KR20080087741A - Novel silicon compound, material thereof and method for producing the same - Google Patents

Abstract

A novel curable silicone compound is provided to show excellent compatibility to other resins and excellent curability. A method for preparing the silicone compound is provided to obtain the curable silicone compound within a short time at low cost. A curable silicone compound is represented by a formula(1) of [RSiO3/2]n[R^1(CH3)2SiO12]m, wherein each R and R^1 is independently H, C6-10 aryl containing group, C1-10 linear or branched alkyl, C4-10 cycloalkyl, C2-3 alkenyl or a group represented by a formula(2), (3) or (4)(wherein I is an integer from 1 to 3 and R^2 is H or methyl); provided that C2-3 alkenyl and at least two of one curable group of the formula(2), (3) or (4) are included in one molecule of the formula(1) and at least one of the R is the curable group; n is an integer from 6-20; m is an integer from 1-6; n/m is 1-10; Mw is 500-5,000; and Mw/Mn is 1.0-1.5. A method for preparing the curable silicone compound comprises the steps of: (a) hydrolyzing RSiX3(wherein R is same as defined above and X is a hydrolyzable group) in the presence of a basic catalyst, where a mol ratio of the RSiX3 and the basic catalyst is 4-10:1, and in a mixture solvent of a polar solvent and a non-polar solvent to prepare a silsesquioxane compound including hydroxyl of [RSiO3/2]n[HO1/2]m(wherein R, n and m are same as defined above); and (b) reacting the silsesquioxane with monochlorosilane.

Description

Novel silicon compound and its raw material and manufacturing method of new silicon compound {NOVEL SILICON COMPOUND, MATERIAL THEREOF AND METHOD FOR PRODUCING THE SAME}

The present invention relates to a novel curable silicone compound, a raw material thereof, and a method for producing a curable silicone compound. Specifically, the present invention has a plurality of curable functional groups, and is suitable for use as an electronic material, an optical material, an electron optical material, and the like. A novel curable silicone compound and its raw material, which can be used as an additive for imparting flame retardancy, heat resistance, electrical insulation, surface properties, hardness, optical strength, chemical resistance, transparency, etc. to a material, and to obtain this silicone compound It relates to a manufacturing method.

As for the general formula [RSiO _{3/2] n} silsesquioxane (silsesquioxane) represented by is, many studies have been made so far. Chem. Rev. In 1995, 95 and 1409, a general description of silsesquioxanes by Baney et al. Describes the amorphous structures that do not exhibit any structure other than the silsesquioxanes of ladder structure, fully condensed structure and incomplete condensed structure. Eggplant silsesquioxane and the like have been reported. Furthermore, according to Organometallics, 1991, 10, 2556, silsesquioxanes having an incomplete condensation structure can be obtained by hydrolyzing cyclopentyltrichlorosilane or cyclohexyltrichlorosilane in acetone. Here, the silsesquioxane of a fully condensed structure is composed of a plurality of annular structures, and means to form a closed space (so-called basket-type siloxane resin), and a silsesqui of an incomplete condensed structure. An oxane means that at least 1 or more places of a complete condensation structure are not blocked, and the space is not sealed.

For silsesquioxanes having such a fully condensed or incompletely condensed structure, for example, modifiers of thermoplastic resins, flame retardants of polymer materials, heat resistance, weather resistance, electrical insulation, surface properties, hardness, and mechanical strength And additives for improving chemical resistance and the like. In recent years, in order to use as a building block of a polymer, the method of introduce | transducing various functional groups in order to provide compatibility and polymerizability with other resin is examined. Generally, silsesquioxanes having a silanol group (Si-OH) at the terminal are well known, and new silsesquioxanes are induced by using the reactivity of silanol. In addition, an incomplete condensed structure silsesquioxane having Si-ONa as a reactive active group is synthesized by hydrolyzing a silane compound having a trifunctional hydrolyzable group in the presence of a monovalent alkali metal hydroxide in an organic solvent. The derivative of silsesquioxane is proposed by making chlorosilane which has a functional group react (refer patent document 1 and 2).

However, in general, derivatives of silsesquioxane are poor in compatibility with other resins and cannot be mixed uniformly, or they whiten when they are coated, or bleed out from the coating. There is a problem such as a limitation. In addition, in order to use a conventional derivative of silsesquioxane as a building block of a polymer, such as when using it as an electronic material or an optical material, it is expected that the derivative itself has curability, but as far as the inventors know, There are no reported cases with sufficient features.

Patent Document 1 WO2002 / 094839 Pamphlet

Patent Document 2: WO2003 / 024870 Brochure

Thus, the present inventors have studied diligently to solve the problems of conventional silsesquioxane derivatives related to compatibility with other resins, curability, etc., and as a result, molecular weight distribution is controlled and a plurality of predetermined curable functional groups are obtained. The eggplant succeeded in synthesizing the hydroxyl group-containing silsesquioxane, and found that the curable silicone compound obtained by using the hydroxyl group-containing silsesquioxane as a raw material can solve all these problems, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a novel curable silicone compound having excellent compatibility with other resins and excellent curability.

Another object of the present invention is to provide a hydroxyl group-containing silsesquioxane compound serving as a raw material for obtaining the curable silicone compound.

