JP2006274082A - Method for producing organic silicon compound having radically polymerizable group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an organic silicon compound having a radically polymerizable group, by which the organic silicon compound having the radically polymerizable group can stably be produced without gelling during its production. <P>SOLUTION: This method for producing the organic silicon compound having the radically polymerizable group (for example, methacryloyl, acryloyl, vinyl, styryl, or allyl group) is characterized by using an N-nitrosophenylhydroxylamine salt as a polymerization inhibitor. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an organosilicon compound having a radical polymerizable group by utilizing a hydrolytic condensation reaction.

  Silicon compounds having various reactive functional groups have been proposed as raw materials for hybrid materials having both organic and inorganic properties. For example, Patent Document 1 discloses a photocationic curable silsesquioxane compound having an oxetanyl group. Patent Document 2 discloses a silicon-containing curable resin composition having a radically polymerizable (meth) acryloyl group. Furthermore, Patent Document 3 discloses a method for producing a polyorganosiloxane having a (meth) acryloyl group with improved storage stability.

When producing or storing a compound having a radical polymerizable group such as the above (meth) acryloyl group, a polymerization inhibitor is usually added. This is to prevent further polymerization of the product so as to obtain the product safely and efficiently during production and to improve the storage stability of the product during storage.
As the polymerization inhibitor, hydroquinones such as hydroquinone and methylhydroquinone, quinones such as p-benzoquinone, N-nitrosophenylhydroxylamine salts and the like are widely used. In Patent Document 4, N-nitrosophenylhydroxylamine salt is used, and (meth) acryloyl groups such as isocyanate ethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, and reactive groups such as isocyanate groups, epoxy groups, etc. A method is disclosed in which a compound having a reaction is reacted while avoiding polymerization by a (meth) acryloyl group. Patent Document 2 and Patent Document 3 do not disclose any polymerization inhibitor.

JP-A-11-29640 JP 2000-234024 A JP 2005-23257 A JP 7-138307 A

  An object of this invention is to provide the manufacturing method by which the silicon compound which has a radically polymerizable group is obtained stably, without gelatinizing during manufacture.

  As a result of intensive investigations to solve the above problems, the present inventors can easily obtain a silicon compound having a radical polymerizable group even in a reaction involving a silanol group by using a specific polymerization inhibitor. As a result, the present invention has been completed.

（式中、Ｒ^１はラジカル重合性基を有する有機基であり、Ｘ^１は加水分解性基である。）
（Ｒ^２）_ｎＳｉＸ^２ _４−ｎ （２）
（式中、Ｒ^２はアルキル基、シクロアルキル基、アリール基又はパーフルオロアルキル基であり、Ｘ^２は加水分解性基であり、ｎは０〜２の整数である。）

（式中、Ｒ^３はアルキル基、シクロアルキル基又はアリール基である。） The present invention is shown below.
1. A method for producing a silicon compound having a radical polymerizable group, which comprises using an N-nitrosophenylhydroxylamine salt as a polymerization inhibitor.
2. The silicon compound having a radical polymerizable group is represented by the hydrolytic condensate of the organosilicon compound [A] represented by the following formula (1) or the organosilicon compound [A] and the following formula (2). 2. A hydrolytic cocondensate with the organosilicon compound [B] and / or the compound [C] that generates an organosilicon compound represented by the following formula (3) in the reaction system: A method for producing a silicon compound having a radical polymerizable group.

(In the formula, R ¹ is an organic group having a radical polymerizable group, and X ¹ is a hydrolyzable group.)
(R ² ) _n SiX ² _4-n (2)
(In the formula, R ² is an alkyl group, a cycloalkyl group, an aryl group or a perfluoroalkyl group, X ² is a hydrolyzable group, and n is an integer of 0 to 2.)

(In the formula, R ³ represents an alkyl group, a cycloalkyl group, or an aryl group.)

  According to the present invention, a silicon compound having a radical polymerizable group can be stably obtained without gelation during production.

The present invention will be described in detail below.
The production method of the present invention is to produce a silicon compound having a radical polymerizable group (hereinafter referred to as “silicon compound [Z]”) using N-nitrosophenylhydroxylamine salt as a polymerization inhibitor. By using this N-nitrosophenylhydroxylamine salt, radical polymerization of the silicon compound [Z] can be prevented when removing the organic solvent used in the production of the silicon compound [Z]. As radical polymerization proceeds, the silicon compound [Z] gels and cannot be used.

