JP4451204B2 - Composite and production method thereof - Google Patents

Description

  The present invention relates to a composite containing a silicon-containing polymer and a method for producing the same.

  As one of the methods for modifying a polymer substance, there is a compounding with an inorganic substance. As one of the techniques, a so-called sol-gel method has been tried. Specifically, attempts have been made to perform hydrolysis and polycondensation of metal alkoxides in the presence of a polymer substance or in a polymerization system of raw material monomers of the polymer substance. According to this method, a composite composed of a polymer substance and a metal oxide (for example, silica) can be obtained. This method has been attempted for various polymer materials such as olefin polymers, acrylic polymers, vinyl alcohol polymers, and siloxane polymers.

  In recent years, application to coating applications has been energetically studied. For example, composites composed of a vinyl alcohol polymer and a metal oxide have been disclosed (for example, see Patent Documents 1 and 2).

As another example, a method of forming a coating film by hydrolytic condensation of tetraethoxysilane in the presence of a vinyltrimethoxysilane radical polymer is disclosed (see Non-Patent Document 1).
JP-A-8-99390 JP-A-9-278968 Journal of the Ceramic Society of Japan, Vol. 105, p555 (1997)

  Currently, further improvements in properties are desired for conventional composites containing metal oxides and polymeric substances. For example, a composite used for a coating film is required to further improve mechanical properties.

  In view of such a situation, an object of the present invention is to provide a composite having excellent mechanical properties such as bending strength and a method for producing the same.

  As a result of studies to achieve the above object, the present inventors have found that a composite having excellent mechanical properties can be obtained by using a specific silicon-containing polymer and a specific metal-containing compound. The present invention is based on this new finding.

The first complex of the present invention is a complex comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer, wherein the compound (I) is at least one selected from a halogen atom and an alkoxy group. one group of atoms is at least one compound containing silicon bonded is, the silicon-containing polymer, monomer (a) derived from the structural unit (a) and structural units derived from the monomer (B) The monomer (A) is at least one compound represented by the following formula (1), and the monomer (B) is represented by the following formula (2): At least one compound represented.

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

［式中、Ｒ ⁵ およびＲ ⁶ はそれぞれ独立に水素原子またはアルキル基である。Ｒ ⁷ およびＲ ⁸ はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、水酸基および（ＣＲ ⁹ ＝ＣＨ ₂ ）で表される基（ただしＲ ⁹ は水素原子またはアルキル基である）から選ばれる１つの原子団である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]

Moreover, the 2nd composite_body | complex of this invention is a composite_body | complex containing the oxide of silicon and a silicon-containing polymer, Comprising: The said silicon-containing polymer is a structural unit (A) derived from a monomer (A). ) And the structural unit (B) derived from the monomer (B), and the monomer (A) is at least one compound represented by the above formula (1), and the monomer (B) is at least one compound represented by the above formula (2) .
The third complex of the present invention is a complex comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer, and the compound (I) is selected from a halogen atom and an alkoxy group. It is at least one compound containing silicon to which at least one atomic group is bonded, and the silicon-containing polymer is derived from a structural unit (A) derived from the monomer (A) and a monomer (B). The monomer (A) is at least one compound represented by the above formula (1), and the monomer (B) comprises two or more carbon- And at least a part of the plurality of structural units (A) contained in the silicon-containing polymer is a condensed and / or silyl group having the atomic group (G). Or it is hydrolytically condensed.
Moreover, the 4th composite_body | complex of this invention is a composite_body | complex containing the oxide of silicon and a silicon-containing polymer, Comprising: The said silicon-containing polymer is a structural unit (A) derived from a monomer (A). ) And the structural unit (B) derived from the monomer (B), and the monomer (A) is at least one compound represented by the above formula (1), and the monomer (B) is at least one compound containing two or more carbon-carbon double bonds, and in at least some of the plurality of structural units (A) contained in the silicon-containing polymer, The silyl group having (G) is condensed and / or hydrolyzed.

［式中、Ｒ ¹ は水素原子またはアルキル基である。Ｒ ² 、Ｒ ³ およびＲ ⁴ はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ ² 、Ｒ ³ およびＲ ⁴ から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

［式中、Ｒ ⁵ およびＲ ⁶ はそれぞれ独立に水素原子またはアルキル基である。Ｒ ⁷ およびＲ ⁸ はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、水酸基および（ＣＲ ⁹ ＝ＣＨ ₂ ）で表される基（ただしＲ ⁹ は水素原子またはアルキル基である）から選ばれる１つの原子団である。］ The first method of the present invention for producing a composite is a method of polymerizing a plurality of types of monomers including a monomer (A) and a monomer (B) to obtain a silicon-containing polymer. A mixture comprising a first step, at least one selected from compound (I), a hydrolyzate of compound (I) and a hydrolysis condensate of compound (I), the silicon-containing polymer, and a solvent. A second step of preparation. The monomer (A) is at least one compound represented by the following formula (1), and the monomer (B) is at least one compound represented by the following formula (2) . The compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]

Moreover, the second method of the present invention for producing a composite is to obtain a silicon-containing polymer by polymerizing plural kinds of monomers including the monomer (A) and the monomer (B). A mixture comprising a first step, at least one selected from compound (I), a hydrolyzate of compound (I) and a hydrolysis condensate of compound (I), the silicon-containing polymer, and a solvent. The monomer (A) is at least one compound represented by the above formula (1), and the monomer (B) comprises two or more carbon- It is at least one compound containing a carbon double bond, and the polymerization is carried out at a temperature of 80 ° C. or higher in the presence of a polymerization initiator having an activation energy for decomposition of 30 kcal / mol or higher. ) Is a small amount selected from a halogen atom and an alkoxy group Both of at least one compound containing a silicon single atomic groups bonded.

  The composite obtained by the production method of the present invention constitutes another aspect of the composite of the present invention. The lump of the present invention consists of the complex of the present invention.

  According to the present invention, a composite that is transparent and excellent in mechanical properties such as bending strength and compressive strength can be obtained. The composite of the present invention can be used as a substitute for a metal material in a specific field.