Further, another object of the present invention is to provide a method for producing a curable silicone compound in which the curable silicone compound can be obtained in a short time and at low cost.

That is, the present invention is the following general formula (1)

_{[RSiO 3/2] n [} R 1 (CH 3) 2 SiO 1/2] m

It is a curable silicone compound represented by.

[Where R and R ¹ are a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or Formulas (2) to (4)

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and in R and R ¹ , each of the substituents may be the same as or different from each other. In 1 molecule represented by 1), it has two or more hardenable functional groups selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4), and at least 1 of R is the said hardenable functional group. . In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.]

Moreover, this invention is following General formula (5)

_{[RSiO 3/2] n [} HO 1/2] m

It is a hydroxyl group containing silsesquioxane compound represented by the.

[Wherein R is a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2 ) To (4)

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and R may be the same or different from each other, but R in one molecule represented by the general formula (5) At least 1 of is a hardenable functional group selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4). In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.]

Moreover, this invention is a manufacturing method of said curable silicone compound, General formula (6)

RSiX ₃

[Wherein R is a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2 ) To (4)

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), X represents a hydrolyzable group, and is at least one silicon compound represented by at least one kind. One or more silicon compounds in which R of the silicon compound of R is an alkenyl group having 2 to 3 carbon atoms and any curable functional group selected from the group consisting of the formulas (2) to (4) include RSiX ₃ : basic catalyst = 4 to In the presence of a basic catalyst in the range of 10 mol: 1 mol, hydrolyzing in a mixed solvent of a polar solvent and a nonpolar solvent, the following general formula (5)

_{[RSiO 3/2] n [} HO 1/2] m

(Wherein R is the same as above) n represents an integer of 6 to 20, m represents an integer of 1 to 6, and n / m is in the range of 1 to 10. After producing | generating, it is made to react with monochlorosilane, The manufacturing method of the curable silicone compound characterized by the above-mentioned.

In the method for producing a curable silicone compound in the present invention, the silicon compound represented by the general formula (6) is first hydrolyzed in the presence of a predetermined solvent and a basic catalyst, and the hydroxyl group content represented by the general formula (5) A silsesquioxane compound is obtained and the hydroxyl group-containing silsesquioxane compound is reacted with monochlorosilanes to obtain a curable silicone compound of the general formula (1).

Here, with respect to each R of the silicon compound in the general formula (6) and the general formula (7) described later, specific examples of substituents other than hydrogen atoms include vinyl, allyl and the like as alkenyl having 2 to 3 carbon atoms. Can be mentioned. Examples of linear or branched alkyl groups of 1 to 10 include methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl , Octyl, 2,2,4-trimethylpentyl, nonyl, decyl, and the like. Cyclopentyl, cyclohexyl, etc. are mentioned as a C4-C10 cycloalkyl group. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-vinylphenyl, 4- (1-methylvinyl) phenyl, 4- (3-butenyl) phenyl, naphthyl, and the like. Can be mentioned. As an example of said Formula (2), methacryloxymethyl, 3-methacryloxypropyl, 3-acryloxypropyl, etc. are mentioned. 3-glycidoxypropyl etc. are mentioned as an example of said Formula (3). As an example of said formula (4), 2- (3, 4- epoxycyclohexyl) ethyl etc. are mentioned. In addition, these functional groups are general and are not limited to these. The curable silicone compound of General formula (1) has at least 2 or more curable functional groups. That is, if the curable silicone compound of General formula (1) consists of 16 silicon, for example, the silicon compound of General formula (6) and (7) so that at least 12.5 mol% or more of all R may be said hardenable functional group. Adjust the dose of

In addition, X in General formula (6) is a hydrolysable group, As an example, a chlorine atom or a C1-C4 alkyloxy group (alkoxyl group) is mentioned. Among these, as an alkoxyl group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, etc. are mentioned. Especially, it is preferable that it is a highly reactive methoxy group.

About the silicon compound represented by General formula (6), at least 1 type of silicon compound R is any hardenable functional group selected from the group which consists of a C2-C3 alkenyl group and following formula (2)-(4) Use at least one silicon compound.

Further, for the amount of the basic catalyst used in the hydrolysis reaction of the silicon compound represented by the general formula (6), a silicon compound (RSiX ₃₎ the ratio of the basic catalyst, RSiX _3: = 4 to 10 mol basic catalyst: Make it 1 mole. When the usage-amount of a basic catalyst is in this range, generation | occurrence | production of a high molecular weight silsesquioxane compound will be prevented and the hydroxyl group containing silsesquioxane compound of the incomplete condensation type | mold described below can be obtained. When the amount of the basic catalyst used is less than the above range, the condensation reaction is accelerated to cause gelation. On the contrary, when the amount of the basic catalyst is used, the condensation reaction is suppressed, and the reaction is not completed with a large amount of unreacted silanol groups remaining.

About the basic catalyst used when hydrolyzing the silicon compound represented by General formula (6), it is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyl trimethylammonium, for example. Ammonium hydroxide salts, such as hydroxide and benzyl triethylammonium hydroxide, are mentioned. Among them, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. On the other hand, a basic catalyst is normally used as aqueous solution.