The N-nitrosophenylhydroxylamine salt may be either a metal salt or an ammonium salt, and can be used singly or in combination of two or more when producing the silicon compound [Z].
Examples of the metal salt include aluminum, copper, iron (III), tin, zinc, magnesium, and the like, and an aluminum salt that is a more stable chelate is preferable. The structure of this aluminum salt is shown in the following formula (4).

  The polymerization inhibitor is usually added to the reaction system when the reaction with the raw material compound for polymerization such as a monomer is completed. The amount used is selected depending on the type and amount of the radical polymerizable group possessed by the silicon compound [Z], but is usually 0.5 to 10,000 ppm with respect to the mass of the silicon compound [Z], preferably 5 to 500 ppm. If the amount of the polymerization inhibitor used is too large, the product containing the silicon compound [Z] may be colored or the physical properties of a cured product formed using the silicon compound [Z] may be reduced.

  In the present invention, the raw material compound used for producing the silicon compound [Z] is not particularly limited, but a silicon compound having a radical polymerizable group is used. Examples of the radical polymerizable group include a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, and an allyl group. These may be used alone or in combination of one or more. In this silicon compound, the radical polymerizable group may be directly bonded to the silicon atom, or may be bonded via another atom or a functional group.

  In the present invention, a preferable silicon compound [Z] is a hydrolytic condensate (hereinafter referred to as “silicon compound [Z1]”) of the organosilicon compound [A] represented by the following formula (1), or the organic compound. Silicon compound [A], organosilicon compound [B] represented by the following formula (2), and / or organosilicon compound represented by the following formula (3) (hereinafter referred to as “organosilicon compound [C ′]”) Is a hydrolysis cocondensate (hereinafter referred to as “silicon compound [Z2]”) with the compound [C] that is generated in the reaction system.

（式中、Ｒ^１はラジカル重合性基を有する有機基であり、Ｘ^１は加水分解性基である。）
（Ｒ^２）_ｎＳｉＸ^２ _４−ｎ （２）
（式中、Ｒ^２はアルキル基、シクロアルキル基、アリール基又はパーフルオロアルキル基であり、Ｘ^２は加水分解性基であり、ｎは０〜２の整数である。）

（式中、Ｒ^３はアルキル基、シクロアルキル基又はアリール基である。）

(In the formula, R ¹ is an organic group having a radical polymerizable group, and X ¹ is a hydrolyzable group.)
(R ² ) _n SiX ² _4-n (2)
(In the formula, R ² is an alkyl group, a cycloalkyl group, an aryl group or a perfluoroalkyl group, X ² is a hydrolyzable group, and n is an integer of 0 to 2.)

(In the formula, R ³ represents an alkyl group, a cycloalkyl group, or an aryl group.)

（式中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は炭素数１〜６のアルキレン基である。） In the above formula (1) representing the organosilicon compound [A], R ¹ is an organic group having a radical polymerizable group, and at least one selected from a methacryloyl group, an acryloyl group, a vinyl group, a styryl group, and an allyl group. It is an organic functional group containing 20 or less carbon atoms. Among these, an organic functional group having 20 or less carbon atoms having a methacryloyl group or an acryloyl group (see the following formula (5)) is preferable.

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkylene group having 1 to 6 carbon atoms.)

In the above formula (5), R ⁵ is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group having 1 carbon atom or a trimethylene group having 3 carbon atoms. It is. Accordingly, preferred organic functional groups represented by the above formula (5) are 3- (methacryloxy) methyl group, 3- (acryloxy) methyl group, 3- (methacryloxy) propyl group and 3- (acryloxy) propyl group. .
In the above formula (5), when R ⁴ has 2 or more carbon atoms, it is difficult to obtain or synthesize, and when R ⁵ has 7 or more carbon atoms, silicon compound [Z] is used. The surface hardness of the formed cured product may not be sufficient.

In the above formula (1), the radical polymerizable group R ¹ may be directly bonded to the silicon atom or indirectly bonded via a functional group such as an alkylene group, a phenylene group, or an ester group. Also good.

