JP2014040582A - Method for manufacturing silicon-containing polymer particulates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing silicon-containing polymer particulates capable of yielding silicon-based polymer composite particles having small diameters, of homogeneously controlling the molecular weight and particle diameter thereof, and of manufacturing heteromorphically structured silicon-containing polymer particulates of non-hollow structures, core-shell structures, and/or hollow structures.SOLUTION: The provided method for manufacturing silicon-containing polymer particulates includes a step of performing living polymerization by using an alkoxysilyl group-substituted allene monomer.

Description

The present invention can produce silicon-based polymer composite particles having a small particle diameter, and can uniformly control the molecular weight and particle diameter, and suitably produces silicon-containing polymer fine particles such as a solid structure, a core-shell structure, and a hollow structure. The present invention relates to a method for producing fine silicon-containing polymer particles.

Conventionally, inorganic particles such as ceramics have been used alone or in combination with organic polymers for various purposes such as ultraviolet absorption, wear resistance, and imparting optical / electromagnetic properties.
On the other hand, organic resin particles are used in toners for electrophotography, matting, colorants and the like by utilizing flexibility, adhesion, and processability which are characteristics of polymers.
On the other hand, in the field of electronic component bonding materials and the like, inorganic particles have insufficient elasticity and crack when mixed or compressed, whereas organic resin particles have insufficient heat resistance. Because of the problem of melting and deformation during mixing with a material or in a heating process, there is a demand for fine particles that have both heat resistance and hardness of inorganic particles and elasticity and affinity of organic resin particles.

On the other hand, in order to achieve excellent properties of the inorganic material and the organic material at the same time, a composite material of both is used. However, the compatibility between the inorganic material and the organic material is generally not sufficient.
In addition, a method of copolymerizing an organic monomer and an inorganic monomer and a method of polymerizing a silane coupling agent are also performed, but the structure has a structure in which an organic component and an inorganic component are randomly arranged, and the required heat resistance and Elasticity was not obtained.
Furthermore, in Patent Document 1, after swelling seed particles with a swelling solvent containing a polyvalent metal alkoxide, the seed particles are polymerized by an unsaturated double bond in the polyvalent metal alkoxide, and then the alkoxy group of the polyvalent metal alkoxide is changed. A process for hydrolysis and condensation is described.
However, the particles formed in the production method are not uniform in molecular weight, and the alkoxy groups of the metal alkoxide are randomly arranged, so that hydrolysis polycondensation does not proceed densely, and sufficient heat resistance There is a problem that elasticity cannot be obtained.

Japanese Patent Laid-Open No. 07-265686

The present invention can produce silicon-based polymer composite particles having a small particle diameter, and can uniformly control the molecular weight and particle diameter, and suitably produces silicon-containing polymer fine particles such as a solid structure, a core-shell structure, and a hollow structure. It is an object of the present invention to provide a method for producing silicon-containing polymer fine particles that can be produced.

The present invention is a method for producing silicon-containing polymer fine particles having a step of conducting living polymerization using an alkoxysilyl group-substituted allene monomer.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention can uniformly control the molecular weight and particle diameter of the resin by producing silicon-containing polymer fine particles by conducting living polymerization using an alkoxysilyl group-substituted allene monomer. In addition, the inventors have found that silicon-containing polymer fine particles in which silicon is uniformly distributed on the particle surface can be produced, and have completed the present invention.

The method for producing silicon-containing polymer fine particles of the present invention includes a step of performing living polymerization using an alkoxysilyl group-substituted allene monomer.

The living polymerization refers to polymerization in which a molecular chain grows without the polymerization reaction starting from an initiator being hindered by a side reaction such as a termination reaction or a chain transfer reaction.
In the present invention, by using such living polymerization, a polymer having a uniform molecular weight can be obtained if the polymerization reaction starts simultaneously, and silicon-containing polymer fine particles having a uniform particle diameter can be obtained.
Further, by using the above living polymerization, a polymerization reaction in an aqueous medium can be performed, and polymers having various substituents can be obtained.