  Embodiments of the present invention will be described below. In the following description, specific compounds are exemplified as compounds that exhibit a specific function, but the present invention is not limited to these. Moreover, as long as there is no description in particular, the illustrated material may be used independently and may be used in combination of 2 or more type.

(Complex)
The composite of the present invention is a composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer.

Compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded. As shown in the so-called sol-gel method, silicon of compound (I) is linked via oxygen by a hydrolysis condensation reaction. When this hydrolysis-condensation reaction proceeds sufficiently, the hydrolysis-condensation product of compound (I) substantially becomes a silicon oxide (for example, silicon oxide particles having a functional group on the surface). The hydrolyzed condensate of the compound (I) in the present invention includes a product obtained by partially hydrolyzing and condensing the compound (I). The present invention encompasses hydrolyzed condensate of the compound (I), the complex is an oxide of silicon, i.e., a complex containing the oxides of silicon and silicon-containing polymer. In the latter case, “hydrolysis condensate of compound (I)” can be read as “ silicon oxide” in the following description of the composite.

Since compound (I) is at least one compound containing silicon (Si), a highly transparent composite can be obtained. Si may be classified as a similar metal element, but in this specification, it will be described as a metal element. In addition to the hydrolysis condensate of compound (I), a hydrolysis condensate of a compound containing phosphorus (P) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded may be used. In addition to the hydrolysis condensate of compound (I), a hydrolysis condensate of a compound containing boron (B) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded may be used.

  Examples of the halogen atom contained in the compound (I) include chlorine and bromine. Examples of the alkoxy group contained in the compound (I) include a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, a butoxy group, and a t-butoxy group.

Examples of the atomic group bonded to silicon other than the halogen atom and the alkoxy group include an alkyl group. The number of atomic groups bonded to silicon is equal to the valence of silicon . In a typical example, the atomic group bonded to silicon consists of only a halogen atom, only an alkoxy group, or only a halogen atom and an alkoxy group. Such compound (I) is represented by the following formula.

M (OR) _mn X _n
[Wherein, M represents a silicon atom. R represents an alkyl group (carbon number is preferably 6 or less). X represents a halogen atom. m is equal to the valence of the silicon atom M. n is an integer of 0 or more and m or less. ]

Specific examples of the compound (I) include silicon alkoxides such as tetramethoxysilane, tetraethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; tetra And halogenated silanes such as chlorosilane and tetrabromosilane .

  Hereinafter, the silicon-containing polymer contained in the composite of the present invention will be described. The silicon-containing polymer is a copolymer containing a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B). The monomer (A) is at least one compound represented by the following formula (1).

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

Examples of the alkyl group applicable to R ¹ , R ² , R ³ and R ⁴ include alkyl groups such as a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ² , R ³ and R ⁴ include chlorine and bromine. Examples of the alkoxy group applicable to R ² , R ³ and R ⁴ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; benzyloxy group And aralkyloxy groups such as In a typical example of R ^{2 to} R ⁴ , R ² , R ³ and R ⁴ are each independently a halogen atom or an alkoxy group.

At least one selected from R ² , R ³ and R ⁴ is preferably a halogen atom or an alkoxy group. In monomer (A-1) which is a preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are halogen atoms. In monomer (A-2) which is another preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are alkoxy groups. In monomer (A-3), which is another preferred example of monomer (A), R ¹ is a hydrogen atom, R ^{2 to} R ⁴ are either an alkoxy group or a halogen atom, and at least 1 One is an alkoxy group and at least one is a halogen atom. Specific examples of the monomer (A) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyldiethoxyethylsilane. Vinylethoxydimethylsilane, vinylethoxydiethylsilane, vinyltris (2-methoxyethoxy) silane, and vinyltrichlorosilane.

  Examples of the monomer (B) include triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate, divinyl adipate, divinyl succinate, divinyl ether, divinyl sulfone, divinyl phthalate, diallyl phthalate, and divinyl. Benzene or the compounds described below can be mentioned.

The monomer (B) is a group represented by (CR ⁵ ═CH ₂ ) (where R ⁵ is a hydrogen atom or an alkyl group) and a group represented by (CR ⁶ ═CH ₂ ) (where R ^{6 is} R ^6). Is preferably a hydrogen atom or an alkyl group) and is preferably at least one compound containing a silicon atom to which is bonded. In this case, the monomer (B) includes two or more vinyl groups (including the case where R ⁵ and / or R ⁶ is an alkyl group) bonded to a silicon atom. Since such a compound contains two carbon-carbon double bonds, a polymer having a crosslinked structure introduced into the main chain can be obtained by using the compound. In particular, when using a monomer in which a group represented by (CR = CH ₂ ) (where R is a hydrogen atom or an alkyl group) is directly bonded to a silicon atom, the monomer (B) and By improving the polymerizability with the monomer (A), a silicon-containing polymer having a higher molecular weight can be obtained, and when a crosslinked structure is introduced, the silicon-containing polymer in which the main chain of the polymer is strongly constrained Since a polymer is obtained, the effect of improving the mechanical properties of a composite containing the polymer is obtained.

  Moreover, it is preferable that a monomer (B) is at least 1 type of compound represented by the following formula | equation (2).

［式中、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子またはアルキル基である。Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、水酸基および（ＣＲ⁹＝ＣＨ₂）で表される基（ただしＲ⁹は水素原子またはアルキル基である）から選ばれる１つの原子団である。］

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]

At least one selected from R ⁷ and R ⁸ is preferably a halogen atom, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ), and particularly preferably a halogen atom or an alkoxy group. preferable.

Examples of the alkyl group applicable to R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ⁷ and R ⁸ include chlorine and bromine. Examples of the alkoxy group applicable to R ⁷ and R ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; aralkyl such as benzyloxy group An oxy group is mentioned.