In the formula (1), the hydrolyzable group X ¹ is not particularly limited as long as it is a functional group having hydrolyzability. For example, a halogen atom, a C1-C20 alkoxy group, a C3-C10 cycloalkoxy group, a C6-C10 aryloxy group, etc. are mentioned. Of these, an alkoxy group, a cycloalkoxy group, and an aryloxy group are preferable. Examples of the alkoxy group include a methoxy group, ethoxy group, n- and i-propoxy group, n-, i- and t-butoxy group. Examples of the cycloalkoxy group include a cyclohexyloxy group. Examples of the aryloxy group include a phenyloxy group. The hydrolyzable group X ¹ is more preferably an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a methoxy group and an ethoxy group because the hydrolysis reaction is easily controlled.
In the above formula (1), each X ¹ may be the same as or different from each other.

  Examples of the organosilicon compound [A] represented by the above formula (1) include 3- (acryloxy) methyltrimethoxysilane, 3- (acryloxy) methyltriethoxysilane, 3- (acryloxy) ethyltrimethoxysilane, 3 -(Acryloxy) ethyltriethoxysilane, 3- (acryloxy) propyltrimethoxysilane, 3- (acryloxy) propyltriethoxysilane, 3- (methacryloxy) methyltrimethoxysilane, 3- (methacryloxy) methyltriethoxysilane, 3 -(Methacryloxy) ethyltrimethoxysilane, 3- (methacryloxy) ethyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3- (methacryloxy) propyltriethoxysilane and the like. Of these, 3- (acryloxy) propyltrimethoxysilane, 3- (acryloxy) propyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane and 3- (methacryloxy) propyltriethoxysilane are preferred.

Next, in the above formula (2) representing the organosilicon compound [B], R ² is an alkyl group, a cycloalkyl group, an aryl group, or a fluoroalkyl group.
When R ² is an alkyl group, the preferred carbon number is 1-20, more preferably 1-12, and even more preferably 1-6.
When R ² is a cycloalkyl group, the preferable carbon number is 3 to 10, more preferably 5 to 8, and still more preferably 5 to 6.
When R ² is an aryl group, the preferable carbon number is 6 to 10, more preferably 6 to 8, and further preferably 6 to 7.

When R ² is a fluoroalkyl group, the fluoroalkyl group may be one in which part of the hydrogen atoms in the alkyl group is substituted with fluorine atoms, or all of the hydrogen atoms are substituted with fluorine atoms. Or a perfluoroalkyl group. A preferable carbon number is 2-20, More preferably, it is 2-12, More preferably, it is 2-10.

When R ² is a fluoroalkyl group, a functional group represented by the following formula (6) is preferable.
—R ⁶ — (CF ₂ ) _m —CF ₃ (6)
(In the formula, R ⁶ is an alkylene group having 1 to 4 carbon atoms, and m is an integer of 0 to 10).

In the above formula (2), the hydrolyzable group X ² is not particularly limited as long as it is a functional group having hydrolyzability. The hydrolyzable group X ² can be the same as the hydrolyzable group X ¹ in the above formula (1) representing the organosilicon compound [A].

In said formula (2), n is an integer of 0-2. Regardless of the value of n, each X ² may be the same or different. When n is 2, each R ² may be the same as or different from each other.

The organosilicon compound [B] represented by the above formula (2) is exemplified below.
When n is 0, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like can be mentioned.
When n is 1, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, cyclohexyltri Methoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, 1H, 1H, H, 2H-perfluorodecyltriethoxysilane, and the like.
Moreover, when n is 2, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, etc. are mentioned. .

  Next, the organosilicon compound [C ′] is a compound generated by hydrolysis of the compound [C] in a reaction system using the compound [C]. The occurrence of the organosilicon compound [C ′] represented by the above formula (3) in the reaction system can be confirmed by gas chromatography, liquid phase chromatography, or the like.

In the above formula (3) representing the organosilicon compound [C ′], R ³ is an alkyl group, a cycloalkyl group or an aryl group. Therefore, this compound [C ′] is an organosilicon compound having no radical polymerizable group and one silanol group.

When R ³ is an alkyl group, the preferred carbon number is 1-6, more preferably 1-4. Preferred examples of the alkyl group are methyl group, ethyl group, n- and i-propyl group, n-, i- and t-butyl group.
When R ³ is a cycloalkyl group, the preferred carbon number is 3 to 10, more preferably 5 to 8. A preferred example of the alkyl group is a cyclohexyl group.
Moreover, when R < ³ > is an aryl group, a preferable carbon number is 6-10, More preferably, it is 6-8. A preferred example of the aryl group is a phenyl group.