The living polymerization is not particularly limited, and for example, living anionic polymerization, living radical polymerization, living cation polymerization, living coordination polymerization and the like can be employed. Of these, living coordination polymerization is preferred.
In the present invention, the living polymerization is preferably performed by a dispersion polymerization method. Moreover, when performing living polymerization by a post process, it is preferable to perform living block copolymerization on the conditions accompanied by non-uniform | heterogenous. Thereby, it becomes easy to obtain particles having not only a molecular weight but also a uniform particle diameter. The dispersion polymerization method means that the monomer is polymerized in a solvent in which the monomer is dissolved but the polymer obtained by polymerizing the monomer is not dissolved, and the deposited polymer is spheroidized by the action of interfacial tension, electrostatic repulsion, etc. It is a polymerization method characterized by this.

As the initiator used in the living polymerization, for example, various transition metal catalysts including a π-allyl nickel catalyst can be used.
The π-allyl nickel catalyst is composed of allyl compounds such as allyl halide and allyl acetate, organic nickel such as bis (1,5-cyclooctadiene) nickel (hereinafter referred to as Ni (COD) ₂ ), triphenylphosphine. And phosphine such as tributylphosphine, triphenoxyphosphine, triethoxyphosphine, and the like.

Examples of the allyl compound include allyl trifluoroacetate, allyl methyl acetate, allyl cyanomethyl acetate, and the like. Of these, allyl trifluoroacetate is particularly preferable.
Moreover, it is preferable that an allyl compound shall be 1-30 weight part with respect to 100 weight part of allene monomers. If the allyl compound is less than 1 part by weight, the polymerization may not proceed. If it exceeds 30 parts by weight, the polymerization rate may be too high to obtain a stable fine particle shape. More preferably, it is 2 to 10 parts by weight.

When organic nickel is added to the allyl compound, the organic nickel is preferably 100 to 5000 parts by weight with respect to 100 parts by weight of the allyl compound. More preferably, it is 400-1000 weight part.
Moreover, when adding phosphine to the said allyl compound, it is preferable that phosphine shall be 25-200 weight part with respect to 100 weight part of allyl compounds. More preferably, it is 50-150 weight part.

The living polymerization is preferably carried out by a so-called dispersion polymerization method in which an allene monomer is dissolved but a polymer obtained by polymerizing the allene monomer is polymerized in a solvent that does not dissolve in order to synthesize the fine particle shape stably. Such a solvent is called a poor solvent. If a solvent that does not dissolve the allene monomer is used, the reactivity of the allene monomer with the initiator becomes extremely slow, and the polymerization may not proceed. In addition, when a solvent that dissolves a polymer obtained by polymerizing an allene monomer is used, although polymerization proceeds, it may be difficult to obtain a fine particle shape. Such a solvent is not particularly limited, for example, non-polar solvents such as hexane, cyclohexane, octane, toluene, xylene, methylene chloride, water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl High polar solvents such as ketone, tetrahydrofuran, dioxane, N, N-dimethylformamide can be used. These solvents may be used alone or in combination of two or more. In these, it is preferable to mix water, methanol, and ethanol suitably, or to use toluene and a methylene chloride.
Moreover, it is preferable that the addition amount of a solvent shall be 400-100000 weight part with respect to 100 weight part of said allene monomers. If the amount is less than 400 parts by weight, aggregation or coarse particles may occur in the polymerization process. On the other hand, if it exceeds 100,000 parts by weight, the polymer obtained by polymerization will not form a fine particle shape while being dissolved in the solvent, or even if a fine particle shape is obtained, the amount from the solvent is very small. Isolation may be difficult. More preferably, it is 900-9900 weight part. More preferably, it is 1150-4900 weight part.

In the living polymerization, a dispersion stabilizer is preferably used in order to stably synthesize the fine particle shape. When a dispersion stabilizer is used, it is possible to prevent fine particles formed by polymerization from forming an aggregate or forming coarse particles. Examples of such a dispersion stabilizer include poly (N-vinylpyrrolidone), polyvinyl alcohol, methyl cellulose, ethyl cellulose, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyethylene glycol, and the like. In particular, poly (N-vinylpyrrolidone), polymethyl methacrylate and the like are preferable.
The dispersion stabilizer is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the allene monomer. If the amount is less than 1 part by weight, fine particles formed by polymerization may be united to form an aggregate or coarse particles may be formed. When the amount exceeds 100 parts by weight, the viscosity of the solvent becomes high, stirring is not performed uniformly, and there is a possibility that aggregates are formed. More preferably, it is 5 to 50 parts by weight. More preferably, it is 10-40 weight part.