Examples of the monomer (B) represented by the formula (2) will be described below. In the first monomer (B-1), at least one of R ⁷ and R ⁸ is an alkoxy group, and preferably R ⁷ and R ⁸ are both alkoxy groups. In the second monomer (B-2), at least one of R ⁷ and R ⁸ is a halogen atom, and preferably R ⁷ and R ⁸ are both halogen atoms. In the third monomer (B-3), R ⁷ is a vinyl group, and R ⁸ is an alkoxy group, a halogen atom, or an alkyl group. In the monomers (B-1) to (B-3), R ⁵ and R ⁶ may be a hydrogen atom or an alkyl group.

  Specific examples of the compound represented by the formula (2) include, for example, diethoxydivinylsilane, dimethoxydivinylsilane, methoxymethyldivinylsilane, dichlorodivinylsilane, methyltrivinylsilane, chlorotrivinylsilane, methoxytrivinylsilane, ethoxytrivinylsilane. Is mentioned.

  The monomer (A) described above and the monomer (B) described above can be polymerized in any combination. For example, the monomer (A-1) and the monomer (B-1), (B-2), or (B-3) may be combined. Moreover, you may combine a monomer (A-2) and a monomer (B-1), (B-2), or (B-3). Moreover, you may combine a monomer (A-3) and a monomer (B-1), (B-2), or (B-3). An example of such a combination is shown in the examples. The combination of structural units constituting the silicon-containing polymer is determined according to the combination of monomers at the time of polymerization.

  The monomer (A), the monomer (B) and the compound (I) may be commercially available or synthesized by a known method.

  The preferred proportion of the structural unit (A) and the structural unit (B) in the total structural unit of the silicon-containing polymer is determined depending on the types of the monomer (A) and the monomer (B) as materials and the silicon content to be obtained. Since it changes according to the purpose of use of the composite containing the polymer, it cannot be generally defined. In a typical example, the ratio of the structural unit (A) to the total structural unit of the silicon-containing polymer is in the range of 70 to 99.5 mol%, and the structural unit (B ) Is preferably in the range of 0.5 to 30 mol%. The molar ratio of structural unit (A) / structural unit (B) is in the range of 70/30 to 99.5 / 0.5. By setting the molar ratio of structural unit (A) / structural unit (B) within this range, gelation during polymerization can be prevented and a high molecular weight polymer can be obtained. Moreover, this molar ratio becomes like this. Preferably it is the range of 85 / 15-97 / 3, More preferably, it is the range of 85 / 15-95 / 5.

  The silicon-containing polymer contained in the composite of the present invention typically comprises only the structural unit (A) and the structural unit (B), or substantially comprises only the structural unit (A) and the structural unit (B). However, as long as the effect of the present invention is obtained, other structural units may be included.

  The silicon-containing polymer preferably has a number average molecular weight of 10,000 or more, more preferably 12000 or more, and further preferably 15000 or more. When the number average molecular weight is 10,000 or more, the mechanical properties (for example, bending strength and compressive strength) of the composite containing the silicon-containing polymer are particularly good. The upper limit of the number average molecular weight is not particularly limited, but is preferably within a range that dissolves in the above-described polar organic solvent. The number average molecular weight and the weight average molecular weight referred to in the present specification are values in terms of polystyrene measured by GPC (Gel Permeation Chromatography) as described in Examples.

  Further, the molecular weight distribution of the silicon-containing polymer, that is, the value represented by the ratio “Mw / Mn” of the weight average molecular weight Mw and the number average molecular weight Mn is preferably 2 to 15, more preferably 3 to 12. More preferably, it is the range of 4-12. When the molecular weight distribution is in a preferred range, the mechanical properties of the resulting composite are good.

  In the complex of the present invention, the ratio of the hydrolysis condensate of compound (I) contained in the complex is preferably in the range of 1.5% by weight to 70% by weight. By setting it as this range, the composite_body | complex excellent in mechanical physical properties, such as bending strength, can be obtained. The ratio is more preferably in the range of 2.5 to 60% by weight, and further preferably in the range of 5 to 50% by weight.

  The proportion of the silicon-containing polymer contained in the composite is preferably in the range of 15 to 97% by weight. By setting it as this range, the composite_body | complex excellent in mechanical physical properties, such as bending strength, can be obtained. The ratio is more preferably in the range of 20 to 95% by weight, and further preferably in the range of 25 to 90% by weight.

Since the silicon-containing polymer contained in the composite of the present invention has a plurality of structural units (A) derived from the monomer (A), it has at least one atomic group (G). It has a plurality of silyl groups. In the composite of the present invention, the silyl group having the atomic group (G) is condensed and / or hydrolyzed with another functional group in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer. Condensation is preferred. At least a part of the silyl group having the atomic group (G) may be condensed directly with another functional group or may be condensed after hydrolysis. When the silyl group having the atomic group (G) is condensed and / or hydrolytically condensed, mechanical properties such as bending strength are improved. The other functional group to which the silyl group having the atomic group (G) is condensed and / or hydrolyzed is a functional group contained in the hydrolytic condensate of the compound (I) (or a function present on the surface of the silicon oxide). Group), but may be another functional group in the silicon-containing polymer (for example, a silyl group having one atomic group (G) and a silyl group having another atomic group (G)). And / or hydrolytic condensation). The condensation of the silyl group having the atomic group (G) of the structural unit (A) can be confirmed by measuring the spectrum of silicon by solid-state NMR.

  When the structural unit (B) in the silicon-containing polymer has a silyl group directly bonded to a functional group that can contribute to condensation and / or hydrolysis condensation of a halogen atom, an alkoxy group, a hydroxyl group, etc., At least a part of these silyl groups may be condensed and / or hydrolytically condensed with other functional groups as in the case of the silyl group having the atomic group (G) in the structural unit (A).

  The complex of the present invention is typically composed of only the hydrolysis condensate of compound (I) and the silicon-containing polymer, or substantially only of these, but other substances may be used as long as the effects of the present invention can be obtained. May be included. For example, the composite of the present invention may be made of other materials such as polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, styrenic block copolymer, etc. A polymer may be included. The composite of the present invention further comprises a stabilizer, a lubricant, a pigment, an impact resistance improver, a processing aid, a crystal nucleating agent, a reinforcing agent, a colorant, a flame retardant, a weather resistance improver, an ultraviolet absorber, and an antioxidant. Agents, hydrolysis resistance improvers, fungicides, antibacterial agents, light stabilizers, antistatic agents, silicone oil, antiblocking agents, mold release agents, foaming agents, fragrances, etc .; glass fibers, polyester fibers Ingredients such as various fibers such as talc, silica, wood powder, and various coupling agents may be included.