In the above formula (3), each R ³ may be the same as or different from each other.

  Examples of the organosilicon compound [C ′] represented by the above formula (3) include trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, benzyldimethylsilanol, diphenylmethylsilanol, butyldimethylsilanol, phenyl Examples thereof include dimethylsilanol.

  Therefore, as the compound [C] for generating the organosilicon compound [C ′] in the reaction system, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tripropylethoxysilane, Trimethylsilyl acetate, trimethylsilyl benzoate, triethylsilyl acetate, triethylsilyl benzoate, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, diphenylmethoxymethylsilane, diphenylethoxymethylsilane, ethoxytriphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexa Propyl disiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1,3-diphe Le-1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl-1,1,3,3-tetraphenyl disiloxane, and the like.

  When the compound [C] comes into contact with water during the reaction, a hydrolysis reaction occurs, and the organosilicon compound [C ′] represented by the general formula (3) is generated in the reaction system. When a hydrolysis catalyst coexists in the reaction system, this hydrolysis reaction is usually accelerated.

Among the organosilicon compounds [Z] in the present invention, the silicon compound [Z1] is a polymer obtained by hydrolytic condensation of one or more of the organosilicon compounds [A] represented by the above formula (1). is there.
Moreover, silicon compound [Z2] is a polymer shown by following (i)-(iii).
(I) A polymer obtained by hydrolytic cocondensation of one or more of the organosilicon compound [A] and one or more of the organosilicon compound [B].
(Ii) A polymer obtained by hydrolytic cocondensation of at least one organic silicon compound [A], at least one organic silicon compound [B], and at least one compound [C].
(Iii) A polymer obtained by hydrolytic cocondensation of at least one organic silicon compound [A] and at least one compound [C].

  In the above (i) and (ii), by changing the amount of the organosilicon compound [B] used, the content of the radical polymerizable group in the obtained silicon compound [Z2] is also changed. The curability of the composition containing Z2] and further the physical properties of the cured product can be improved.

In the above (i) and (iii) using the compound [C], the compound [C] is charged together with the organosilicon compound [A] and / or the organosilicon compound [B] and hydrolyzed cocondensation. (Hereinafter referred to as “collective charging method”), and after hydrolyzing (co) condensing the organosilicon compound [A] and / or the organosilicon compound [B], the compound [C] is added. Hydrolysis cocondensation (hereinafter referred to as “post-addition method”) may also be used.
In the case of producing by the batch charging method, the viscosity of the hydrolyzed condensate can be lowered, and the condensate can be easily handled. In the case of producing by a post-addition method, the condensate has a high molecular weight, but has a relatively low viscosity and good workability.

  In the present invention, the organosilicon compound [Z] is usually hydrolyzed in an organic solvent by the batch charging method or the post-addition method, and the organosilicon compound [A], the organosilicon compound [B], and / or [C]. It is obtained by a production method including a step of condensing, a step of adding an N-nitrosophenylhydroxylamine salt, and a step of removing the used organic solvent.

  The amount of water used in the hydrolysis-condensation step is the amount of water required to completely hydrolyze the hydrolyzable group contained in the organosilicon compound [A], organosilicon compound [B] or compound [C]. When it is 1 equivalent, it is preferably an amount corresponding to 0.5 to 10 equivalents, more preferably 1 to 5 equivalents.

  The pH of the reaction system in the hydrolysis condensation step is preferably an acidic atmosphere of 0.5 to 4.5, more preferably 0.5 to 3.0. When the pH is less than 0.5, hydrolysis of the (meth) acrylic acid ester portion may occur simultaneously, and the curability of the product may be lowered. On the other hand, if the pH exceeds 4.5, for example, the hydrolysis and condensation reaction rates may decrease under weak acidity, and a long time may be required for production.

  In order to set it as said acidic atmosphere, acidic catalysts, such as hydrochloric acid, a sulfuric acid, phosphoric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, carbonic acid, can be used, for example. Of these, hydrochloric acid is preferred. Moreover, these acidic catalysts can be used individually by 1 type or in combination of 2 or more types.

  The organic solvent used at the time of hydrolysis is not particularly limited, and examples thereof include alcohols such as methanol, ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, toluene, 1,4-dioxane, hexane, ligroin and the like. These can be used alone or in combination of two or more, but it is preferable to make the reaction system a uniform solution.