Specific examples of the living polymerization include a method in which a solvent and an alkoxysilyl group-substituted allene monomer are added to a previously prepared π-allylnickel catalyst in a nitrogen-substituted polymerization vessel and stirred for several hours at room temperature. The polymerization temperature is preferably 0 to 90 ° C. from the viewpoint of the reaction rate.

The alkoxysilyl group-substituted allene monomer is a monomer having an allene group and an alkoxysilyl group.
In the present invention, by using the above alkoxysilyl group-substituted allene monomer in living polymerization, the alkoxysilyl group and the silanol group hydrolyzate thereof are uniformly arranged in the molecule, and as a result, polycondensation is efficiently performed. As a result, a strong siloxane bond is formed. Therefore, silicon-containing polymer fine particles that are extremely heat-resistant and hard are obtained. In addition, if the organic part is baked in this state, it can be converted into silica fine particles.
Further, since the reaction in the molecule is preferentially performed, the reaction between the silicon-containing polymer fine particles is small, and fine particles with little aggregation are obtained.

The alkoxysilyl group-substituted allene monomer is a compound having a structure represented by the following formula (1).

In formula (1), R ¹ is an alkoxy group.

The structure represented by “CH ₂ ═C═CH—” in the compound represented by the formula (1) is an allene group.
The structure represented by “—Si—R ¹ ” is an alkoxysilyl group.

Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a 2-methoxyethoxysilyl group, an acetoxymethylsilyl group, a propoxysilyl group, and a butoxysilyl group. Or an ethoxysilyl group is preferable.

The portion represented by “—Si—R ² ” is not particularly limited, but is preferably an alkoxysilyl group so as to increase the number of reaction points from the viewpoint of high heat resistance and high hardness.
Moreover, - although there is no particular limitation on the portion indicated by "Si-R ^3", high heat resistance, from the viewpoint of high hardness, as more reactive sites is increased, it is preferable that the alkoxysilyl group.
From the viewpoint of further increasing heat resistance and hardness, it is more preferable that both “—Si—R ² ” and “—Si—R ³ ” are alkoxysilyl groups.
Furthermore, “—Si—R ¹ ”, “—Si—R ² ”, and “—Si—R ³ ” may be different from each other, but are preferably the same composition from the viewpoint of uniformity. That is, it is preferable to have three alkoxysilyl groups. More preferably, all are methoxysilyl groups and ethoxysilyl groups.

R ⁴ is not particularly limited, and examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group, phenoxy group, methyl group, ethyl group, propyl group, butyl group, phenyl group, and benzyl group. It is done.
Of these, a methoxy group and an ethoxy group are preferred because of the ease of preparing an allene monomer.

Examples of the alkoxysilyl group-substituted allene monomer include 1-triethoxysilyl-1-methoxyallene, 1-trimethoxysilyl-1-methoxyallene, 1-triethoxysilyl-1-ethoxyallene, and 1-trimethoxysilyl. -1-ethoxyallene, 1-triethoxysilylallene, 1-trimethoxysilylallene, 1-triethoxysilyl-1-methylallene, 1-trimethoxysilyl-1-methylallene, 1-triethoxysilyl-1- Phenoxy allene, 1-trimethoxysilyl-1-phenoxy allene, 1-triethoxysilyl-1-phenyl allene, 1-trimethoxysilyl-1-phenyl allene and the like can be mentioned.
Of these, 1-triethoxysilyl-1-methoxyallene is preferable.

Examples of the method for producing the alkoxysilyl group-substituted allene monomer include a method of reacting an allene monomer with chlorosilanes under strongly basic conditions.