  The composite of the present invention contains a hydrolyzed condensate of compound (I) and a silicon-containing polymer, and is characterized by high mechanical properties such as hardness and bending strength and high translucency. In particular, when the hydrolysis condensate of compound (I) and the silicon-containing polymer are condensed (bonded), particularly excellent mechanical properties are exhibited. According to the present invention, it is possible to obtain a composite having a three-point bending strength of 100 MPa or more.

  The composite of the present invention can be used in the form of a lump or thin film. The lump of the present invention is transparent and hard, and is excellent in mechanical properties such as bending strength. Therefore, it can be preferably used as a material for dental, optical and electric / electronic parts. The lump of the present invention is suitable as a cutting material (for example, a denture material). The lump of the present invention can have a size of 0.4 cm square or more. The composite of the present invention can be used for various applications such as paints, inks, adhesives, pressure-sensitive adhesives, compatibilizing agents, and sealing materials.

(Production method of composite)
Hereinafter, a method for producing the composite will be described. According to the production method of the present invention, the above-described composite can be produced. The composite manufactured by the manufacturing method of the present invention constitutes another aspect of the composite of the present invention.

The production method of the present invention includes a first step of obtaining a silicon-containing polymer by polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B). Further, this production method comprises at least one selected from compound (I), a hydrolyzate of compound (I), and a hydrolyzed condensate of compound (I), and the silicon-containing polymer obtained in the first step. A second step of preparing a mixture comprising a solvent. The monomer (A) is at least one compound represented by the above formula (1). The monomer (B) is at least one compound containing two or more carbon-carbon double bonds. Compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded.

  Since the compound applicable to the monomer (A) and the monomer (B) and the combination thereof have been described above, redundant description will be omitted. Moreover, since the compound applicable to compound (I) was also mentioned above, the overlapping description is abbreviate | omitted.

  First, the first step (polymerization step) for obtaining a silicon-containing polymer will be described. The first step can be performed according to a known polymerization method such as anionic polymerization, cationic polymerization, radical polymerization, etc., but is preferably performed by radical polymerization. When carried out by radical polymerization, the polymerization step is preferably carried out at a temperature of 80 ° C. or higher in the presence of a polymerization initiator. The polymerization initiator to be used is not particularly limited, but the activation energy for the decomposition of the polymerization initiator is preferably 30 kcal / mol or more. The activation energy is more preferably 35 kcal / mol or more. Specific examples of the polymerization initiator having an activation energy of 30 kcal / mol or more include cumene hydroperoxide, t-butyl hydroperoxide, sec-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide. , T-amyl peroxide, t-butyl-α-cumyl peroxide, 1,4-dimethylhydroperoxide, t-butyl perbenzoate, 2,2′-azobis (2-methylpropane), 1,1′- And azobis (cyclohexane-1-carbonitrile). In particular, the polymerization step is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator, and the polymerization initiator is cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide. It is preferably at least one selected from oxide, t-butyl perbenzoate, and 1,1′-azobis (cyclohexane-1-carbonitrile). These polymerization initiators have a decomposition activation energy of 35 kcal / mol or more.

  The amount of the polymerization initiator used is preferably in the range of 0.01 to 0.5 mol, more preferably 0.02 to 0.2 mol, per mol of all the monomers (plural types of monomers). More preferably, it is the range of 0.03-0.1 mol. When the usage-amount of a polymerization initiator exists in a preferable range, a higher molecular weight silicon-containing polymer is easy to be obtained.

  The preferred proportion of monomer (A) and monomer (B) in all monomers (plural monomers) is the type of monomer (A) and monomer (B) and the resulting composite Since it changes according to the purpose of use of the body, it cannot be specified unconditionally. In a typical example, the ratio of the monomer (A) in the total monomer (a plurality of monomers) is in the range of 70 to 99.5 mol%, and the monomer ( The proportion of B) is in the range of 0.5 to 30 mol%. The molar ratio of monomer (A) / monomer (B) is preferably in the range of 70/30 to 99.5 / 0.5, more preferably in the range of 85/15 to 97/3. More preferably, it is in the range of 85/15 to 95/5.

  In the first step in the present invention, typically, only monomer (A) and monomer (B), or substantially only monomer (A) and monomer (B) are polymerized. However, as long as the effect of the present invention is obtained, another monomer different from the monomer (A) and the monomer (B) may be polymerized.

  In the first step of the present invention, the polymerization step may be performed by bulk polymerization without using a solvent, or the polymerization step may be performed in the presence of a solvent. When carrying out the polymerization step in the presence of a solvent, it is preferable to use an organic solvent as the solvent. As the organic solvent, for example, dioxane, chlorobenzene, methyl benzoate, toluene, xylene, mesitylene, decalin, ethylene glycol dimethyl ether, and acetonitrile can be used.

  When the polymerization step is carried out in the presence of a solvent, a polymerizable mixture containing the monomer (A), the monomer (B) and an organic solvent is prepared. During the polymerization step, the mixture is preferably bubbled with an inert gas. Moreover, it is preferable to perform a superposition | polymerization process in inert gas atmosphere. For example, nitrogen gas or argon gas can be used as the inert gas. The temperature of the mixture in the polymerization step is preferably adjusted to 80 ° C. or higher, and more preferably adjusted to 100 ° C. or higher (for example, 120 ° C. or higher). The temperature of the mixture is preferably adjusted to 50 ° C. or less of the boiling point of the monomer (A), and more preferably adjusted to 40 ° C. or less (eg, 30 ° C. or less) of the boiling point of the monomer (A). .