In addition, it is preferable to perform the organic solvent used at the time of hydrolysis using the biphasic system of a polar solvent and a nonpolar solvent from a reaction rate control viewpoint. Among these, alcohols such as methanol, ethanol and 2-propanol can be cited if specific examples are given for the polar solvent. If a specific example is given about a nonpolar solvent, toluene, xylene, benzene, etc. are mentioned. Among these, 2-propanol and toluene are preferable. About the volume ratio of a polar solvent and a nonpolar solvent, it is preferable that it is polar solvent / nonpolar solvent = 1/5-5/1, and 1/2 is more preferable.

About reaction conditions of a hydrolysis reaction, 0-60 degreeC is preferable and 20-40 degreeC of reaction temperature is more preferable. When the reaction temperature is lower than 0 ° C., the reaction rate is slowed down and the hydrolyzable groups remain in the unreacted state, which consumes a lot of reaction time. On the other hand, when the reaction temperature is higher than 60 ° C., the condensation reaction proceeds too fast. As a result, the high molecular weight of the hydrolysis product is promoted. Moreover, 2 hours or more of reaction time is preferable. If the reaction time does not satisfy 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.

Although the presence of water is essential in the said hydrolysis reaction, this may be supplied from the aqueous solution of a basic catalyst, and you may add it as water separately. The amount of water is more than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. If it is less than this range, the hydrolyzable group remains in an unreacted state. On the contrary, if the amount is increased, the reaction proceeds faster and causes gelation.

After the completion of the hydrolysis reaction, for example, the solution is neutralized with a weakly acidic aqueous solution, washed with saline, or the like, and sufficiently removed the basic catalyst, water, and other impurities in the system, followed by drying with anhydrous magnesium sulfate. It can dry and a hydroxyl-containing silsesquioxane compound can be collect | recovered by using means, such as concentrated under reduced pressure. At this time, in order to completely neutralize, it is preferable to add an weakly acidic aqueous solution excessively, specifically 1.0-1.5 times with respect to the molar ratio of a basic catalyst, and 1.25 times are more preferable. If a small amount of basic catalyst remains, the remaining silanol groups react to form a high molecular weight. As the weakly acidic aqueous solution, dilute sulfate aqueous solution, dilute hydrochloric acid aqueous solution, citric acid aqueous solution, acetic acid aqueous solution, ammonium chloride aqueous solution, malic acid aqueous solution, phosphoric acid aqueous solution, oxalic acid aqueous solution, and the like can be used.

The hydroxyl-containing silsesquioxane compound obtained above can be represented by following General formula (5).

_{[RSiO 3/2] n [} HO 1/2] m

[Wherein R is a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2 ) To (4)

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and R may be the same or different from each other, but R in one molecule represented by the general formula (5) At least 1 of is a hardenable functional group selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4). In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.]

The hydroxyl group-containing silsesquioxane compound represented by the general formula (5) is an incompletely condensed silsesquioxane because it is considered to have some silanol groups at the terminals and not form a completely closed space.

And monochlorosilane is made to react with the hydroxyl-containing silsesquioxane compound represented by General formula (5). Monochlorosilane used at this time, Preferably it is following General formula (7)

It is good to be indicated by. Provided that R ¹ is an aryl containing group having 6 to 10 carbon atoms, a straight or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2), ( 3), (4)

(Wherein I is an integer of 1 to 3, and R ² represents a hydrogen atom or a methyl group).

Specific examples of the monochlorosilane represented by the general formula (7) include dimethylvinylchlorosilane, dimethylallylchlorosilane, trimethylchlorosilane, dimethylethylchlorosilane, dimethylpropylchlorosilane, dimethyl-1-methylethylchlorosilane, Dimethylbutylchlorosilane, dimethyl-2-methylpropylchlorosilane, dimethyl-1,1-dimethylethylchlorosilane, dimethylpentylchlorosilane, dimethylhexylchlorosilane, dimethyl-1,1,2-trimethylpropylchlorosilane, dimethylheptyl Chlorosilane, Dimethyloctylchlorosilane, Dimethyl-2,2,4-trimethylpentylchlorosilane, Dimethylnonylchlorosilane, Dimethyldecylchlorosilane, Dimethylcyclopentylchlorosilane, Dimethylcyclohexylchlorosilane, Dimethylphenylchlorosilane, Dimethyl- 4-methylphenylchlorosilane, dimethyl-4-methoxyphenylchlorosilane, dimethyl-4-vinylphenylchlorosilane, dimethyl-4- (1-methylvinyl) phenylchlorosilane, dimethyl-4 -(3-butenyl) phenylchlorosilane, dimethylnaphthylchlorosilane, dimethyl methacryloxymethylchlorosilane, dimethyl-3-methacryloxypropylchlorosilane, dimethyl-3-acryloxypropylchlorosilane, dimethyl-3- Glycidoxy propylchlorosilane, dimethyl-2- (3,4-epoxycyclohexyl) ethylchlorosilane, dimethylchlorosilane, etc. can be illustrated. Here, the curable silicone compound of General formula (1) has at least 2 or more curable functional groups. For example, if the curable silicone compound of General formula (1) consists of 16 silicon, at least 12.5 mol% of all R and R <^1> is a C2-C3 alkenyl group and Formula (2)-(4). The injection amount of the silicon compounds of the general formulas (6) and (7) is adjusted to be any curable functional group selected from the group consisting of. That is, if the formula (6) and (7) in the silicon compound, each of the substituents R and R ¹ as required to use a different mixture of two or more.

