JPH07165921A - New silicone compound - Google Patents

Abstract

PURPOSE:To produce the subject silicone compound useful as a modified silicone oil, etc., by reacting a tetraalkoxysilane, a glycidoxypropylalkyldialkoxysilane and methacryloxypropyltrialkoxysilane. CONSTITUTION:This compound is synthesized by conducting a cohydrolysis and condensation reaction of (A) a tetraalkoxysilane of the formula Si(OR<1>)4 (R<1> is a 1 to 8C saturated alcohol-derived alkoxy), (B) a 3- glycidoxyprolylalkyldialkoxysilane of formula I (R is a 1 to 8C saturated hydrocarbon group, an alkenyl, especially preferably a 1 to 2C saturated hydrocarbon or vinyl; R<2> is same as R<1>) and (C) a 3-methacryloxypropyltrialkoxysilane of formula II (R<3> is same as R<1>) in the presence of an acid catalyst in a condensed organotin catalyst-containing mixture solvent with water in an amount of 3 to 4 times the total amount of the silanes on molar base. For example, a compound represented by formula III [(x') is 2.0 to 0.5; (m), (n) and (l) are each a positive integer of >=3], having a terminal silanol group and exhibiting an oil state at ordinary temperatures is exemplified.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silicone compound and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, silane coupling agents have been put into practical use for glass-reinforced FRP applications since about 1947, and Dow Conning's E.P.
It is a silane compound whose application has been developed by the above. Even today, it is widely used as a binder that acts mainly between the thermosetting resin and the feeler to suppress the improvement of hot water resistance and the deterioration of electrical properties. Recently, in addition to the purpose of improving strength, it has been used as a fiber treatment agent as a chemical for giving slimy feel and impact resilience, and added for the purpose of improving orientation and strength by being added during the manufacture of plastic magnets. In addition, vinyl silane coupling agents are suitable for coating electric wires as a simple crosslinking agent for polyethylene. The silane coupling agent having a 3-glycidoxypropyl group is added to the epoxy resin compound and effectively used for maintaining the characteristics of the IC encapsulant, and also used as a dye-type hard coat agent for plastic lenses. There is. On the other hand, the silane coupling agent of 3-methacryloxypropyltrialkoxysilane is a glass fiber reinforced unsaturated polyester resin composite material (F
It is an indispensable binder for RP).
It is also used as an essential coupling agent in the production of artificial marble containing acrylic resin silica. The recently announced co-hydrolysates include tetramethoxysilane and 3
-Glycidoxypropyltrimethoxysilane has been trial-produced, but unlike the present invention, it is an oil having an extremely low viscosity in which a considerable amount of alkoxy groups remain. This seeks development as a so-called polymerized silane coupling agent, and is completely similar in structure and function. Further, conventionally, a polymethylsiloxane main chain having an alkoxy group as a pendant has also been proposed, but in both cases, the problem of compatibility with an organic resin becomes a major bottleneck and its application cannot be developed.

[0003]