  The polymerization initiator may be mixed in advance with the monomer (A) or the monomer (B), or may be added to the above-described polymerizable mixture. The total amount of the polymerization initiator may be added at once, or may be added in several divided portions. Although there is no particular limitation on the timing of adding the polymerization initiator, it is preferable to add the polymerization initiator after starting bubbling with an inert gas. The polymerization initiator may be added after adjusting the mixture to the polymerization temperature, or may be added before adjusting the mixture to the polymerization temperature. In particular, when using a polymerization initiator having an activation energy of 30 kcal / mol or less, it is preferable to add the polymerization initiator after adjusting the mixture to the polymerization temperature.

  In the first step of the present invention, the monomer (A) and the monomer (B) are copolymerized, and the presence of the monomer (B) dramatically increases the molecular weight of the resulting silicon-containing polymer. Can be large. In the first step of the present invention, a silicon-containing polymer having a number average molecular weight of 10,000 or more, more preferably 12000 or more, and further preferably 15000 or more can be obtained. In addition, by using a monomer containing a silicon atom as the monomer (B), the properties (for example, bending strength and compressive strength) expected for a composite containing a silicon-containing polymer to be obtained are high. A complex is obtained.

  The production method of the present invention may further include a step of removing a component dissolved in the hydrocarbon solvent from the silicon-containing polymer obtained by the polymerization step. According to this step, since the low molecular weight component dissolved in the hydrocarbon solvent can be removed, a silicon-containing polymer having a higher number average molecular weight, for example, a silicon-containing polymer having a number average molecular weight of 15000 or more is obtained. The low molecular weight component can be removed, for example, by immersing the silicon-containing polymer in a hydrocarbon solvent and then performing filtration. A high molecular weight silicon-containing polymer is usually not soluble in a hydrocarbon solvent and can be easily separated by filtration. The silicon-containing polymer having a larger number average molecular weight thus obtained is usually a polar organic solvent (for example, tetrahydrofuran; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; methanol, ethanol, propanol, ethylene glycol, etc.) A polymer that dissolves in alcohol, chloroform, dimethyl sulfoxide, acetone, sulfolane, etc.) and is not produced by gelation (hydrolytic condensation reaction between polymers).

  The hydrocarbon solvent is a solvent composed of hydrocarbon, and for example, at least one selected from n-hexane, cyclohexane, n-heptane, toluene, benzene and xylene can be used. Among these, n-hexane is preferable. The amount of the hydrocarbon solvent to be used is not particularly limited, but it is preferably 5 to 100 times the weight of the silicon-containing polymer, more preferably 10 to 50 times the weight. The temperature of the hydrocarbon solvent to be used is not particularly limited, but when the boiling point of the hydrocarbon solvent is T ° C., the temperature is preferably in the range of 20 ° C. to T ° C., and 20 ° C. to (T-20) ° C. A range is more preferable. The time for immersing the silicon-containing polymer in the hydrocarbon-based solvent is not particularly limited, but it is preferably immersed for 30 minutes or more, and more preferably for 60 minutes or more. The immersion of the silicon-containing polymer in the hydrocarbon solvent is preferably performed with stirring or shaking.

  Hereinafter, the second step will be described. In the following description, the compound (I), the hydrolyzate of the compound (I), and the hydrolysis condensate of the compound (I) may be collectively referred to as the compound (I) component. The hydrolyzate of compound (I) includes a product obtained by partially hydrolyzing compound (I) and a product obtained by completely hydrolyzing compound (I). The hydrolyzed condensate of compound (I) includes those obtained by partially hydrolyzing and condensing compound (I) and those obtained by completely hydrolyzing and condensing compound (I).

  Hydrolysis and / or hydrolysis condensation of compound (I) may occur with some functional groups or with all functional groups. The hydrolyzate and / or hydrolysis condensate of compound (I) can be produced by a known method, for example, a method used in a sol-gel method. An example of the method for producing the hydrolyzate and / or hydrolysis condensate of compound (I) will be described below.

  First, a reaction solution containing an organic solvent, water, compound (I), and, if necessary, a catalyst is prepared. The reaction solution can be prepared, for example, by dissolving compound (I) in an organic solvent and then adding water and a catalyst. In the prepared reaction solution, the compound (I) is hydrolyzed and / or hydrolyzed and condensed to form a solution composed of the component (I) and a solvent (hereinafter sometimes referred to as “solution (Sa)”). can get. The degree of condensation of the hydrolyzed condensate of compound (I) can be controlled by the amount of organic solvent and water used, the temperature of the reaction solution, and the like.

The organic solvent is not particularly limited as long as it is a solvent in which compound (I) is dissolved. For example, alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used, and when a compound containing silicon bonded to an alkoxy group is used as compound (I), the same kind as the alkoxy group contained in compound (I) Alcohol having the molecular structure (alkoxy component) is more preferably used. For example, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent used is not particularly limited, but the concentration of compound (I) in the reaction solution is preferably in the range of 1 to 90% by weight, more preferably 10 to 80% by weight, More preferably, it is in the range of 60% by weight.

  The preferred amount of water used for hydrolysis and / or hydrolysis condensation of compound (I) varies depending on the type of compound (I) and the desired hydrolyzate and / or hydrolysis condensate, but usually, It is preferably in the range of 0.05 to 10 mol, based on 1 mol of the alkoxy group or halogen atom of compound (I) used (the total when both are mixed), and 0.1 to 4 mol The range is more preferable, and the range of 0.2 to 3 mol is more preferable. When the amount of water used is in this range, the resulting composite is excellent in mechanical properties such as bending strength and compressive strength. In addition, when adding a component containing water, for example, when adding hydrochloric acid as a catalyst as described later, the amount of water added may be determined in consideration of the amount of water introduced by the component. preferable.