In addition, the reaction of the hydroxyl group-containing silsesquioxane compound of the general formula (5) with the monochlorosilane is preferably performed under basic conditions. There is no restriction | limiting in particular about basic conditions, A well-known reaction method can be used, For example, tetrahydrofuran is used as an organic solvent, The hydroxyl group containing silsesqui of General formula (5) in presence of triethylamine as a base. An oxane compound and monochlorosilane may be made to react, or a hydroxyl group containing silsesquioxane compound and a monochlorosilane may be made to react using a pyridine as a solvent and a base.

Regarding the reaction conditions of the hydroxyl group-containing silsesquioxane compound and monochlorosilane, for example, the hydroxyl group-containing silsesquioxane compound is dissolved in 0.1 to 2.0 M of tetrahydrofuran, and at least one equivalent of triethyl to the hydroxyl group. A monochlorosilane was used at room temperature under an inert gas atmosphere such as nitrogen, or a mixed solution obtained by using an amine or a hydroxyl group-containing silsesquioxane dissolved in 0.1 to 2.0 M pyridine with respect to the hydroxyl group-containing silsesquioxane. It is dripped over time, and after that, stirring is performed at room temperature for 2 hours or more. At this time, when reaction time is short, reaction may not be completed. After completion | finish of reaction, toluene and water are added, the curable silicone compound of General formula (1) is melt | dissolved in toluene, and the salt produced | generated by reaction is dissolved in a water layer and removed. The organic layer is dried using a drying agent such as magnesium sulfate, and the curable silicone compound of the general formula (1) can be obtained by removing the used base and the solvent by vacuum concentration.

About the amount of monochlorosilane used, for example, in the case of the monochlorosilane represented by General formula (7), the amount sufficient to capture the silanol group of the hydroxyl group containing silsesquioxane compound represented by General formula (5) Preferably, it is 1.0-1.5 times of theoretical amount. There is no problem even if it is added in excess, but when untreated, if unreacted monochlorosilane remains, disiloxane will produce | generate, and purification will become difficult. On the other hand, disiloxane produced during the post-treatment can be removed by concentration under reduced pressure as long as the boiling point is low. What is necessary is just to carry out reaction of theoretically high boiling point, and to not produce unreacted monochlorosilane and to not produce a disiloxane.

And the curable silicone compound represented by following General formula (1) can be obtained by reaction of the said hydroxyl-containing silsesquioxane compound and monochlorosilane.

_{[RSiO 3/2] n [} R 1 (CH 3) 2 SiO 1/2] m

[Where R and R ¹ are a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms or the above formula (2) to (4) (wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and in R and R ¹ , each substituent is the same or different. Although it may be sufficient, at least one molecule | numerator represented by General formula (1) has 2 or more of any hardenable functional groups selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4), and at least in R One is said curable functional group. In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.] When not used as a building block of a polymer unless two or more curable functional groups are contained in one molecule, sufficient network cannot be expanded by crosslinking. Because it is not desirable.

Since the silicone compound represented by General formula (1) is derived from the incomplete condensation silsesquioxane represented by General formula (5), it has the structure similar to the basket type siloxane. That is, the silicone compound represented by General formula (1) has the characteristic of the basket-type siloxane, and is excellent in compatibility with other resin.

In addition, since the curable silicone compound of General formula (1) is synthesize | combined from the hydroxyl-containing silsesquioxane compound of the said General formula (5) as a raw material, molecular weight distribution is controlled and Mw of the obtained silicone compound is 500-5,000, Preferably it is 500-2,000 and Mw / Mn which shows distribution of molecular weight exists in the range of 1.0-1.5 (Mw: weight average molecular weight, Mn: number average molecular weight).

According to this invention, the curable silicone compound containing two or more curable functional groups can be obtained in high yield. In addition, this curable silicone compound is compatible with silicone curable resins and organic curable resins, and can be widely used as a raw material for hydrosilylation and radically polymerizable resin compositions. Moreover, the flame retardancy, heat resistance, electrical insulation, It can also be used as an additive for improving surface characteristics, hardness, optical strength, chemical resistance and the like.

In addition, since the hydroxyl group-containing silsesquioxane compound in the present invention has a highly reactive hydroxyl group, it is possible to derive a useful novel curable silicone compound having the above characteristics and to be used as a means for synthesizing yields with good yield. have.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example and a comparative example. In addition, the scope of the present invention is not limited by these Examples.

<Example 1>

In a reaction vessel equipped with a stirrer and a dropping lot, 205 mL of 2-propanol (IPA) and 411 mL of toluene were added as a solvent, and 54.9 g (156 mmol) of 26% aqueous tetramethylammonium hydroxide (TMAH solution) was added as a basic catalyst. It was. Furthermore, IPA 136 mL, trimethoxymethylsilane (Toray Dow Corning Silicone Co., Ltd. SZ-6070) 46.6 g (342 mmol), and trimethoxy vinylsilane (Shin-Etsu Kagaku Kogyo Co., Ltd. KBM) were added to the dropping lot. 50.7 g (342 mmol) was added and the reaction vessel was added dropwise at room temperature over 3 hours with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, 10% aqueous citric acid solution was added, followed by stirring for 2 hours to neutralize. The aqueous layer was extracted with toluene, the organic layer was washed twice with saturated brine, and the organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 46.1 g (yield 86%) of a hydrolyzate (hydroxyl-containing silsesquioxane compound). This hydroxyl-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.