The present invention does not utilize the residual alkoxy group which has been proposed so far, but includes a silanol group which is rich in crosslinkability and reactivity and is stable at room temperature, and which has a three-dimensional structure. -Providing polysiloxanes functionalized with glycidoxypropyl groups. It is also possible to obtain a cured product of this silanol group by polycondensation with a methyl polymer or polysiloxane cross-linking. Of course, the contained epoxy group can be subjected to a usual polymerization reaction, and because of its good compatibility with the epoxy resin, it is possible to carry out a homogeneous polymerization which was not possible with conventional polysiloxanes, so that a new demand can be created. The methacryloxy group contained is P
It is possible to copolymerize with methacrylic resins such as MMA, and because of the good compatibility of the compound of the present invention, it is possible to form a homogeneous polymer, which was not possible with conventional polysiloxanes, so that new demand can be created. SC having methacryloxypropyl group
SCA having A and a glycidoxypropyl group is equivalent to or slightly more expensive than methyl-modified silicone oil by itself. Multifunctional polyorganosiloxanes made from these materials have high organic functional group content. Also, the price will be higher. Therefore, it is necessary to reduce the content of the organic functional group and reduce the cost. In order to convert an alkoxy group into a silanol group without leaving an alkoxy group by co-hydrolysis of a tetraalkoxysilane and an organofunctional alkoxysilane coupling agent, at least 3 times the molar amount of silane, preferably 3.5 times the molar amount of silane. It is necessary to react more than a mole of water. For this purpose, the hydrophilic solvent used must be in an amount sufficient to dissolve the added water. It has been found that a silane coupling agent which satisfies the above conditions and which is hydrolyzed for a long time only with an acid catalyst like S520 can be solved by adding a condensation catalyst such as an organic tin compound. Among the reaction raw materials relating to the present invention, ethyl orthosilicate has a hydrolysis rate by itself which is a rate at which the monomer disappears within 20 minutes at room temperature. However, when the hydrolysis is started by mixing with S520, a significant delayed reaction occurs. Occurs. In addition, the hydrolysis rate of 3-methacryloxytrialkoxysilane alone in the reaction raw materials is such that the monomer disappears within 30 minutes at room temperature. As a method of overcoming the difference in hydrolysis rate due to the difference in these raw materials, a sequential three-stage hydrolysis condensation method in which raw materials with a fast hydrolysis rate are divided into three sequential steps to react, or a combination that causes a significant delay in hydrolysis by mixing the raw materials The problem was solved by devising a two-step hydrolysis and condensation method that avoids In the present invention, the SCA having a methacryloxypropyl group and the SCA having a glycidoxypropyl group are further incorporated with a tetraalkoxysilane which is cheaper than these SCA to increase the chemically active silanol group and reduce the cost. I measured it. As is clear from the above description, an object of the present invention is to provide a novel silicone compound and a method for producing the same, in which the above-mentioned problems are solved.

[0004]

The present invention has the following constitutions (1) to (5). (1) Tetraalkoxysilane represented by the general formula Si (OR ¹ ) ₄ and the general formula 4

[Chemical 4] 3-glycidoxypropylalkyldialkoxysilane represented by

[Chemical 5] The co-hydrolysis and condensation reaction of 3-methacryloxypropyltrialkoxysilane represented by the formula (3) with an acid catalyst in a mixed solvent containing an organotin condensation catalyst with 3 to 4 times the molar amount of water of the silane is carried out. A method for producing a novel polysiloxane having both a silanol group and a 3-glycidoxypropyl group and a 3-methacryloxypropyl group which are stable at room temperature.
Here, as the alkyl group R, a C _{1 to} C ₈ saturated hydrocarbon group or an alkenyl group is used, and particularly preferably a C _{1 to} C ₂ saturated hydrocarbon group or a vinyl group is used. The alkoxy groups R ¹ , R ² and R ³ are made from C _{1 to} C ₈ saturated alcohols. (2) The following formula 6

[Chemical 6] Organopolysiloxane that is in an oil state at room temperature. However, the compound of formula 1 in which the silanol group x is in the range of 2.0 to 0.5, the polymer end group is a silanol group, and m, n, and l are each a positive integer of 3 or more. (3) In the above item (1), tetraalkoxysilane / 3-methacryloxypropyltrialkoxysilane /
Prior to the co-hydrolysis and condensation reaction of 3-glycidoxypropylalkyldialkoxysilane, tetraalkoxysilane was hydrolyzed by adding a catalytic amount of an acid catalyst and 3 to 4 times the molar amount of water to the total amount of silane, and then hydrolyzing the same. 3-methacryloxypropyltrialkoxysilane is added and hydrolyzed, and a catalytic amount of the organotin catalyst and a predetermined molar ratio of 3 are added.
-A method for producing the above organopolysiloxane compound by a sequential three-step hydrolysis condensation method in which glycidoxypropylalkyldialkoxysilane is added to cause a cohydrolysis condensation reaction. (4) In the above item (1), tetraalkoxysilane / 3-methacryloxypropyltrialkoxysilane /
Prior to the co-hydrolysis and condensation reaction of 3-glycidoxypropylalkyldialkoxysilane, tetraalkoxysilane was hydrolyzed by adding a catalytic amount of an acid catalyst and water in an amount of 3 to 4 times the total amount of silane. Production of the organopolysiloxane compound by a two-step hydrolysis condensation method in which an organotin catalyst and a predetermined molar ratio of 3-methacryloxypropyltrialkoxysilane and 3-glycidoxypropylalkyldialkoxysilane are added to cause a cohydrolysis condensation reaction. Law. (5) The tetraalkoxysilane is tetramethoxysilane or tetraethoxasilane, and the 3-methacryloxypropyltrialkoxysilane is either 3-methacryloxypropyltrimethoxysilane or 3-methacryloxypropyltris (methoxyethoxy) silane. Wherein the 3-glycidoxypropyl dialkoxysilane is a combination of any of three silanes, which is 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropylmethyldiethoxysilane, and A method for producing the compound according to item (1).