  The reaction temperature in the hydrolysis condensation step is preferably 10 to 120 ° C, more preferably 20 to 80 ° C. Moreover, reaction time becomes like this. Preferably it is 2 to 30 hours, More preferably, it is 4 to 24 hours.

  After the hydrolysis condensation step, N-nitrosophenylhydroxylamine salt is added to the reaction system as a polymerization inhibitor. The conditions for the addition are not particularly limited. Usually, the N-nitrosophenylhydroxylamine salt is added directly to the reaction system at a temperature lower than the boiling point of the solvent used, and then stirred and dissolved uniformly.

  After the addition of the polymerization inhibitor, the organic solvent is removed. This step is carried out by a normal distillation operation under normal pressure or reduced pressure. In this organic solvent removing step, water remaining in the reaction system together with the organic solvent, a compound formed by hydrolysis of the hydrolyzable group (for example, ethanol when the hydrolyzable group is an ethoxy group) Etc. are removed together.

In the silicon compound [Z] obtained by the above method, the hydrolyzable group X ¹ (and hydrolyzable group X ² ) bonded to the organosilicon compound [A] (and the organosilicon compound [B]) is hydrolyzed. The skeleton contains a three-dimensional siloxane bond (Si—O—Si) formed as described above. The silicon compound [Z] includes a silsesquioxane compound having a ladder-like, cage-like, or random structure. This silsesquioxane compound may be used alone or in combination of two or more having different structures or molecular weights.

  It is preferable that 90% or more of the hydrolyzable groups of the organosilicon compound [A] (and the organosilicon compound [B]) are condensed in the silicon compound [Z]. It is further preferred that all are condensed. If the ratio of the remaining hydrolyzable groups exceeds 10%, the silsesquioxane structure is not sufficiently formed, so that the hardness of the cured product may be lowered, or the storage stability of the composition may be lowered. Here, “all of the hydrolyzable groups are substantially condensed” is confirmed, for example, by confirming that no peak based on the hydrolyzable groups is observed in the obtained polyorganosiloxane in the NMR chart. Can do.

  Further, the silicon compound [Z] obtained by the above method preferably has a number average molecular weight by gel permeation chromatography (GPC) of 600 to 5,000, more preferably 1,000 to 3,000. When the number average molecular weight is less than 600, sufficient hardness may not be obtained for a cured product formed from the composition containing the silicon compound [Z]. On the other hand, when the number average molecular weight exceeds 5,000, the viscosity of the silicon compound [Z] becomes too high, and the workability during handling may be lowered.

  The organosilicon compound obtained by the production method of the present invention uses a N-nitrosophenylhydroxylamine salt as a polymerization inhibitor, so that the desired structure and physical properties are not lowered, and the curing is excellent in curability. It is useful as an adhesive composition, and a cured product excellent in hardness, scratch resistance and heat resistance can be formed by the composition.

  Examples The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the following number average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC), and a viscosity is a measured value by a rotational viscometer.

Example 1
In a reactor equipped with a stirrer and a thermometer, 131.2 g (0.56 mol) of 3- (acryloxy) propyltrimethoxysilane, 49.9 g (0.28 mol) of methyltriethoxysilane, 22.7 g of hexamethyldisiloxane (0.14 mol) and 80 g of isopropyl alcohol were charged to obtain a raw material mixture. Thereafter, 50.9 g of an aqueous 0.8% hydrochloric acid solution (consisting of 12 mmol of HCl and 2.80 mol of H ₂ O) was added dropwise while stirring the raw material mixture to initiate the reaction. Further, stirring was continued at 25 ° C., and the progress of the reaction was followed by GPC. The reaction was completed when the raw silicon compound almost disappeared (24 hours after the start of dropping of the hydrochloric acid aqueous solution).
Next, 200 ppm of N-nitrosophenylhydroxylamine / aluminum salt represented by the following formula (7) was added to the reaction system as a polymerization inhibitor, and the mixture was stirred and dissolved. Thereafter, the solvent was distilled off under reduced pressure, a condensation product having an acryloyl group as a radical polymerizable group, slightly yellow transparent, a number average molecular weight of 1,400, and a viscosity of 11,110 mPa · s. I got a thing.