In the present invention, if necessary, other allene monomers such as hydrocarbon-based allene monomers and functional group-containing allene monomers may be copolymerized.
Examples of the hydrocarbon-based allene monomer include phenoxyallene, allene (1,2-propadiene), methylallene, ethylallene, propylallene, butylallene, isopropylallene, hexylallene, phenylallene, benzylallene, dimethylallene, and diethyl. Examples include allene, dihexyl allene, diphenyl allene, substituted alkyl butadiene ether, arenic acid ester, polyoxyethylene allenyl alkyl ether, and the like.
Examples of the phenoxyallene include phenoxyallene, (4-tert-butylphenoxy) allene, (4-nitrophenoxy) allene, and (4-acetylphenoxy) allene. Among these, phenoxyallene is preferable from the viewpoint of excellent reactivity and uniformity of particle diameter.

Examples of the functional group-containing allene monomer include carboxymethyl allene, 2-carboxyethyl allene, dicarboxymethyl allene, 2,2-dicarboxyethyl allene, aminomethyl allene, 2-aminoethyl allene, cyanomethyl allene, 2 -Cyanoethyl allene, hydroxyethyl allene, etc. are mentioned.
Of these, hydroxyethylallene is preferred from the viewpoint of excellent reactivity and uniformity of particle diameter.

The addition amount of the alkoxylyl group-substituted allene monomer is preferably 1 to 100 molar equivalents when the total allenic monomer including the alkoxylyl group-substituted allene monomer and the other allenic monomer is 100 molar equivalents. . By setting it within the above range, uniform silicon-containing polymer fine particles having no aggregation can be obtained. More preferably, it is 10-90 molar equivalent.

As for the addition amount of the whole allene monomer which combined the said alkoxy silyl group substituted allene monomer and other allene monomers, a preferable minimum is 5 molar equivalent with respect to 1 molar equivalent of an initiator, and a preferable upper limit is 1000 molar equivalent. When the addition amount of the whole allene monomer is less than 5 molar equivalents, it may be difficult to form silicon-containing polymer fine particles, and when it exceeds 1000 molar equivalents, aggregation of silicon-containing polymer fine particles may be caused.
The more preferable lower limit of the addition amount of the entire allene monomer is 15 molar equivalents, and the more preferable upper limit is 200 molar equivalents.

Examples of the shape of the silicon-containing polymer fine particles obtained by the method for producing silicon-containing polymer fine particles of the present invention include a solid shape, a hollow shape, a core-shell shape, a network shape, and a vesicle shape. In particular, in the present invention, hollow particles having a high hollowness and a small particle diameter can be suitably produced.

The method for producing silicon-containing polymer fine particles of the present invention is not particularly limited as long as it has a step of performing living polymerization using the above alkoxysilyl group-substituted allene monomer.
Method (X) for performing only the step of conducting living polymerization using the alkoxysilyl group-substituted allene monomer,
Method (A) of performing Step 2 of performing polymerization using another allene monomer after performing Step 1 of performing living polymerization using the alkoxysilyl group-substituted allene monomer.
Method (B) of performing Step 2 of performing living polymerization using the alkoxysilyl group-substituted allene monomer after performing Step 1 of polymerizing the other allene monomer.
Is mentioned.

The method X is a method suitable for obtaining particles having a solid structure made of a polymer of an alkoxysilyl group-substituted allene monomer.
In the method A and method B, since the amount of the inorganic component by the alkoxysilyl group-substituted allene monomer and the amount of the organic component by the other allene monomer can be adjusted, the ratio of the inorganic component to the organic component in the particles is accurately controlled. There is an advantage that you can.

In the method A, when there are many alkoxysilyl group-substituted allene monomers, core-shell particles in which the polymer of the other allene monomer is the core and the polymer of the alkoxysilyl group-substituted allene monomer is the shell are obtained. When the amount of allene monomer is small, vesicle particles are obtained in which the inside is hollow, the outermost layer is a polymer of an alkoxysilyl group-substituted allene monomer, and the intermediate layer is a polymer of another allene monomer.
In the method B, when there are many alkoxysilyl group-substituted allene monomers, core-shell particles in which the polymer of the alkoxysilyl group-substituted allene monomer is the core and the polymer of the other allene monomer is the shell are obtained. When the amount of substituted allene monomers is small, vesicle particles are obtained in which the inside is hollow, the outermost layer is a polymer of another allene monomer, and the intermediate layer is a polymer of an alkoxysilyl group-substituted allene monomer.