The structure and effect of the present invention will be described in detail below. The present invention has the general formula 7

[0006]

[Chemical 7]

The present invention relates to a method for producing an organopolysiloxane compound containing 3-methacryloxypropyl group and 3-glycidoxypropyl group represented by and 0.5 to 2.0 silanol groups stable at room temperature. (Where x,
y, l, m and n are the same as in the above case. ) The mole ratio of the tetraalkoxysilane (A), which is a constituent of the present invention, the mole of 3-methacryloxypropyltrialkoxysilane (B), and the mole of 3-glycidoxypropylalkyldialkoxysilane (C), is (A). ) /
(B) = 1.0 or less, and (C) / (B) = 2.
When the reaction is performed at 0 or more and 6.0 or less, the produced organopolysiloxane compound exhibits an oil state when isolated at room temperature. In the case of (A) / (B) / (C) = 1/1/1, a resinous solid is obtained at room temperature, and (A) /
In the case of (B) / (C) = 1/1/6, an oil partially containing gel is obtained at room temperature. Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetra-n-propoxysilane. Tetramethoxysilane or tetraethoxysilane is advantageously used, judging from the hydrolysis rate and Si content.
That is, a commercially available product such as tetraethoxysilane (orthoethyl silicate manufactured by Tama Chemical Co., Ltd.) can be used. On the other hand, as the trialkoxysilane coupling agent having a 3-methacryloxypropyl group, those having an alkoxy group made of a C _{1 to} C ₈ saturated alcohol or those made of cellosolve are suitable. A methoxy group or a methoxyethoxy group may be mentioned depending on the hydrolysis rate. That is, commercially available products such as 3-methacryloxypropyltrimethoxysilane (Sila Ace S710 manufactured by Chisso Corp.) and 3-methacryloxypropyltris (methoxyethoxy) silane (M8558 manufactured by Huls America) can be used.

On the other hand, in the dialkoxy silane coupling agent containing a 3-glycidoxypropyl group, the alkyl group R
Is a C ₁ -C ₈ saturated hydrocarbon group or an alkenyl group, but a C ₁ -C ₂ saturated hydrocarbon group or a vinyl group is particularly preferably used. The two alkoxy groups are also preferably those prepared from a C _{1 to} C ₈ saturated alcohol, and particularly preferably a methoxy group or an ethoxy group depending on the hydrolysis rate. That is, 3-glycidoxypropylmethyldimethoxysilane (Sila Ace S520 manufactured by Chisso Corporation) and 3-glycidoxypropylmethyldiethoxysilane (CF silane KBE manufactured by Shin-Etsu Chemical Co., Ltd.)
402) and other commercially available products can be used.

Next, regarding an acid as a hydrolysis catalyst, the acid concentration is not particularly specified as long as a catalytic amount of acid is present. For example, there is a method in which a diluted acid is added by a specified amount of water.
As the type of acid, any of an organic acid such as acetic acid, an inorganic acid such as hydrochloric acid and sulfuric acid, or a strongly acidic ion exchange resin can be used, but an inorganic acid having a high hydrolysis rate is preferably recommended.

Any of a wide variety of materials that act as silanol condensation catalysts can be used in the present invention. Such materials include, for example, organotin compounds such as dibutyltin dilaurate, stannous acetate, stannous octoate, or metals such as zinc naphthenate, zinc octoate, 2-ethylhexanoic acid and cobalt naphthenate. Mention may be made of carboxylates, titanium esters and chelates.
Preferred compounds are organotin compounds, especially tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate. The amount of condensation catalyst is not particularly limited as long as it is a catalytic amount, but is generally 0.05% or less of the total amount of silane.

The amount of water for sufficient hydrolysis needs to be added in an amount of 3 to 4 times, preferably 3.5 times or more the mol of the total silane. The reaction solvent may be a hydrophilic solvent alone, but a mixed solvent of hydrophilic solvent and a mixed solvent of lipophilic and hydrophilic solvent are also applicable. For example, methanol,
A hydrophilic solvent such as ethanol, acetone, tert-butanol, diacetone alcohol, etc., or a mixed solvent such as xylene / alcohol, toluene / alcohol etc. can also be used.

