a polymerization based on a heavy bond proceeds, a polymerization inhibitor is added to the polymer during the synthesis and distillation purification thereof, and various polymerization inhibitors have been proposed.

For example, hydroquinone, 2,5-di-t-butylhydroquinone, and copper acetate are known to be effective as polymerization inhibitors for acrylic functional silanes (see Japanese Patent Publication No. 38-2136), and methacryl functionalities are known. Simultaneous addition of hydroquinone and water-soluble alcohol (see Japanese Examined Patent Publication No. 40-6,212) is used to improve the storage stability of silane, and phenyl-α-is used as a polymerization inhibitor for the production of (meth) acrylic functional silane. Aromatic amines such as naphthylamine and N, N'-dinaphthyl-p-phenylenediamine, phenolic compounds such as hydroquinone, and copper powder are known to be effective (see Japanese Patent Publication No. 42-23332).

As a polymerization inhibitor for distilling the methacryl-functional silane, 2,5-di-t-butylbenzoquinone (see JP-A-60-239,491) is a (meth) acryl-functional silane. P as a polymerization inhibitor during continuous synthesis
-Methoxy-phenol, 2,6-di-t-butyl-4-
Phenols such as methyl-phenol, aromatic amines such as diphenylenediamine, and aromatic sulfur compounds such as phenothiazine have been proposed (JP-A-62-28).
It has been proposed that hindered phenol is effective as a polymerization inhibitor during the synthesis of methacryl-functional silane and during distillation purification (see Japanese Patent Laid-Open No. 63-188,689).

[0005]

However, none of the above-mentioned various polymerization inhibitors that have been proposed so far have sufficient polymerization-inhibiting ability, and the effect thereof is particularly notable when kept at a high temperature. There is a disadvantage that it becomes scarce and gelation often occurs in the tank, and there is a demand for the development of a more useful polymerization inhibitor.

[0006]

The present invention relates to a method for producing an unsaturated double bond-containing organosilicon compound, which has solved such disadvantages, and it has at least 1 in the molecule.
A) 2,2-diphenyl-1-picryl hydrazyl, b) galvinoxyl, c) 1,3,5-triphenyl
It is characterized by adding at least one compound selected from ferdazyl.

That is, as a result of various investigations by the present inventors on a polymerization inhibitor for an unsaturated double bond in an organic silicon compound containing an unsaturated double bond, the high temperature of the unsaturated double bond-containing organic silicon compound was found to be high. In the polymerization below, radical polymerization is dominant, and therefore the polymerization inhibitor to be used here is a stable radical and is a compound that reacts with a radical substance to convert to a stable compound. Found to be valid, and described above
Confirm that a), b), and c) are useful, about the type of organic silicon compound to be used in the present invention, the type of polymerization inhibitor used here, the addition amount, etc. To complete the present invention. This will be described in more detail below.

[0008]

The present invention relates to a method for producing an organic silicon compound containing an unsaturated double bond. The organic silicon compound containing an unsaturated double bond used in the present invention has a CH ₂ = CH- group, CH ₂ = CH-CH ₂ -group, CH ₂ = C (CH ₃ ) -C in the molecule.
H ₂ -group, CH ₂ = CH- (CH ₂ ) ₂ -group, CH ₂ = CH- (CH ₂ ) ₄ -group, CH ₂ = CH
- (CH _{2) 8} - vinyl groups, such as groups,

[0009]

[Chemical 2] (Meth) acrylic groups such as (where R ³ represents H or CH ₃ )

[0010]

[Chemical 3] Styryl groups, such as

[0011]

[Chemical 4] At least one polymerizable functional group such as a Butadier group represented by (wherein R ³ represents a hydrogen atom or a methyl group).
Any compound may be used as long as it contains one.

However, this is especially true for the general formula

[0013]

[Chemical 5] , R ¹ is a hydrogen atom or a methyl group, R ² is -CH ₂ -,-
(CH ₂ ) _3- , -CH ₂ -CH (CH ₃ ) -CH ₂ -,-(CH ₂ ) ₆ ,-(CH ₂ ) ₁₀ -,-
(CH _{2) 11} - ₂ divalent hydrocarbon group represented by, X is -Cl, -OCH _3,
A group represented by -OC ₂ H ₅ or -OSi (CH ₃ ) ₃ and a (meth) acryl-functional silane in which m is 1, 2 or 3 are preferable, and the following are exemplified. .

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

[0025]

[Chemical 17]

In the present invention, in order to inhibit the polymerization during the production or distillation purification of the above-mentioned organic silicon compound containing an unsaturated double bond, a) 2,2-
Diphenyl-1-picryl hydrazyl

[Chemical 18] b) Galvinoxyl

[Chemical 19] Or c) 1,3,5-triphenyl ferdazyl

[Chemical 20] At least one compound selected from the above is added.