The catalyst used for hydrolysis and / or hydrolysis condensation of compound (I) is not particularly limited, and an acid catalyst or an alkali catalyst can be used. Among these, it is preferable to use an acid catalyst. As the acid catalyst, a known acid catalyst can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, and maleic acid can be used. . Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable. The preferred amount of the acid catalyst to be used varies depending on the kind of the catalyst to be used, etc., but is usually preferably in the range of 1 × 10 ⁻⁵ to 10 mol, more preferably 1 mol of the silicon atom of the compound (I) used. Is in the range of 1 × 10 ^{−4 to} 5 mol, more preferably in the range of 5 × 10 ⁻⁴ to 1 mol. When the amount of the acid catalyst used is within this range, a composite having excellent mechanical properties such as bending strength and compressive strength can be obtained.

  The temperature of the reaction solution when performing the hydrolysis and / or hydrolysis condensation reaction of compound (I) is not particularly limited, but is usually in the range of 2 to 100 ° C, preferably in the range of 4 to 60 ° C, More preferably, it is the range of 6-50 degreeC. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.1. It is in the range of ~ 6 hours. The atmosphere of the reaction system is not particularly limited, and an atmosphere such as an air atmosphere, a carbon dioxide atmosphere, a nitrogen stream, or an argon atmosphere can be employed.

  In the second step, a mixture containing the compound (I) component, the silicon-containing polymer, and the solvent (hereinafter sometimes referred to as the mixture (S)) is prepared. The method for preparing the mixture (S) is not particularly limited, and for example, the mixture (S) can be prepared by adding a silicon-containing polymer to the solution (Sa). The silicon-containing polymer may be added as it is, or may be added in the form of a solution in which it is dissolved (hereinafter sometimes referred to as “solution (Sb)”). The method for mixing the solution (Sa) and the solution (Sb) is not particularly limited. However, in order to obtain a uniform mixture, it is preferable to mix and stir them. When producing the mixture (S) by this method, the solvent contained in the mixture (S) is an organic solvent contained in the solution (Sa), a solvent in the solution (Sb), or a mixed solvent of both.

  The solvent of the solution (Sb) is not particularly limited as long as it is a solvent in which the silicon-containing polymer is dissolved. For example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; Glycerin; acetonitrile; dimethylformamide; dimethyl sulfoxide; sulfolane and the like can be used alone or in combination. Among these, alcohols such as methanol and ethanol are preferable. Although there is no limitation in particular in the usage-amount of a solvent, it is preferable that it is the quantity from which the density | concentration of a silicon containing polymer will be 1-50 weight% (more preferably 5-30 weight%, for example 5-20 weight%).

In the second step of the present invention, compound (I) that has not undergone hydrolysis or hydrolysis condensation can be used as the component (I). Even when such a compound (I) is used, the method for preparing the mixture (S) is not particularly limited. For example, a silicon-containing polymer and water and optionally a catalyst are added to a solution in which the compound (I) is dissolved. Can be prepared. The silicon-containing polymer may be added as it is, or may be added in the form of a solution (solution (Sb)) as described above. There is no particular limitation on the method of mixing the solution in which the compound (I) is dissolved, the solution (Sb), water, and optionally the catalyst to be added, but in order to obtain a uniform mixture, these are mixed and stirred. Is preferred. When preparing the mixture (S) by this method, the solvent contained in the mixture (S) is an organic solvent contained in the solution in which the compound (I) is dissolved, a solvent of the solution (Sb), or a mixed solvent of both. . As the organic solvent used in the solution in which the compound (I) is dissolved, the organic solvent used in the solution (Sa) can be used. The preferred amount of water used varies depending on the type of compound (I), etc., but is usually 1 mol of the alkoxy group or halogen atom of compound (I) used (the total when both are present). On the other hand, the range is preferably 0.05 to 10 mol, more preferably 0.1 to 4 mol, and still more preferably 0.2 to 3 mol. When the amount of water used is in this range, the resulting composite is excellent in mechanical properties such as bending strength and compressive strength. Moreover, as a catalyst which can be added by the case, the catalyst quoted in one example of the manufacturing method of the hydrolyzate or hydrolysis-condensation product of compound (I) as mentioned above can be used. The preferred amount of catalyst used varies depending on the type of catalyst used and the like, but is usually preferably in the range of 1 × 10 ⁻⁵ to 10 moles, more preferably, relative to 1 mole of silicon atom of the compound (I) used. The range is 1 × 10 ^{−4 to} 5 mol, and more preferably 5 × 10 ⁻⁴ to 1 mol. When the amount of the catalyst used is within this range, a composite having excellent mechanical properties such as bending strength and compressive strength can be obtained.

  There is a particular limitation on the concentration of solids contained in the mixture (S) obtained in the second step of the present invention (compound (I) component, silicon-containing polymer, and total concentration of solids that can be added, which will be described later). However, it is preferably in the range of 1 to 50% by weight, more preferably in the range of 2 to 30% by weight (for example, in the range of 3 to 15% by weight). By setting the solid content concentration contained in the mixture within this range, a composite having better mechanical properties such as bending strength and compressive strength can be obtained.

  The solid content concentration of the mixture (S) can be controlled at any stage of preparing the mixture (S). For example, the solid content concentration of the solution (Sa) and / or the solution (Sb) may be adjusted in advance so that the solid content concentration of the mixture (S) falls within a preferable range. Moreover, you may adjust solid content concentration of a mixture (S) by adding a solvent after mixing a solution (Sa) and a solution (Sb).

The ratio of the compound (I) component and the silicon-containing polymer contained in the mixture (S) is not particularly limited, but the weight ratio of silicon in the compound (I) component to the weight of the silicon-containing polymer is 0.01. Is preferably in the range of -1.1, more preferably in the range of 0.02-0.7, and still more preferably in the range of 0.05-0.5.

  The mixture (S) may contain other components in addition to the compound (I) component and the silicon-containing polymer. Specifically, the above-described substances may be included as other substances that the complex of the present invention may include.

  After obtaining the mixture (S) in the second step, the complex can be obtained by removing the solvent from the mixture (S). The method for removing the solvent is not limited. For example, the mixture (S) may be poured into a molding die and dried, or may be dried after coating the mixture (S) on a substrate. . By pouring the mixture (S) into a molding die and drying it, lumps having various shapes are obtained. Moreover, a thin film is obtained by coating and drying a mixture (S).