In the production of the organopolysiloxane according to the present invention, the sequential three-step hydrolysis condensation method or the two-step hydrolysis condensation method occupies an important position in the invention. That is, when tetraalkoxysilane such as ethyl orthosilicate is hydrolyzed alone in the presence of an acid catalyst, the monomer disappears at room temperature in ten and several minutes when measured by a gas chromatographic (GC) check method, and a trialkoxysilane such as S710 is used. Silane also has a relatively high hydrolysis rate, and the monomer and oligomer components disappear in about 20 minutes at room temperature. On the other hand, a dialkoxy silane coupling agent such as S520 has a significantly longer hydrolysis time than tetraalkoxysilane, and the hydrolysis time is 4
Only less than 0% was hydrolyzed. It was found that the addition of the condensation catalyst described above is effective in accelerating this. However, ethyl orthosilicate and S710 and S52
When an attempt is made to carry out a cohydrolysis condensation reaction by batch-mixing 0 with 0, the hydrolysis of ethyl orthosilicate under the condition without a condensation catalyst causes a significant delay which requires several days. Of course S52
The hydrolysis of 0 is also slow. When a condensation catalyst is added, the hydrolysis of S520 is promoted and it hydrolyzes in several hours, but again, about 40% of the charge of ethyl orthosilicate remains after 3 days. It is unclear why such a large reaction delay occurs. In view of such a fact, in the present invention, ethyl orthosilicate is hydrolyzed with a specified amount of water in the presence of an acid catalyst and then a specified mole of S710 is added to cause a cohydrolysis condensation reaction.
Further, a condensation catalyst and a specified mole of S520 are added to cause a cohydrolysis condensation reaction. According to such a sequential three-step hydrolysis condensation reaction, the reaction can be completed in 3 to 5 hours at room temperature. Alternatively, ethyl orthosilicate is hydrolyzed with a specified amount of water in the presence of an acid catalyst, followed by condensation catalyst and specified moles of S710 and S520.
Is added to cause a cohydrolysis condensation reaction. According to this two-step hydrolysis-condensation reaction, the reaction can be completed within one day at room temperature. Therefore, it is expected that the structural morphology of the polymer in the sequential three-step hydrolysis condensation method or the two-step hydrolysis condensation reaction method will be a block copolymer.

Further, according to the present invention, a novel compound having a silanol group which is stable at room temperature in an organopolysiloxane which has been subjected to a co-hydrolysis condensation reaction, and which has an epoxy oxygen amount corresponding to a charged mole and a methacrylate equivalent to a charged mole is isolated. I succeeded. The organic solvent used for isolation is a hydrophilic solvent at a low temperature,
Distill off at moderate temperature as lipophilic solvents and water azeotropes of these solvents. Bath temperature 140-1 to remove remaining water
Heat dry at 50 ° C.

To measure the solubility of the organopolysiloxane oil obtained in the present invention, 100 mg of the silicone oil sample of the present invention was placed in a glass sample tube and 1 m
It was carried out by the method of adding 1 of each solvent and observing the solubility by visual observation. The results were displayed in 5 grades: easily soluble, soluble, slightly soluble (slightly cloudy), slightly soluble (white cloudy), and insoluble. The organopolysiloxane oil according to the present invention is soluble in many solvents such as toluene and alcohol. This property is a property that methyl silicone oil does not have.

It can be confirmed that the organopolysiloxane compound of the present invention is generally a compound represented by the above general formula by means of the following (a) to (d). (A) Analysis of infrared absorption spectrum (IR) Characteristic absorption of Si—OH around 3450 cm ⁻¹ , 300
Several absorptions based on CH bonds near 0 ^{-1 to} 2900 ^-1 ,
Broad absorption of Si—O—Si around 1100 ^{−1 to} 1000 ⁻¹ appears. 3450 cm ^-1 absorbance of the absorption peak and 2940 cm ^-1 vicinity of the absorption peak in the vicinity (log I
_{The 0} / I) ratio is an index of the relative value of the silanol group content rate. That is, if this value is 1.0 or less, it is an oil having a silanol group that is stable at room temperature. This value is 1.0
The above is an organopolysiloxane polymer that exhibits a resin-state solid upon heating at several tens of degrees Celsius. (B) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR) The number and bonding mode of hydrogen atoms in the organopolysiloxane compound of the present invention, and (Si) -OH depending on deuterium substitution.
It is possible to know the number of (Si) -OH from the ratio of hydrogen atoms. The relationship between the structural formula and the signal of the compound obtained in Example 1 described later is as shown in Chemical Formula 8 below and Table 1.