A hydroxyl group obtained in the above-containing silsesquioxane compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [HO 1/2] is shown in Figure 1 the results of the GPC measurement of _m. From FIG. 1, Mw was 1188 and Mw / Mn was 1.326.

Also, shown in the hydroxyl group-containing silsesquioxane compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [HO 1/2] 2 also the result of measuring the ¹ H-NMR of the _m . 2, the peak of vinyl group, methyl group, and silanol group was confirmed. _{[CH 3 SiO 3/2]} k: [CH 2 = CHSiO 3/2] j: [HO 1/2] bar for comparing The integration of the _m, 2.989: 3.000: 1.067, and the functional group ratio is 0.966: 1.000 : 1.067. Therefore, n is the sum of k and j, so n / m = 1.843. In addition, the ratio of k: j: m derived from Mw = 1188 and n / m = 1.84 is calculated as 7.479: 7.753: 8.226, which is a condensate having Si of 15, including 8 hydroxyl groups and 8 curable functional groups. Was confirmed.

Next, 36.3 g (31 mmol) of hydroxyl group-containing silsesquioxane compounds and 207 mL of pyridine were measured and substituted in a reaction vessel equipped with a stirrer and a dropping lot. 36.0 g (331 mmol) of trimethylchlorosilane (PRX-24 manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to the dropping lot, and the mixture was added dropwise at room temperature over 1 hour. It stirred at room temperature for 2 hours after completion | finish of dripping. After stirring for 2 hours, 207 mL of toluene and 207 mL of purified water were added to separate an organic layer and an aqueous layer. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 45.7 g (97% yield) of the curable silicone compound. This curable silicone compound was a colorless liquid soluble in various organic solvents.

The curable silicone compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [(CH 3) 3 SiO 1/2] is shown in Figure 3 the results of the GPC measurement of _m. From the measurement result of GPC (FIG. 3), Mw = 1520 and Mw / Mn = 1.270.

The curable silicone compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [(CH 3) 3 SiO 1/2] is shown in Figure 4 the result of measuring the ¹ H-NMR of _m. And 8.699, k: from Figure _{4 [CH 2 = CHSiO 3/} 2] j: [CH 3 SiO 3/2] k + [(CH 3) 3 SiO 1/2] m ever secrete a bar 3.000 compared to a: The integral ratio of j: m was 2.989: 3.000: 5.801 and the ratio of k: j: m was 0.966: 1.000: 0.645. Therefore, n is the sum of k and j, so n / m = 3.05. On the other hand, the number of hydroxyl groups of the hydroxyl group-containing silsesquioxane compound and the number of trimethylsilyl groups of the curable silicone compound is considered to be due to partial condensation of silanol groups in the presence of pyridine.

Moreover, the ratio of k: j: m derived from Mw = 1520 and n / m = 3.05 was calculated to be 7.469: 7.743: 5.020, and it was confirmed that Si was a condensate having 20 and contained eight curable functional groups.

<Example 2>

To a reaction vessel equipped with a stirrer and a dropping lot, 60 mL of 2-propanol (IPA) and 120 mL of toluene were added as a solvent, and 16.1 g (45.9 mmol) of a 26% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) was added as a basic catalyst. It was. Further, 40 mL of IPA and 29.6 g (200 mmol) of trimethoxy vinyl silane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were added to the dropping lot, and the reaction vessel was added dropwise at room temperature over 3 hours with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, 10% aqueous citric acid solution was added and stirred for 2 hours to neutralize. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 14.3 g (92% recovery) of a hydrolyzate (hydroxyl-containing silsesquioxane compound). This hydroxyl-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.

The hydroxyl group-containing silsesquioxane compound _{[CH 2 = CHSiO 3/2} ] n [HO 1/2] is shown in Figure 5 the results of the GPC measurement of _m. It was Mw = 850 and Mw / Mn = 1.162 from the GPC measurement result (FIG. 5).

Next, 10.8 g (12.7 mmol) of hydroxyl group-containing silsesquioxane compound and 82.5 mL of pyridine were measured and nitrogen-substituted in a reaction vessel equipped with a stirrer and a dropping lot. 20.7 g (172 mmol) of dimethylvinylchlorosilane (made by Toray Dow Corning Silicone Co., Ltd.) was put into the dripping lot, and it was dripped over 1 hour at room temperature. It stirred at room temperature for 2 hours after completion | finish of dripping. After stirring for 2 hours, 82.5 mL of toluene and 82.5 mL of purified water were added to separate an organic layer and an aqueous layer. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to give 14.1 g (recovery rate 90) of a curable silicone compound. This curable silicone compound was a colorless liquid soluble in various organic solvents.