In the above method A, it is preferable that the living polymerization at the time of performing step 1 is performed by living coordination polymerization. That is, Step 1 of living coordination polymerization using an alkoxysilyl group-substituted allene monomer, and a copolymer of the alkoxysilyl group-substituted allene monomer are copolymerized with other allene monomers other than the alkoxysilyl group-substituted allene monomer. It is preferable to carry out the method having step 2.

The silicon-containing polymer fine particles obtained by the method for producing silicon-containing polymer fine particles of the present invention have a preferred lower limit of the average particle diameter of 0.001 μm and a preferred upper limit of 5 μm. If the average particle size is less than 0.001 μm, the polymer may be too small to obtain hardness or elasticity as a polymer. When the average particle diameter exceeds 5 μm, the particles may aggregate during polymerization. A more preferable lower limit of the average particle diameter is 0.002 μm, and a more preferable upper limit is 3 μm.
The average particle diameter of the silicon-containing polymer fine particles means an average value of diameters obtained by observing 50 silicon-containing polymer fine particles randomly selected using an optical microscope or an electron microscope.

The average upper limit of the CV value of the average particle size of the silicon-containing polymer fine particles is 80%. When the CV value exceeds 80%, the particle size distribution becomes too wide. A more preferable upper limit of the CV value is 50%. The CV value is a numerical value indicated by a percentage (%) of a value obtained by dividing the standard deviation by the average particle diameter.

The silicon-containing polymer fine particles obtained in the present invention can be suitably used as a filler for bonding materials for electronic parts, a refractive index control agent, a heat insulating material, a dielectric constant control agent, and the like.

According to the present invention, silicon-based polymer composite particles having a small particle diameter can be obtained, and the molecular weight and particle diameter can be controlled uniformly, and silicon-containing polymer fine particles such as a solid structure, a core-shell structure, and a hollow structure are suitable. It is possible to provide a method for producing silicon-containing polymer fine particles that can be produced easily.

It is the microscope picture which observed the particle | grains obtained in Example 2 using the transmission electron microscope. It is the microscope picture which observed the particle | grains obtained in Example 3 using the transmission electron microscope. It is the microscope picture which observed the particle | grains obtained in Example 4 using the transmission electron microscope. It is the microscope picture which observed the particle | grains obtained in Example 5 using the transmission electron microscope. It is the microscope picture which observed the particle | grains obtained in Example 6 using the transmission electron microscope. It is the microscope picture which observed the particle | grains obtained in Example 7 using the transmission electron microscope.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Table 1 shows whether the production method is applicable to the above-described method X, method A, or method B. In Method A and Method B, the monomer used in Step 1 was the first monomer, and the monomer used in Step 2 was the second monomer.

Example 1
A stir bar was placed in a 5 mL test tube and purged with nitrogen. Thereafter, 0.01 mmol (0.00275 g) of bis (1,5-cyclooctadiene) nickel, 0.012 mmol (0.00314 g) of triphenylphosphine, 0.012 mmol (0.00185 g) of allyl trifluoroacetate, 1 mL of ethanol (1.2500 g), polyvinylpyrrolidone 10% ethanol solution 0.1 mL (0.125 g), 1-triethoxysilyl-1-methoxyallene 0.5 mmol (0.1175 g) is added, polymerization is performed for 24 hours, and silicon is contained. Polymer fine particles were obtained.

(Example 2)
A stir bar was placed in a 5 mL test tube and purged with nitrogen. Thereafter, 0.01 mmol (0.00275 g) of bis (1,5-cyclooctadiene) nickel, 0.012 mmol (0.00145 g) of allyl bromide, 1 mL (1.16 g) of toluene, 1-triethoxysilyl-1-methoxy Allene (0.2 mmol, 0.0470 g) was added and polymerization was performed for 24 hours to obtain a solution in which the silicon-containing polymer was uniformly dissolved.
Thereafter, 0.012 mmol (0.00314 g) of triphenylphosphine and 0.2 mmol (0.0168 g) of hydroxyethyl allene were added, and polymerization was further performed for 24 hours to obtain silicon-containing polymer fine particles.