  Drying conditions vary depending on the state of the molded or coated mixture (S). Usually, drying temperature becomes like this. Preferably it is the range of 10-180 degreeC, More preferably, it is the range of 20-160 degreeC (for example, the range of 20-140 degreeC). As the molded product becomes thicker, it is preferable to dry at a lower temperature. The drying temperature in the case of producing a thick molded product by pouring the mixture (S) into a mold is preferably in the range of 10 to 80 ° C, more preferably in the range of 20 to 60 ° C. During drying, it is preferable to control the volatilization rate of the solvent during drying, if necessary. The volatilization rate can be controlled, for example, by adjusting the sealing degree of the dry atmosphere.

  The material of the mold into which the mixture (S) is poured is not particularly limited as long as it functions as a mold, and various plastics such as polymethacrylate, polyacrylate, and polystyrene, metal, glass, gypsum, and the like can be applied. Various shapes of lumps can be obtained by changing the shape of the mold to be molded. For example, lumps of shapes such as prisms, cylinders, sheets, and tubes can be obtained. In the composite of the present invention, a lump of at least 0.4 cm square or more can be obtained. Moreover, when forming into a film on a base material, there is no limitation in particular in the material of a base material, For example, resin, such as a polyethylene terephthalate, metal, glass, a sintered compact, etc. are applicable.

  In the production method of the present invention, in the mixture (S), hydrolysis condensation of the compound (I) component and condensation reaction of the compound (I) component and the silicon-containing polymer (for example, hydrolysis condensation reaction) proceed. In particular, the condensation reaction proceeds in the step of removing the solvent from the mixture (S). By this condensation reaction, a composite having particularly excellent mechanical properties can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the Shin-Etsu Chemical Co., Ltd. thing was used for the silane compound used in the following Examples. Measurements in the following examples were carried out by the following methods.

(1) Measurement of number average molecular weight and weight average molecular weight A silicon-containing polymer was dissolved in tetrahydrofuran so that the concentration was 0.5% by weight, and used as a sample for GPC (Gel Permeation Chromatography) measurement. The measurement of GPC was performed using Shimadzu Corporation Chromatopack CR-4A (main body), RID-6A (refractive index detector), and CIO-6A (column oven). As the column, HSG-4OH (Shimadzu Corporation) was used. Tetrahydrofuran was used as the eluent, and the eluent was allowed to flow at a flow rate of 1.0 mL / min. The column oven was set to 40 ° C. A calibration curve for determining the molecular weight was prepared using polystyrene standard (polystyrene standard sample manufactured by Chemco Co., Ltd.). That is, polystyrene having a known molecular weight was dissolved in tetrahydrofuran so as to have a concentration of 0.5% by weight, GPC measurement was performed, and a calibration curve showing the relationship between elution time and molecular weight was prepared. The number average molecular weight and weight average molecular weight of the silicon-containing polymer were determined from the GPC elution curve (elution time-elution amount) of the silicon-containing polymer and the calibration curve. Further, the molecular weight distribution, that is, the value of “weight average molecular weight / number average molecular weight” was calculated.

(2) Measurement of flexural strength of composites A prism having a size of approximately 4 mm (vertical) x 4 mm (horizontal) x 20 mm (height) made of the composites of Examples and Comparative Examples was produced, and Shimadzu Corporation The three-point bending strength was measured using a manufactured autograph. The measurement was performed by setting the distance between fulcrums to 10 mm and applying a static load at a crosshead speed of 1 mm / min. The bending strength was calculated from the resistance value against the static load when the fracture or crack occurred and the cross-sectional area of the prism used, and the average value of the six specimens was taken as the bending strength value. The cross-sectional area of the prism was determined by measuring the vertical and horizontal dimensions of the prism with calipers.

(3) Measurement of solid-state NMR The complex of the Example and the comparative example was crushed, and a solid-state NMR spectrum of silicon was obtained by CP-MAS method using JNM-DX270 manufactured by JEOL. By observing the absorption spectrum of silicon contained in the polymer in the range of −150 to 30 ppm, at least a part of the structural unit (A) constituting the silicon-containing polymer is condensed and / or hydrolyzed. It was confirmed.

<Example 1>
A silicon-containing polymer was prepared by the following method. First, 1740 mmol of trimethoxyvinylsilane (monomer (A)) and 260 mmol of diethoxydivinylsilane (monomer (B)) were added to a flask equipped with a reflux tube under a nitrogen atmosphere. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in an oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued for 5 hours after adding the polymerization initiator while stirring the mixture and in an oil bath. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither the monomer (A) nor the monomer (B) remained in the reaction product in the flask. A part of the obtained polymer was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 12500, a weight average molecular weight of 113,000, and a molecular weight distribution of 9.0.

A part of the obtained polymer was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the structure was analyzed by ¹ H-NMR. As a result, a peak corresponding to the methine proton bonded to the silicon atom was confirmed at 0.7 ppm, a peak corresponding to the methylene proton in the main chain was observed at 1.2 ppm, and a peak corresponding to the methyl group in the ethoxysilyl group was observed. A peak corresponding to the methyl proton in the methoxysilyl group and the methylene proton in the ethoxysilyl group was observed at 3.6 ppm. From the integrated value of each peak, the molar ratio between the structural unit (A) derived from the monomer (A) and the structural unit (B) derived from the monomer (B), [structural unit (A) / structure The unit (B)] value was calculated to be approximately 9/1.

  The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb1) having a solid content concentration of 10% by weight.

  On the other hand, 100 parts by weight of tetraethoxysilane was dissolved in 100 parts by weight of ethanol, 17 parts by weight of water and 1.2 parts by weight of 12N hydrochloric acid were added, and stirred at room temperature for 30 minutes to obtain a solution (Sa1). Immediately after the solution (Sa1) was obtained, 96 parts by weight of the solution (Sb1) was added to 100 parts by weight of the solution (Sa1) while stirring the solution (Sa1), and then stirred at room temperature for 30 minutes. Thus, a mixture (S1) was obtained.