The curable silicone compound _{[CH 2 = CHSiO 3/2} ] n [CH 2 = CH (CH 3) 2 O 1/2] is shown in Figure 6 the results of the GPC measurement of _m. Mw = 1226 and Mw / Mn = 1.133 from the GPC measurement result (FIG. 6).

The curable silicone compound _{[CH 2 = CHSiO 3/2} ] n [CH 2 = CH (CH 3) 2 O 1/2] is shown in Figure 7 the results of measuring the ¹ H-NMR of _m. Fig from _{7 [CH 2 = CHSiO 3/} 2] n: [CH 2 = CH (CH 3) 2 O 1/2] The integration of the bar compared to 11.375 _m: was 6.000. Therefore, the ratio of n: m was 1.000: 0.358 and n / m = 2.79.

In addition, the ratio of n: m derived from Mw = 1226 and n / m = 2.79 was calculated to be 7.114: 2.547, confirming that it is a condensate having Si of 9 and including 9 curable functional groups.

<Example 3>

In a reaction vessel equipped with a stirrer and a dropping lot, 48 mL of 2-propanol (IPA) and 194 mL of toluene were added as a solvent, and 9.6 g (27 mmol) of 26% aqueous tetramethylammonium hydroxide (TMAH aqueous solution) was added as a basic catalyst. It was. Furthermore, IPA 32 mL, trimethoxy vinyl silane (11.9 g (80 mmol) of KBM 1003 by Shin-Etsu Chemical Co., Ltd.), and 3-glycidoxy propyl trimethoxy silane (Shin-Etsu Chemical Co., Ltd.) were added to the dropping lot. 20.0 g (80 mmol) of LS-2940 (manufactured by Kaisha) was added thereto, and the reaction vessel was added dropwise at room temperature over 3 hours while stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, 10% aqueous citric acid solution was added and stirred for 2 hours to neutralize. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 17.8 g (recovery rate 89%) of a hydrolyzate (hydroxyl-containing silsesquioxane compound). This hydroxyl-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.

The hydroxyl group-containing silsesquioxane compound _{[CH 2 (O) CHCH 2} O (CH 2) 3 SiO 3/2] k [CH 2 = CHSiO 3/2] j [HO 1/2] was measured on GPC _m The results are shown in FIG. It was Mw = 1379 and Mw / Mn = 1.282 from the GPC measurement result (FIG. 8).

Next, 10.8 g (8 mmol) of hydroxyl group-containing silsesquioxane compounds and 82 mL of pyridine were measured and nitrogen-substituted in a reaction vessel equipped with a stirrer and a dropping lot. 20.7 g (171 mmol) of dimethylvinylchlorosilane (made by Toray Dow Corning Silicone Co., Ltd.) was put into the dripping lot, and it was dripped at room temperature over 1 hour. It stirred at room temperature for 2 hours after completion | finish of dripping. After stirring for 2 hours, 82 L of toluene and 82 mL of purified water were added to separate an organic layer and an aqueous layer. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off and concentrated to obtain 11.7 g of a curable silicone compound at 91% recovery. This curable silicone compound was a colorless liquid soluble in various organic solvents.

The curable silicone compound _{[CH 2 (O) CHCH 2} O (CH 2) 3 SiO 3/2] k [CH 2 = CHSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] m The result of measuring GPC of is shown in FIG. From the GPC measurement result (FIG. 9), Mw was 1624 and Mw / Mn was 1.293.

Is a ¹ H-NMR of the curable silicone compound _{[CH 2 (O) CHCH 2} OSiO 3/2] k [CH 2 = CHSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] m The measured result is shown in FIG. From Figure _{10 [CH 2 (O) CHCH} 2 CH 2 CH 2 SiO 3/2] k: [CH 2 = CHSiO 3/2] j: of _{[CH 2 = CH (CH 3} ) 2 O 1/2] m The integral ratio was 2.000: 3.000: 1.496. Therefore, since n is the sum of k and j, the ratio of k: j: m is 1: 1: 0.249 and n / m = 8.032.

In addition, the ratio of n: m derived from Mw = 1136 and n / m = 8.03 was calculated to be 6.028: 6.028: 1.501, confirming that it is a condensate having Si of 14 and including 14 curable functional groups.

<Example 4>

Into a reaction vessel equipped with a stirrer and a dropping lot, 182 mL of 2-propanol (IPA) and 363 mL of toluene were added as a solvent, and 35.9 g (102 mmol) of 26% aqueous tetramethylammonium hydroxide solution (TMAH solution) was added as a basic catalyst. It was. Further, 121 mL of IPA, 44.8 g (303 mmol) of trimethoxy vinyl silane (KBM 1003 manufactured by Shin-Etsu Chemical Co., Ltd.) and 60.0 g (303 mmol) of trimethoxyphenylsilane were added to the dropping lot, It was dripped over 3 hours at room temperature, stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. After stirring for 5 hours, 10% aqueous citric acid solution was added and stirred for 2 hours to neutralize. The aqueous layer was extracted with toluene, and the organic layer was washed twice with saturated brine. The organic layer was dried over magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 56.8 g (recovery rate 88%) of a hydrolyzate (hydroxyl-containing silsesquioxane compound). This hydroxyl-containing silsesquioxane compound was a colorless viscous liquid soluble in various organic solvents.