Comparative Example 1
A condensate was obtained in the same manner as in Example 1 except that 200 ppm of hydroquinone was used as a polymerization inhibitor. The condensate after the solvent was distilled off was gelled and lost fluidity. This gelation is presumed that intermolecular cross-linking has progressed because the hydroxyl group contained in hydroquinone has some interaction with the silanol group produced during the reaction, and the ability to inhibit polymerization is lost or reduced.

Example 2
In a reactor equipped with a stirrer and a thermometer, 536.4 g (2.16 mol) of 3- (methacryloxy) propyltrimethoxysilane, 192.6 g (1.08 mol) of methyltriethoxysilane, and 87.7 g of hexamethyldisiloxane. (0.54 mol) and 356 g of isopropyl alcohol were charged to obtain a raw material mixture. Then, 196.2 g of 0.8% hydrochloric acid aqueous solution was added dropwise while stirring this raw material mixture to initiate the reaction. Further, stirring was continued at 25 ° C., and the progress of the reaction was followed by GPC. The reaction was completed when the raw silicon compound almost disappeared (24 hours after the start of dropping of the hydrochloric acid aqueous solution).
Next, 200 ppm of the N-nitrosophenylhydroxylamine salt used in Example 1 was added to the reaction system and stirred and dissolved. Thereafter, the solvent was distilled off under reduced pressure, and a condensate having a methacryloyl group as a radical polymerizable group, colorless and transparent, a number average molecular weight of 1,500, and a viscosity of 1,060 mPa · s. Got.

Comparative Example 2
A condensate was obtained in the same manner as in Example 2 except that 200 ppm of hydroquinone was used as a polymerization inhibitor. The condensate after the solvent was distilled off was gelled and lost fluidity.

Example 3
In a reactor equipped with a stirrer and a thermometer, 49.2 g (0.21 mol) of 3- (acryloxy) propyltrimethoxysilane, 42.7 g of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (0. 07 mol) and 154 g of isopropyl alcohol were charged to obtain a raw material mixture. Then, while stirring this raw material mixture, 15.3 g of 0.8% hydrochloric acid aqueous solution was added dropwise to initiate the reaction. Further, stirring was continued at 25 ° C., and the progress of the reaction was followed by GPC. The reaction was completed when the raw silicon compound almost disappeared (24 hours after the start of dropping of the hydrochloric acid aqueous solution).
Next, 200 ppm of the N-nitrosophenylhydroxylamine salt used in Example 1 was added to the reaction system and stirred and dissolved. Thereafter, the solvent is distilled off under reduced pressure, and a condensate having an acryloyl group as a radical polymerizable group, colorless and transparent, a number average molecular weight of 1,500, and a viscosity of 4,500 mPa · s. Got.

Comparative Example 3
A condensate was obtained in the same manner as in Example 1 except that 1,000 ppm of hydroquinone was used as a polymerization inhibitor. The condensate after the solvent was distilled off was gelled and lost fluidity.

  The organosilicon compound obtained by the production method of the present invention uses a N-nitrosophenylhydroxylamine salt as a polymerization inhibitor, so that the desired structure and physical properties are not lowered, and the curing is excellent in curability. It is useful as a curable composition, and a cured product having excellent hardness, scratch resistance and heat resistance can be formed by the composition. Therefore, it is suitable for protective films of various substrates such as hard coating agents and antireflection films, optical waveguides and the like. Further, since the content ratio of the inorganic component in the film can be increased, it is also useful as a resist raw material.

Claims (2)

  A method for producing a silicon compound having a radical polymerizable group, which comprises using an N-nitrosophenylhydroxylamine salt as a polymerization inhibitor. The silicon compound having a radical polymerizable group is represented by the hydrolytic condensate of the organosilicon compound [A] represented by the following formula (1) or the organosilicon compound [A] and the following formula (2). The hydrolytic cocondensate with an organic silicon compound [B] and / or a compound [C] that generates an organic silicon compound represented by the following formula (3) in the reaction system. A method for producing a silicon compound having a radically polymerizable group.

(In the formula, R ¹ is an organic group having a radical polymerizable group, and X ¹ is a hydrolyzable group.)
(R ² ) _n SiX ² _4-n (2)
(In the formula, R ² is an alkyl group, a cycloalkyl group, an aryl group or a perfluoroalkyl group, X ² is a hydrolyzable group, and n is an integer of 0 to 2.)

(In the formula, R ³ represents an alkyl group, a cycloalkyl group, or an aryl group.)