  Next, the mixture (S1) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 48 hours, the mixture (S1) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 245 MPa, and a very good result was obtained. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Example 2>
1940 mmol of trimethoxyvinylsilane (monomer (A)) and 60 mmol of diethoxydivinylsilane (monomer (B)) were added to a flask equipped with a reflux tube under a nitrogen atmosphere. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 5 hours after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither monomer (A) nor monomer (B) remained in the reaction product in the flask.

  Next, the entire amount of the obtained polymer was put into 1000 ml of n-hexane and stirred for 60 minutes. After 60 minutes, the polymer that did not dissolve in n-hexane was collected by filtration. The recovered polymer was dried at room temperature under reduced pressure. The weight of the recovered polymer after drying was 15% of the total weight of the monomer (A) and the monomer (B). A part of the polymer thus obtained was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 15500, a weight average molecular weight of 60000, and a molecular weight distribution of 3.9. The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb2) having a solid content concentration of 10% by weight.

  A mixture (S2) was prepared in the same manner as in Example 1 except that the solution (Sb2) was used instead of the solution (Sb1). Next, the mixture (S2) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 60 hours, the mixture (S2) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 283 MPa, and a better result than that of Example 1 was obtained. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Comparative Example 1>
2000 mmol of trimethoxyvinylsilane (monomer (A)) was added to a flask equipped with a reflux tube under a nitrogen atmosphere. The monomer (A) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 5 hours after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that no monomer (A) remained in the reaction product in the flask. A part of the polymer thus obtained was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 3200, a weight average molecular weight of 6100, and a molecular weight distribution of 1.9. The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (SbC1) having a solid content concentration of 10% by weight.

  A mixture (SC1) was prepared in the same manner as in Example 1 except that the solution (SbC1) was used instead of the solution (Sb1). Next, the mixture (SC1) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. The mixture (SC1) gelled after 72 hours. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 43 MPa, which was lower than that of the example. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

  The composite of the present invention can be applied to various fields, and can be used as, for example, a molding material, an insulator material, a coating film, and various compositions. Specifically, it can be used as materials for dental, optical, electrical / electronic parts, paints, inks, adhesives, adhesives, compatibilizers, sealing materials, and the like.

Claims (13)

A composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer,
The compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded,
The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B),
The monomer (A) is at least one compound represented by the following formula (1):
The said monomer (B) is a composite_body | complex which is at least 1 type of compound represented by the following formula | equation (2) .

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ] A complex comprising an oxide and silicon-containing polymer of silicon,
The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B),
The monomer (A) is at least one compound represented by the following formula (1):
The said monomer (B) is a composite_body | complex which is at least 1 type of compound represented by the following formula | equation (2) .

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]   3. The silyl group having the atomic group (G) is condensed and / or hydrolytically condensed in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer. Complex. A composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer,
  The compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded,
  The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B),
  The monomer (A) is at least one compound represented by the following formula (1):
  The monomer (B) is at least one compound containing two or more carbon-carbon double bonds,
  A composite in which a silyl group having the following atomic group (G) is condensed and / or hydrolytically condensed in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer.

[Wherein R ¹ Is a hydrogen atom or an alkyl group. R ² , R ^Three And R ^Four Are each independently an atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group; ² , R ^Three And R ^Four At least one atomic group (G) selected from is a halogen atom, an alkoxy group or a hydroxyl group. ] A composite comprising a silicon oxide and a silicon-containing polymer,
  The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B),
  The monomer (A) is at least one compound represented by the following formula (1):
  The monomer (B) is at least one compound containing two or more carbon-carbon double bonds,
  A composite in which a silyl group having the following atomic group (G) is condensed and / or hydrolytically condensed in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer.

[Wherein R ¹ Is a hydrogen atom or an alkyl group. R ² , R ^Three And R ^Four Are each independently an atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group; ² , R ^Three And R ^Four At least one atomic group (G) selected from is a halogen atom, an alkoxy group or a hydroxyl group. ] The composite according to any one of claims 1 to 5, wherein the silicon-containing polymer has a number average molecular weight of 10,000 or more. A first step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B) to obtain a silicon-containing polymer;
Second step of preparing a mixture comprising at least one selected from compound (I), a hydrolyzate of compound (I) and a hydrolysis condensate of compound (I), the silicon-containing polymer, and a solvent. Including
The monomer (A) is at least one compound represented by the following formula (1):
The monomer (B) is at least one compound represented by the following formula (2) :
The method for producing a complex, wherein the compound (I) is at least one compound containing silicon to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ] The polymerization is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator;
  The method for producing a composite according to claim 7, wherein the activation energy for decomposition of the polymerization initiator is 30 kcal / mol or more. A first step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B) to obtain a silicon-containing polymer;
  Second step of preparing a mixture comprising at least one selected from compound (I), a hydrolyzate of compound (I) and a hydrolysis condensate of compound (I), the silicon-containing polymer, and a solvent. Including
  The monomer (A) is at least one compound represented by the following formula (1):
  The monomer (B) is at least one compound containing two or more carbon-carbon double bonds,
  The polymerization is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator having an activation energy for decomposition of 30 kcal / mol or higher,
  The said compound (I) is a manufacturing method of a composite_body | complex which is at least 1 type of compound containing the silicon | silicone which the at least 1 atomic group chosen from the halogen atom and the alkoxy group couple | bonded.

[Wherein R ¹ Is a hydrogen atom or an alkyl group. R ² , R ^Three And R ^Four Are each independently an atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group; ² , R ^Three And R ^Four At least one atomic group (G) selected from is a halogen atom, an alkoxy group or a hydroxyl group. ] The manufacturing method of the composite_body | complex of any one of Claims 7-9 which further includes the process of removing the said solvent from the said mixture. The number average molecular weight of the said silicon containing polymer is 10,000 or more, The manufacturing method of the composite_body | complex of any one of Claims 7-10. The composite_body | complex obtained by the manufacturing method of any one of Claims 7-11. The lump which consists of a composite_body | complex of any one of Claims 1-6 and Claim 12.