(Example 3)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 2 except that the amount of hydroxyethylallene added was 0.3 mmol (0.0252 g).

Example 4
Silicon-containing polymer fine particles were obtained in the same manner as in Example 2 except that the amount of hydroxyethylallene added was 0.6 mmol (0.0504 g).

(Example 5)
A stir bar was placed in a 5 mL test tube and purged with nitrogen. Thereafter, 0.01 mmol (0.00275 g) of bis (1,5-cyclooctadiene) nickel, 0.012 mmol (0.00314 g) of triphenylphosphine, 0.012 mmol (0.00145 g) of allyl bromide, 1 mL of ethanol (1 .25 g) and 0.2 mmol (0.0168 g) of hydroxyethyl allene were added, and polymerization was performed for 24 hours to obtain a solution in which the polymer was uniformly dissolved.
Thereafter, 0.015 mmol (0.00285 g) of copper iodide and 0.2 mmol (0.0470 g) of 1-triethoxysilyl-1-methoxyallene were added and polymerization was further performed for 24 hours to obtain silicon-containing polymer fine particles.

(Example 6)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 2 except that toluene was changed to methylene chloride.

(Example 7)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 2 except that hydroxyethylallene was changed to 2- (perfluorooctyl) ethyl-2,3-butadienyl ether.

(Example 8)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that 0.5 mmol (0.0950 g) of 1-trimethoxysilyl-1-methoxyallene was used instead of 1-triethoxysilyl-1-methoxyallene. It was.

Example 9
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1, except that 0.5 mmol (0.1250 g) of 1-triethoxysilyl-1-ethoxyallene was used instead of 1-triethoxysilyl-1-methoxyallene. It was.

(Example 10)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that 0.5 mmol (0.1485 g) of 1-triethoxysilyl-1-phenoxyallene was used instead of 1-triethoxysilyl-1-methoxyallene. It was.

(Example 11)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that the addition amount of 1-triethoxysilyl-1-methoxyallene was changed to 0.25 mmol (0.0588 g).

(Example 12)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that the addition amount of 1-triethoxysilyl-1-methoxyallene was changed to 0.75 mmol (0.1763 g).

(Example 13)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that the amount of ethanol added was 12.5 g (10 mL).

(Example 14)
Silicon-containing polymer fine particles were obtained in the same manner as in Example 1 except that 12.5 g (10 mL) of methanol was added instead of 1.25 g (1 mL) of ethanol.

(Comparative Example 1)
A stir bar was placed in a 5 mL test tube and purged with nitrogen. Thereafter, 0.01 mmol (0.0025 g) of 3-methacryloxypropyltrimethoxysilane, 1 mL (1.25 g) of ethanol, and 0.01 mL (0.01 g) of 1N aqueous ammonia were added, and the reaction was performed for 24 hours. Thereafter, 0.001 mmol (0.00016 g) of azobisisobutyronitrile was added, heated to 70 ° C., and subjected to a polymerization reaction for 24 hours to obtain silicon-containing polymer fine particles.

(Comparative Example 2)
20 mg of 1.3 μm polystyrene particles synthesized by soap-free polymerization as seed particles are dispersed in 0.83 mL (0.83 g) of pure water, and 0 containing dibutyl phthalate 46.5 μL (46.5 μg) and benzoyl peroxide 5 mg. A 36% aqueous sodium lauryl sulfate solution (4.2 g) was added, and the mixture was stirred at 30 ° C. for 3 hours. Furthermore, 62 mL (62 g) of 0.8% polyvinyl alcohol aqueous solution containing 6 mL (5.64 g) of methyl methacrylate and 6 mL (6.24 g) of 3-methacryloxypropyltrimethoxysilane was added, and the mixture was stirred at 30 ° C. for 3 hours. Swelled. Subsequently, radical polymerization was performed at 80 ° C. for 15 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 5 mL (5 g) of 0.01N hydrochloric acid was added, and the methoxy group in 3-methacryloxypropyltrimethoxysilane used above was hydrolyzed at 70 ° C. for 3 hours. Aqueous ammonia 0.5 mL (0.5 g) was added and condensed again at 70 ° C. for 3 hours to obtain silicon-containing polymer fine particles.