[0016]

[Chemical 8]

[0017]

[Table 1]

(C) Determination of the amount of epoxy oxygen The amount of oxirane oxygen is determined by the titration method of HBr-acetic acid. (D) Carbon and hydrogen (CH) elemental analysis The carbon and hydrogen content can be known by the micro elemental analysis method.

Viscosity data was measured using a rotational viscometer'VISCONIC 'manufactured by Tokyo Keiki Co., Ltd. at a constant temperature of 25 ° C. In the organopolysiloxanes of Examples 1 to 3 of the present invention, the viscosity was changed proportionally to the sum of the number of moles of orthoethyl silicate + S710 in the range of about 500 cp to 8000 cp. That is, the higher the sum of the mole numbers of orthoethyl silicate + S710, the higher the viscosity. The opposite relationship is the infrared absorption (I
R), ie 345 based on silanols
1720 based on 0 cm ^-1 absorption peak and C = CCOO-
When the ratio of both peaks is taken as the log I ₀ / I absorptance for the intensity of the cm ⁻¹ absorption peak and the relationship with the molar ratio is plotted, the relative silanol amount decreases as the sum of ethyl orthosilicate + S710 increases. Originally, the ethyl orthosilicate component having a three-dimensional structure and the S710 component are increased, and the S520 component, which is a linear polymer component, is relatively decreased. Therefore, the viscosity should be increased and the silanol group should be increased. . However, for some reason, when the relative molar ratio of S520 is 67% or more, an increase in silanol groups and gelation occur. The cause of this is unknown. The number of silanol groups x + y in the NMR measurement result is 2.0 or less.

In the production method by the sequential three-step hydrolysis condensation reaction method or the two-step hydrolysis condensation reaction method of the present invention,
GC by the hydrolysis reaction of the first stage orthoethyl silicate alone
Since neither monomer nor eugomer was detected in the measurement, it is presumed that at least a pentamer or higher oligomer block was formed. From the above viscosity and silanol behavior, it is considered to be a block-like copolymer in the final reaction in the sequential three-step method or the two-step method.

[0021]

The organopolysiloxane of the present invention has a silanol group which is stable at room temperature in the polymer, tetraalkoxysilane and 3-glycidoxypropylalkyldialkoxysilane, as demonstrated in the examples described later. Multifunctional reaction of 3-methacryloxypropyltrialkoxysilane by sequential three-step hydrolysis condensation reaction method or two-step hydrolysis condensation reaction method and having an epoxy group and a methacryloxy group which are organic functional groups of the starting material. It is a polyorganosiloxane. And, the ratio of these two organic functional groups can be changed quite freely by the ratio of the charged raw materials. In the polyorganosiloxane of the present invention, most methyl-based polysiloxanes do not dissolve or have an affinity for organic solvents and organic resins, whereas the organopolysiloxane of the present invention dissolves in many kinds of organic solvents. It also has an affinity for many kinds of organic resins. Due to these characteristics, it can be used not only as a modified silicone oil but also as a release agent, silicone for release paper, silicone for personal care, paint additive, silicone adhesive,
It is a useful compound that can be applied to a wide range of applications such as adhesive sealing materials and modified silicone silants. Further, in a polymer alloy or blend composed of two or more kinds of polymers, it is expected to act on the interface between different kinds of resins to facilitate kneading, and coupling between polymers. The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Synthesis of silanol group-containing polysiloxane-3-methacryloxypropylpolysiloxane-3-glycidoxypropylmethylpolysiloxane copolymer oil Ethyl orthosilicate / S710 / S520 = 1/2/2 (mol) Ethyl silicate 52 made by Tama Chemical Co., Ltd. in a 1 L three-necked flask
g, and toluene / methanol = 60 as a reaction solvent
Add 500 ml of / 40 mixed solvent. As a hydrolysis catalyst, hydrochloric acid and a catalytic amount and 76 ml of water having a molar ratio of 3.5 are added, and the mixture is stirred and reacted at room temperature for 30 minutes. The disappearance of the peak of ethyl orthosilicate is confirmed by gas chromatography (GC). Chisso S520 110g and S710 12
4 g, 0.0 of dibutyltin dilaurate as a condensation catalyst
5 g is added, and a hydrolysis-condensation reaction is performed for 3 to 5 hours with stirring at room temperature. The reaction is terminated by confirming the disappearance of S710 and S520 and their oligomer peaks by GC. Methanol and an azeotropic solvent are distilled off under reduced pressure with a vacuum pump and strong stirring at room temperature. The mixture is heated to 40 ° C. or lower to increase the degree of reduced pressure, and water containing residual toluene and hydrochloric acid is distilled off under strong stirring. The oil thus obtained weighed 119 g and had a theoretical yield of 9
8%, colorless and transparent viscous liquid, containing oxirane oxygen 4.1
%, C44.1%, and H7.0%. Oxirane oxygen 4.2 calculated by empirical formula including the following hypothetical calculation
%, C44.5%, H6.9%, O29.9%, Si1
It was in good agreement with 8.6%. The viscosity was 7,960 centipoise (25 ° C). IR chart and NMR chart are shown in FIGS. 1 and 2. The structural formula of the silicone oil obtained from the analysis of IR and NMR results is as shown in Chemical formula 9 below, and the rational formula is C ₂₈ H _51.8 O _14.1 Si ₅ , where x +
2y = 1.77 and x and y are calculated to be 0.59 respectively.

[0023]

[Chemical 9]

[0024] The absorbance of the absorption peak and 1720 cm ^-1 vicinity of the absorption peak around 3450 cm ^-1 (log I
_{The 0} / I) ratio was 0.37.

Example 2 Synthesis of silanol group-containing polysiloxane-3-methacryloxypropylpolysiloxane-3-glycidoxypropylmethylpolysiloxane copolymer oil Ethyl orthosilicate / S710 / S520 = 1/2/4 (mol) It is produced by a two-step hydrolysis condensation reaction as in Example 1.
However, the charged amount was 1.04 g of ethyl orthosilicate, 50 ml of mixed solvent of toluene / methanol = 60/40, 2.20 ml of 1/10 normal hydrochloric acid solution (first stage), 4.4 of S520.
0g and 2.48g of S710 and 0.01g of dibutyltin dilaurate (second stage) 5 hours later, S520 by GC
And the disappearance of the monomer and oligomer of S710 is confirmed. After completion of the reaction, the solvent is volatilized with a dry nitrogen stream, and then the dried filter paper is made to absorb the separated polka dots containing hydrochloric acid. Residual toluene is volatilized with a hot air of a hair drier so as not to give off odor, and then placed in a 120 ° C. drying oven for 1 hour to dry. The silicone oil thus obtained was a colorless transparent viscous liquid. The viscosity was 770 centipoise (25 ° C). IR chart and NMR chart are shown in FIGS. 3 and 4. The proof that the signal at 1.67 ppm overlapping with the methylene group in NMR was based on OH was confirmed by the deuterium substitution shown in FIG. IR
And the structural formula of the silicone oil obtained from the analysis of the results of NMR is Formula 1 and n = 1, m = 2, l = 4, x + 2y =
It was 2.50. Further, the absorbance of the absorption peak and 1720 cm ^-1 vicinity of the absorption peak near 3450cm ^-1 (logI ₀ / I) ratio was 0.69.

Example 3 Synthesis of silanol group-containing polysiloxane-3-methacryloxypropylpolysiloxane-3-glycidoxypropylmethylpolysiloxane copolymer oil Ethyl orthosilicate / S710 / S520 = 1/1/4 (mol) The basic operation is the same as in Example 2, but the reaction system was a sequential three-stage hydrolysis condensation reaction. The charged amount is 1.04 g of ethyl orthosilicate, 50 ml of a mixed solvent of toluene / methanol = 60/40, and a 1 / 10N hydrochloric acid solution of 1.89 m.
l (1st stage), after 20 minutes, confirmed disappearance of ethyl orthosilicate monomer and oligomer by GC. 30 minutes after adding 1.24 g of S710, the disappearance of the monomer and oligomer of S710 was confirmed by the same GC (second step). 4.40 g of S520 and 0.01 g of dibutyltin dilaurate (third stage) were added, and 5 hours later, the disappearance of monomers and oligomers was also confirmed by GC. After completion of the reaction, the solvent is volatilized with a dry nitrogen stream, and then the dried filter paper is made to absorb the separated polka dots containing hydrochloric acid. Residual toluene is volatilized with a hot air of a hair drier so as not to give off odor, and then placed in a 120 ° C. drying oven for 1 hour to dry. The silicone oil thus obtained was a colorless transparent viscous liquid. The viscosity was 670 centipoise (25 ° C). IR chart and NMR chart are shown in FIG. 6 and FIG.
It was shown to. In addition, 1.67 which overlapped with a methylene group in NMR
The proof that the ppm signal was based on OH was confirmed by the deuterium substitution shown in FIG. The structural formula of the silicone oil obtained by the analysis of the results of IR and NMR is Formula 1 and n =
1, m = 1, l = 4, and x + y = 1.98. In addition, the absorption peak near 3450 cm ^-1 and 1720
Absorbance with absorption peak near cm ^-1 (log I ₀ / I)
The ratio was 0.68.

[Brief description of drawings]

 1 to 9 are explanatory views of an embodiment of the present invention.

1 is an IR chart of the compound of Example 1. FIG.

2 is an NMR chart of the compound of Example 1. FIG.

FIG. 3 is an IR chart of the compound of Example 2.

4 is an NMR chart of the compound of Example 2. FIG.

5 is an NMR chart of the compound of Example 2. FIG.

6 is an IR chart of the compound of Example 3. FIG.

7 is an NMR chart of the compound of Example 3. FIG.

8 is an NMR chart of the compound of Example 3. FIG.

Claims (5)

[Claims] 1. A tetraalkoxysilane represented by the general formula Si (OR ¹ ) ₄ and a general formula 1 3-glycidoxypropylalkyldialkoxysilane represented by the following general formula 2 The co-hydrolysis and condensation reaction of 3-methacryloxypropyltrialkoxysilane represented by the formula (3) with an acid catalyst in a mixed solvent containing an organotin condensation catalyst with 3 to 4 times the molar amount of water of the silane is carried out. A method for producing a novel polysiloxane having both a silanol group and a 3-glycidoxypropyl group and a 3-methacryloxypropyl group which are stable at room temperature.
Here, as the alkyl group R, a C _{1 to} C ₈ saturated hydrocarbon group or an alkenyl group is used, and particularly preferably a C _{1 to} C ₂ saturated hydrocarbon group or a vinyl group is used. The alkoxy groups R ¹ , R ² and R ³ are made from C _{1 to} C ₈ saturated alcohols. 2. The following formula 3 below. Organopolysiloxane that is in an oil state at room temperature. However, the compound of formula 1 in which the silanol group x is in the range of 2.0 to 0.5, the polymer end group is a silanol group, and m, n, and l are each a positive integer of 3 or more. 3. The method according to claim 1, wherein tetraalkoxysilane is used in a catalytic amount prior to the cohydrolysis and condensation reaction of tetraalkoxysilane / 3-methacryloxypropyltrialkoxysilane / 3-glycidoxypropylalkyldialkoxysilane. Acid catalyst and total silane moles 3-4
After hydrolyzing by adding twice the molar amount of water, a predetermined molar ratio of 3
-Sequential three-stage hydrolysis in which methacryloxypropyltrialkoxysilane is added for hydrolysis, and then a catalytic amount of an organotin catalyst and a predetermined molar ratio of 3-glycidoxypropylalkyldialkoxysilane are added for cohydrolysis condensation reaction. A method for producing the organopolysiloxane compound by a decomposition condensation method. 4. The method according to claim 1, wherein tetraalkoxysilane is used in a catalytic amount prior to the cohydrolysis and condensation reaction of tetraalkoxysilane / 3-methacryloxypropyltrialkoxysilane / 3-glycidoxypropylalkyldialkoxysilane. Acid catalyst and total silane moles 3-4
After hydrolyzing by adding twice the molar amount of water, a catalytic amount of an organotin catalyst and a predetermined molar ratio of 3-methacryloxypropyltrialkoxysilane and 3-glycidoxypropylalkyldialkoxysilane are added to carry out a cohydrolysis condensation reaction. A method for producing the above organopolysiloxane compound by a two-step hydrolysis-condensation method. 5. The tetraalkoxysilane is tetramethoxysilane or tetraethoxasilane, and 3-
Methacryloxypropyltrialkoxysilane is 3-
Either methacryloxypropyltrimethoxysilane or 3-methacryloxypropyltris (methoxyethoxy) silane, wherein 3-glycidoxypropyldialkoxysilane is 3-glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropyl Methyldiethoxysilane ,,, and
The method for producing the compound according to claim 1, wherein the compound is any one of the three silanes.