When this is added, the organosilicon compound does not polymerize even if it is held at 100 to 200 ° C. for about 30 hours, so that the desired organosilicon compound can be obtained in a high yield. The advantage is that the reaction can be carried out stably and continuously, and in this case, the maintenance in the reaction tank and the distillation apparatus can be facilitated.

If the amount of the polymerization inhibitor added is less than 1 ppm with respect to the organic silicon compound having an unsaturated double bond, the addition effect will be too small, and if it exceeds 30,000 ppm, the solution will become viscous and will be distilled. Since the yield will be reduced, the range may be 1 to 30,000 ppm, but the preferred range is 10 to 20,000 ppm.

Further, this polymerization inhibitor may be used in combination with various conventionally known polymerization inhibitors, polymerization inhibitors and polymerization inhibitors, and therefore, they are hydroquinone, methylhydroquinone (p-methylphenol), 2,5. -Quinone compounds such as di-t-butylhydroquinone, hindered phenol compounds such as 2,6-di-t-butyl-4-methylphenol, catechols such as t-butylcatechol, diphenylenediamine, phenyl-α -Aromatic amine compounds such as naphthylamine, N, N'-dinaphthyl-p-phenylenediamine, aromatic sulfur compounds such as phenothiazine, copper powder, copper-containing compounds such as copper dimethyldithiocarbamate, ferric chloride, nitro compounds And oxygen may be used in combination.

[0030]

EXAMPLES Next, examples and comparative examples of the present invention will be described. Example 1 Allyl methacrylate was hydrosilylated by reacting trichlorosilane with chloroplatinic acid as a catalyst, and then urea and methanol were added to methoxylize and low boiling components were removed to prepare γ-methacryloxypropyltrimethoxysilane. When analyzed by gas chromatography,
The purity was 95%.

Next, a polymerization inhibitor as shown in Table 1 was added to the γ-methacryloxypropyltrimethoxysilane.
5 g of the product added with 1.0% by weight was placed in a test tube, which was purged with nitrogen, then tightly closed with a rubber stopper, immersed in an oil bath at 170 ° C., and the inside was observed with time to gel the contents. When the time was obtained, the results as shown in Table 1 were obtained, and it was confirmed that those to which the polymerization inhibitor according to the present invention was added had extremely high gelation preventing ability even at high temperatures.

[0032]

[Table 1]

Example 2 The polymerization test of γ-acryloxypropyltrimethoxysilane obtained in Example 1 was conducted in an open system at 150 ° C.
The result as shown in was obtained.

[0034]

[Table 2]

Example 3 To 3 kg of γ-methacryloxypropyltrimethoxysilane used in Example 1, the type and amount of the polymerization inhibitor shown in Table 3 were added, and this was filled with a glass filler having a height of 100 m. The temperature inside the distilling tank is set in a distilling device equipped with a rectifying column
After distilling for 30 hours under the conditions of 130-140 ° C and reduced pressure of 80-10 torr, the situation and yield of γ-methacryloxypropyltrimethoxysilane in the distillation tank at this time were examined. As shown in Table 3, The result was obtained.

[0036]

[Table 3]

[0037]

The present invention relates to a method for producing an organosilicon compound having an unsaturated double bond in the molecule, which comprises adding a) 2,2-diphenyl-1 to this type of organosilicon compound.
-Picryl hydrazyl, b) galvinoxyl, c) 1,
It is characterized by adding at least one compound selected from 3,5-triphenyl ferdazyl. According to this, the compounds a), b) and c) are conventionally known. It has an excellent effect of inhibiting polymerization compared to the polymerization inhibitor of 1. and can prevent the polymerization even when this organic silicon compound is kept at high temperature for a long time. It is possible to improve the yield of the organosilicon compound, to stably and continuously operate this manufacturing process, and to facilitate the maintenance in the reaction tank and the distillation apparatus. Advantages are given.

Claims (2)

[Claims] 1. An organosilicon compound having at least one polymerizable unsaturated double bond in the molecule, a) 2,2-diphenyl-1-picryl hydrazyl, b) galbinoxyl, c) 1, A method for producing an unsaturated double bond-containing organosilicon compound, which comprises adding at least one compound selected from 3,5-triphenyl ferdazyl. 2. An organic silicon compound is represented by the general formula: (Here, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
Divalent hydrocarbon groups to 11, X is _{-Cl, -OCH 3, -OC 2 H} 5 or
-OSi (CH _{3) 3} in the group represented, m is 1, 2 or 3) indicated by (meth) unsaturated double bond-containing organosilicon compound as claimed in claim 1 is an acrylic group-containing silane with Manufacturing method.