The hydroxyl group-containing silsesquioxane compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [HO 1/2] is shown in Figure 11 the results of the GPC measurement of _m. Mw = 1492 and Mw / Mn = 1.436 from the GPC measurement results (Fig. 11).

Next, 53.0 g (36 mmol) of hydroxyl group-containing silsesquioxane compound and 304 mL of pyridine were measured in a reaction vessel equipped with a stirrer and a dropping lot, and nitrogen-substituted. 44.1 g (366 mmol) of dimethylvinylchlorosilane (made by Toray Dow Corning Silicone Co., Ltd.) was put into the dripping lot, and it was dripped over 1 hour at room temperature. It stirred at room temperature for 2 hours after completion | finish of dripping. After stirring for 2 hours, 305 mL of toluene and 305 mL of purified water were added to separate an organic layer and an aqueous layer. The organic layer was washed with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 55.2 g (91% recovery) of a curable silicone compound. This curable silicone compound was a colorless liquid soluble in various organic solvents.

The curable silicone compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] is shown in Figure 12 the results of the GPC measurement of _m. The Mw was 1685 and the Mw / Mn was 1.426 from the GPC measurement result (FIG. 12).

In which the curable silicone compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] 13 the result of measuring the ¹ H-NMR of the _m Indicates. From Figure _{13 [CH 2 = CHSiO 3/} 2] k: [PhSiO 3/2] j: [CH 2 = CH (CH 3) 2 O 1/2] a comparison The integration of the _m bar 13.831: 20.004: 6.000 It was. Therefore, the ratio of k: j: m is 4.610: 4.001: 1.000, and since n is the sum of k and j, n / m = 7.22.

In addition, the ratio k: j: m derived from Mw = 1685 and k + j / m = 7.22 is calculated to be 7.198: 7.198: 1.994, so that Si is a condensate having 17 and contains 8 curable functional groups. Confirmed.

Comparative Example 1

200 mL of toluene was added as a solvent to the reaction vessel provided with a stirrer and a dropping lot, and 39.0 g (21 mmol) of 5% aqueous tetramethylammonium hydroxy solution (TMAH aqueous solution) was added as a basic catalyst. 26.7 g (179 mmol) of toluene, trimethoxymethylsilane (SZ-6070 by Toray Dow Corning Silicone Co., Ltd.), and trimethoxy vinylsilane (KBM 1003 by Shin-Etsu Chemical Co., Ltd. make KBM 1003) to a dropping lot. (179 mmol) was added and a toluene solution of trimethoxyvinylsilane was added dropwise at room temperature over 2 hours while stirring the reaction vessel. After completion of the dropwise addition of trimethoxyvinylsilane, the mixture was stirred for 2 hours without heating, and the reaction solution was allowed to stand for 1 day, after which recondensation was performed. The dropping lot was removed, a dean-stark and a cooling tube were attached to the reaction vessel, heated to a liquid temperature of 75 ° C. to remove the side product methanol, and the toluene was refluxed at a liquid temperature of 105 ° C. Heated. After stirring and refluxing for 3 hours, the reaction was returned to room temperature to complete the reaction. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 33.7 g of the following recondensate (8) in a yield of 72%. This recondensate was a white solid that was poorly soluble in various organic solvents. The GPC chart of the following recondensate 8 obtained is shown in FIG. On the other hand, the recondensation herein refers to the condensation of a trialkoxysilane in the presence of an organic polar solvent and a basic catalyst, hydrolyzing and polycondensation, and condensation of the resulting hydrolysis product in the presence of a nonpolar solvent and a basic catalyst. It is a manufacturing method of quoxane (basket type silsesquioxane resin) (Unexamined-Japanese-Patent No. 2004-143449).

_{[CH 3 SiO 3/2]} i [CH 2 = CHSiO 3/2] h

Comparative Example 2

Toluene 200mL was added as a solvent to the reaction vessel provided with a stirrer and a dropping lot, and 39.0 g (21 mmol) of 5% aqueous tetramethylammonium hydroxide solution (TMAH aqueous solution) was added as a basic catalyst. 60 mL of toluene and 53.0 g (358 mol) of trimethoxyvinylsilane (KBM 1003 available from Shin-Etsu Chemical Co., Ltd.) were added to the dropping lot, and the toluene solution of trimethoxyvinylsilane was added at room temperature while stirring the reaction vessel. It was dripped over time. After completion of the dropwise addition of trimethoxyvinylsilane, the mixture was stirred for 2 hours without heating, and the reaction solution was allowed to stand for 1 day, after which recondensation was performed. The dropping lot was removed, a Deanstock and a cooling tube were attached to the reaction vessel, heated to a liquid temperature of 75 ° C. to remove methanol as a byproduct, and the toluene was heated to reflux at a liquid temperature of 105 ° C. After stirring and refluxing for 3 hours, the reaction was returned to room temperature to complete the reaction. The reaction solution was neutralized with 23.0 g of 10% aqueous citric acid solution, washed with saturated brine, and dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 30.3 g of the following recondensate (9) in a yield of 83%. This recondensate was a white solid that was poorly soluble in various organic solvents. The GPC chart of the following recondensate 9 obtained is shown in FIG. 15.

_{[CH 2 = CHSiO 3/2} ] g

[Compatibility Test]

The compatibility was evaluated by mixing the curable silicone compound obtained in the said Examples 1-4 with silicone type curable resin represented by following (10)-(14) by 1: 1 by weight ratio. In addition, the same evaluation was also made about those obtained in Comparative Examples 1 and 2 above. The results are shown in Table 1. In addition, evaluation was performed visually and the case where it was transparent was made into (circle) and the case where cloudiness was confirmed as x.

10 (11) (12) (13) (14) Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ ○ ○ ○ ○ Recondensate of Comparative Example 1 (8) × × × × × Recondensate of Comparative Example 2 (9) × × × × ×

_{(8): [CH 3 SiO} 3/2] i [CH 2 = CHSiO 3/2] h

_{(9): [CH 2 =} CHSiO 3/2] g

1 is a hydroxyl group-containing silsesquioxane compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [HO 1/2] m in the GPC chart,

Figure 2 is a hydroxyl group-containing silsesquioxane compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [HO 1/2] 1 H-NMR chart of the _m

Figure 3 is a curable silicone compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [(CH 3) 3 SiO 1/2] m in the GPC chart,

4 is a curable silicone compound _{[CH 3 SiO 3/2]} k [CH 2 = CHSiO 3/2] j [(CH 3) 3 SiO 1/2] 1 H-NMR chart of the _m

5 is a hydroxyl group-containing silsesquioxane compound _{[CH 2 = CHSiO 3/2} ] n [HO 1/2] m in the GPC chart,

6 is a curable silicone compound _{[CH 2 = CHSiO 3/2} ] n [CH 2 = CH (CH 3) 2 O 1/2] m in the GPC chart,

7 is a curable silicone compound _{[CH 2 = CHSiO 3/2} ] n [CH 2 = CH (CH 3) 2 O 1/2] 1 H-NMR chart of the _m

8 is a hydroxyl group-containing silsesquioxane compound _{[CH 2 (O) CHCH 2} OSiO 3/2] k [CH 2 = CHSiO 3/2] GPC chart of _j [HO _{1/2] m}

9 is a curable silicone compound _{[CH 2 (O) CHCH 2} OSiO 3/2] k [CH 2 = CHSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] GPC chart of the _m

10 is a curable silicone compound _{[CH 2 (O) CHCH 2} OSiO 3/2] k [CH 2 = CHSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] m 1 H- the NMR chart

11 is a hydroxyl group-containing silsesquioxane compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [HO 1/2] m in the GPC chart,

12 is a curable silicone compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] m in the GPC chart,

13 is a curable silicone compound _{[CH 2 = CHSiO 3/2} ] k [PhSiO 3/2] j [CH 2 = CH (CH 3) 2 O 1/2] 1 H-NMR chart of the _m

14 is a Comparative Example _{1 [CH 3 SiO 3/2} ] i [CH 2 = CHSiO 3/2] GPC chart of the _h

15 is a Comparative Example _{2 [CH 2 = CHSiO 3/} 2] GPC chart of _g

Claims (3)

 General formula (1) _{[RSiO 3/2] n [} R 1 (CH 3) 2 SiO 1/2] m Curable silicone compound represented by. [Where R and R ¹ are a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or Formulas (2) to (4) [Formula 1]

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and in R and R ¹ , each of the substituents may be the same as or different from each other. In 1 molecule represented by 1), it has two or more hardenable functional groups selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4), and at least 1 of R is the said hardenable functional group. . In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.] General formula (5) _{[RSiO 3/2] n [} HO 1/2] m A hydroxyl group-containing silsesquioxane compound represented by. [Wherein R is a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2 ) To (4) [Formula 2]

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and R may be the same or different from each other, but R in one molecule represented by the general formula (5) At least 1 of is a hardenable functional group selected from the group which consists of a C2-C3 alkenyl group and Formula (2)-(4). In addition, n represents the integer of 6-20, m represents the integer of 1-6, and n / m is the range of 1-10. Further, Mw is 500 to 5,000 and Mw / Mn is in the range of 1.0 to 1.5.] As a manufacturing method of the curable silicone compound of Claim 1, following General formula (6) RSiX ₃ [Wherein R is a hydrogen atom, an aryl containing group having 6 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or the following formula (2 ) To (4) [Formula 3]

(Wherein I is an integer of 1 to 3, R ² represents a hydrogen atom or a methyl group), and X represents a hydrolyzable group. &Quot; One or more silicon compounds in which R of the species silicon compound is an alkenyl group having 2 to 3 carbon atoms and any curable functional group selected from the group consisting of the above formulas (2) to (4) are RSiX ₃ : basic catalysts = 4 to In the presence of a basic catalyst in the range of 10 mol: 1 mol, hydrolysis is carried out in a mixed solvent of a polar solvent and a nonpolar solvent, and the following general formula (5) _{[RSiO 3/2] n [} HO 1/2] m (Wherein R is the same as above) n represents an integer of 6 to 20, m represents an integer of 1 to 6, and n / m is in the range of 1 to 10. After the production, the method of producing a curable silicone compound, characterized in that the reaction with monochlorosilane.

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