(Comparative Example 3)
Polymer fine particles not containing silicon were obtained in the same manner as in Example 1 except that 0.5 mmol (0.042 g) of hydroxyethylallene was used instead of 1-triethoxysilyl-1-methoxyallene.

(Comparative Example 4)
In a rubbed test tube with a three-way cock, 0.30 g of poly (N-vinylpyrrolidone) as a dispersion stabilizer and butyl lithium (6.4 mg, 0.10 mmol) as a polymerization catalyst were added, and nitrogen substitution was performed.
Dry toluene (10.0 mL, 8.6 g) was added as a polymerization medium to obtain a butyllithium catalyst solution.
To the resulting butyllithium catalyst solution, hydroxyethylallene (SP value 10.4 (cal / cm ³ ) ^0.5 , 0.84 g, 10 mmol) was added and stirred at 23 ° C. for 1 hour at 350 rpm. By carrying out polymerization, hydrophilic resin particles were obtained.

(Evaluation)
(1) Measurement of average particle diameter Arbitrary 50 particles were observed with a transmission electron microscope, and the number average particle diameter and the CV value of the particle diameter measured with a caliper were measured. Moreover, the structure of the particle | grains obtained by observation by visual observation was determined.
In addition, about the particle | grains obtained in Examples 2-7, the photograph image | photographed using the transmission electron microscope is shown in FIGS.

(2) Measurement of molecular weight distribution The weight average molecular weight and molecular weight distribution of the resin constituting the particles were measured by the following methods. Using column LF-804 manufactured by SHOKO as a column, analysis by gel permeation chromatography is performed, and weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene are calculated. Ratio (Mw / Mn)) was measured.

(3) Measurement of heat resistance 0.1 g of the obtained particles are weighed and put into a crucible, taken out after heating at 500 ° C. for 6 hours in a muffle furnace, weighed again, the weight of particles before heating (a) and after heating From the particle weight (b), the residual ash content was measured using the following formula.
Residual ash content = b / a × 100 (%)
The obtained residual ash content was evaluated according to the following criteria.

XX: 20% or more XX: 5% or more and less than 20% ◯: 1% or more and less than 5% ×: less than 1%

According to the present invention, a silicon-based polymer composite particle having a small particle diameter can be obtained, the molecular weight and the particle diameter can be controlled uniformly, and a deformed structure such as a solid structure, a core-shell structure, or a hollow structure can be obtained. A method for producing silicon-containing polymer particles capable of producing silicon-containing polymer particles can be provided.

Claims (5)

A method for producing silicon-containing polymer fine particles, comprising a step of conducting living polymerization using an alkoxysilyl group-substituted allene monomer. The method for producing fine silicon-containing polymer particles according to claim 1, wherein the alkoxysilyl group-substituted allene monomer has three alkoxysilyl groups. Alkoxysilyl group-substituted allene monomers are 1-triethoxysilyl-1-methoxyallene, 1-trimethoxysilyl-1-methoxyallene, 1-triethoxysilyl-1-ethoxyallene, 1-trimethoxysilyl-1-ethoxy Allene, 1-triethoxysilyl allene, 1-trimethoxysilyl allene, 1-triethoxysilyl-1-methyl allene, 1-trimethoxysilyl-1-methyl allene, 1-triethoxysilyl-1-phenoxy allene, 1 It is at least one selected from the group consisting of -trimethoxysilyl-1-phenoxyallene, 1-triethoxysilyl-1-phenylallene, and 1-trimethoxysilyl-1-phenylallene The method for producing silicon-containing fine polymer particles according to claim 1. 2. The method for producing silicon-containing polymer fine particles according to claim 1, wherein the living polymerization is carried out by a dispersion polymerization method. Step 1 of living coordination polymerization using an alkoxysilyl group-substituted allene monomer;
Step 2 of copolymerizing the polymer of the alkoxysilyl group-substituted allene monomer with another allene monomer other than the alkoxysilyl group-substituted allene monomer
The method for producing silicon-containing fine polymer particles according to claim 1, wherein: