JP2006022250A - Composite and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite excellent in mechanical properties such as flex strength and its manufacturing method. <P>SOLUTION: The composite contains a hydrolysis condensate of compound (I) and a silicon-containing polymer. The weight ratio of the hydrolysis condensate to the silicon-containing polymer is in the range of 1:99-85:15. Compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from halogen atoms and alkoxy groups. The silicon-containing polymer contains a structural unit derived from e.g. a monomer (E) [wherein, R<SP>24</SP>, R<SP>25</SP>and R<SP>26</SP>are each independently one atomic group (G) selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxy group; and at least one atomic group selected from R<SP>24</SP>, R<SP>25</SP>and R<SP>26</SP>is an alkoxy group, a halogen atom or a hydroxy group]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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 (see, for example, 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).

A complex of a polymer substance and a metal oxide can be formed as a lump, but many of the conventional complexes are used in the form of a coating film or a film, and are mechanical as a lump. There were few examples that examined the physical properties. As an example of a composite mass containing a large amount of inorganic substance, tetraethoxysilane is hydrolyzed and polycondensed in the presence of a copolymer of 3-trimethoxysilylpropyl methacrylate and methyl methacrylate, and the composite mass is obtained. Is disclosed (see Non-Patent Document 2). However, according to studies by the inventors, the lump of the document has a characteristic of being a transparent lump but has a low bending strength (80 MPa or less). In addition, the composition obtained by hydrolytic condensation of tetraethoxysilane in the presence of a vinyltrimethoxysilane radical polymer used for the above coating film application is a case where the present inventor molded it as a lump. The mass was low (50 MPa or less) and low in mechanical strength.
JP-A-8-99390 JP-A-9-278968 Journal of the Ceramic Society of Japan, Vol. 105, p555 (1997) Materials Letters, Vol. 13, p261 (1992)

  Currently, there is a demand for further expansion of composites containing metal oxides and polymer materials, but conventional composites that have been used in the form of coating films and films have increased in thickness. It tends to be easy to crack. Therefore, there is a demand for a composite that exhibits excellent mechanical properties even when used as a mass.

  In view of such a situation, an object of the present invention is to provide a composite that can be used as a lump and has excellent mechanical properties, 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 composite of the present invention is a composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer, wherein the weight ratio of the hydrolysis condensate and the silicon-containing polymer is from 1:99 to 85:15, and the compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded. The coalescence includes at least one structural unit selected from the following structural unit (A1), structural unit (A2), structural unit (A3), structural unit (B1), structural unit (B2), and structural unit (B3). It is characterized by that.

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

[Wherein R ⁴ , R ⁵ and R ⁶ are each independently one atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ⁴ , R ⁵ and R ⁶ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]

[Wherein R ⁷ , R ⁸ and R ⁹ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ⁷ , R ⁸ and R ⁹ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]

[Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently one atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹⁰ , R ¹¹ and R ¹² One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]

[Wherein, R ¹³ , R ¹⁴ and R ¹⁵ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹³ , R ¹⁴ and R ¹⁵ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]

[Wherein R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹⁶ , R ¹⁷ and R ¹⁸ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
The structural units (A1) to (A3) and (B1) to (B3) are at least one structural unit represented by the chemical formulas (A1) to (A3) and (B1) to (B3), respectively. It is.

  Further, the method of the present invention for producing a composite includes a first step of obtaining at least one silicon-containing polymer selected from a first silicon-containing polymer and a second silicon-containing polymer, and a compound ( A mixture containing at least one selected from I), a hydrolyzate of the compound (I), and a hydrolysis condensate of the compound (I), the at least one silicon-containing polymer, and a solvent is prepared. Wherein the compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded, and the first silicon The containing polymer is a polymer obtained by polymerizing a monomer containing the following monomer (E), and the second silicon-containing polymer is unsaturated of the first silicon-containing polymer. Little bond And also a polymer obtained by hydrogenating a part.

[Wherein R ²⁴ , R ²⁵ and R ²⁶ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ²⁴ , R ²⁵ and R ²⁶ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
The monomer (E) is at least one compound represented by the chemical formula (E).

  The composite produced 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 a metal atom (M) 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, the metal atom (M) of the compound (I) is linked through oxygen by a hydrolysis condensation reaction. When this hydrolysis-condensation reaction proceeds sufficiently, the hydrolysis-condensation product of compound (I) substantially becomes a metal oxide (for example, metal 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 metal atom (M) is an atom selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, Sb, V, Ta, W, La and Nd It is preferable that Among these, considering the ease of control of the sol-gel reaction, at least one selected from Si, Al, Ti, and Zr is more preferable. Among these, silicon (Si) is preferable because a highly transparent composite can be obtained. Note that although B and Si may be classified as similar metal elements, in this specification, they will be described as metal elements.

  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 the metal atom (M) other than the halogen atom and the alkoxy group include an alkyl group. The number of atomic groups bonded to the metal atom (M) is equal to the valence of the metal atom (M). In a typical example, the atomic group bonded to the metal atom (M) 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 metal 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 metal 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 Halogenated silanes such as chlorosilane and tetrabromosilane; alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium; titanium halides such as tetrachlorotitanium; trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum , Alkoxy aluminum compounds such as tributoxy aluminum and diethoxy aluminum chloride; tetraethoxy zirconium, tetraisopropyl Po carboxymethyl zirconium, and the like alkoxy zirconium compound such as methyl triisopropoxy zirconium.

  Hereinafter, the silicon-containing polymer contained in the composite of the present invention will be described. The silicon-containing polymer includes at least one selected from the structural unit (A1), the structural unit (A2), the structural unit (A3), the structural unit (B1), the structural unit (B2), and the structural unit (B3). A polymer containing structural units. These structural units can be formed by polymerizing a monomer containing the monomer (E) described later, but can also be formed by other methods.

In the structural units (A1) to (A3) and (B1) to (B3), examples of the alkyl group applicable to R ^{1 to} R ¹⁸ include alkyl groups such as a methyl group, an ethyl group, and a propyl group. Examples of the halogen atom applicable to R ^{1 to} R ¹⁸ include chlorine and bromine. Examples of the alkoxy group applicable to R ^{1 to} R ¹⁸ 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. Preferable examples of the structural units (A1) to (A3) and (B1) to (B3) are structural units derived from the monomers (E-1) to (E-3) described later.

  Desirable proportions of the structural units (A1) to (A3) and (B1) to (B3) cannot be generally defined. However, when the structural units (A1), (A3), (B1) and (B3) are contained in the complex, the compound (I) and its hydrolysis are via a functional group directly bonded to the main chain of the polymer. By combining the condensate and the polymer, the mechanical strength of the composite increases. The ratio of the sum of the structural units (A1), (A3), (B1) and (B3) to the sum of the structural units (A1) to (A3) and (B1) to (B3) is 70 mol% or more. From the viewpoint of the mechanical strength of the composite. The sum of the structural units (A1) and (B1) with respect to the sum of the structural units (A1) to (A3) and (B1) to (B3) is preferably 70 mol% or more, more preferably 80 mol% or more. is there. In consideration of coloring and transparency of the composite, the ratio of the structural unit (B1) to the total of the structural units (A1) to (A3) and (B1) to (B3) is preferably 50 mol% or more. , 60 mol% or more is more preferable, and 70% or more is more preferable.

  The silicon-containing polymer contained in the composite of the present invention typically has only one of the structural units (A1), (A2), (A3), (B1), (B2), (B3), or substantially Although it consists only of structural units (A1) to (A3) and (B1) to (B3), a small amount of other structural units may be included as long as the effects of the present invention are obtained.

  The total proportion of the structural units (A1) to (A3) and (B1) to (B3) in the total structural units of the silicon-containing polymer is preferably 30 mol% or more, more preferably 40 mol% or more. For example, it is 50 mol% or more. That is, the proportion of other structural units is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. The other structural unit is preferably at least one structural unit selected from a structural unit derived from the following monomer (C) and a structural unit derived from the following monomer (D).

[Wherein, R ¹⁹ , R ²⁰ and R ²¹ each independently represents an alkyl group. ]

[Wherein, R ²² represents a hydrogen atom or an alkyl group, and R ²³ represents a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyl group or a cyano group. ]

  The monomers (C) and (D) are at least one compound represented by the chemical formulas (C) and (D), respectively. Specific examples of the monomers (C) and (D) will be described later.

  When the silyl groups of the structural units (A1) to (A3) and (B1) to (B3) contained in the silicon-containing polymer are combined with the compound (I) and its hydrolysis condensate, a strong structure is formed. Can do. In particular, in the structural units (A1), (A3), (B1) and (B3), a silyl group directly bonded to the main chain is bonded to the compound (I) and its hydrolysis condensate, thereby providing high mechanical properties. Is expressed.

  The number average molecular weight of the silicon-containing polymer is preferably 8,000 or more, more preferably 9,000 or more, and still more preferably 10,000 or more. When the number average molecular weight is 10,000 or more, the mechanical properties (for example, tensile strength, tensile elongation, flexibility) 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 organic solvent described above. In addition, the number average molecular weight and weight average molecular weight as used in this specification are the values of the polymethylmethacrylate conversion measured by GPC (Gel Permeation Chromatography) as described in an Example.

  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 in the range of 1 to 5, more preferably 1 It is the range of -2, More preferably, it is the range of 1-1.5. By setting the value of “Mw / Mn” in the range of 1 to 2, the solubility of the polymer chain of the silicon-containing polymer becomes uniform, and a more uniform composite can be formed. The physical properties are particularly good.

  In the composite, when the amount of the polymer is too small, the bending strength of the composite is lowered, and when it is too much, the hardness of the composite tends to be lowered. In order to maintain high mechanical properties, 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 to 85% by weight. By setting the ratio within this range, a composite having excellent mechanical properties such as bending strength can be obtained. The ratio is more preferably in the range of 10 to 60% by weight, and still more preferably in the range of 20 to 50% by weight. The ratio of the silicon-containing polymer contained in the composite is preferably in the range of 10 to 99% by weight, more preferably in the range of 30 to 90% by weight, and in the range of 40 to 80% by weight. Is more preferable. The weight ratio of the hydrolyzed condensate of compound (I) to the silicon-containing polymer is in the range of 1:99 to 85:15, preferably in the range of 10:90 to 60:40, and more preferably. Is in the range of 20:80 to 50:50. In addition, the weight of the hydrolysis-condensation product of the compound (I) described here indicates the weight when the compound (I) is completely hydrolyzed and condensed to form a metal oxide.

  Since the silicon-containing polymer has any one of the structural units (A1) to (A3) and (B1) to (B3), one atom selected from an alkyl group, an alkoxy group, a halogen atom, and a hydroxyl group It has a plurality of substituted silyl groups having a group (G). In the composite of the present invention, it is preferable that at least a part of these substituted silyl groups having the atomic group (G) is condensed and / or hydrolytically condensed with other functional groups. At least a part of these substituted silyl groups may be condensed directly with other functional groups, or may be condensed after hydrolysis. When these substituted silyl groups are condensed and / or hydrolyzed, mechanical properties such as bending strength are improved. The other functional group on which the silyl group having the atomic group (G) is condensed and / or hydrolyzed is a functional group (or a functional group present on the surface of the metal oxide) contained in the hydrolytic condensate of the compound (I). But may be other functional groups in the silicon-containing polymer (for example, a silyl group having one atomic group (G) and a silyl group having another atomic group (G)). Condensation and / or hydrolytic condensation). The condensation of the silyl group having the atomic group (G) of the structural units (A1) to (A3) and the structural units (B1) to (B3) can be confirmed by measuring the silicon spectrum by solid-state NMR.

  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 0.3 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, the manufacturing method of a composite_body | complex is demonstrated. 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 at least one silicon-containing polymer selected from the first silicon-containing polymer and the second silicon-containing polymer. Further, this production method comprises at least one selected from compound (I), a hydrolyzate of compound (I), and a hydrolysis condensate of compound (I), at least one silicon-containing polymer, and a solvent. A second step of preparing a mixture comprising: Compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded. The first silicon-containing polymer is a polymer obtained by polymerizing a monomer containing the following monomer (E). The second silicon-containing polymer is a polymer obtained by hydrogenating at least part of the unsaturated bonds of the first silicon-containing polymer.

[Wherein R ²⁴ , R ²⁵ and R ²⁶ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ²⁴ , R ²⁵ and R ²⁶ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]

At least one selected from R ²⁴ , R ²⁵ and R ²⁶ is preferably an alkoxy group. In monomer (E-1) which is a preferred example of monomer (E), R ^{24 to} R ²⁶ are alkoxy. In monomer (E-2) which is another preferred example of monomer (E), R ²⁴ and R ²⁵ are alkoxy groups, and R ²⁶ is an alkyl group. In monomer (E-3) which is another preferred example of monomer (E), R ²⁴ is an alkoxy group, and R ²⁵ and R ²⁶ are alkyl groups. Specific examples of the monomer (E) include, for example, 2-triethoxysilyl-1,3-butadiene, 2-trimethoxysilyl-1,3-butadiene, 2-triisopropoxysilyl-1,3-butadiene. 2-dimethylethoxysilyl-1,3-butadiene, 2-dimethylmethoxysilyl-1,3-butadiene, 2-dimethylisopropoxysilyl-1,3-butadiene, 2-methyldiethoxysilyl-1,3-butadiene 2-methyldimethoxysilyl-1,3-butadiene, 2-methyldipropoxysilyl-1,3-butadiene, 2-diethylethoxysilyl-1,3-butadiene, 2-diethylmethoxysilyl-1,3-butadiene, 2-diethylisopropoxysilyl-1,3-butadiene, 2-ethyldiethoxysilyl-1,3-butadiene Down, 2-ethyl-dimethoxy silyl-1,3-butadiene, and 2-ethyl-dipropoxy silyl-1,3-butadiene.

  The first step may include a step of obtaining the first silicon-containing polymer by polymerizing the monomer. According to this step, a polymer containing at least one structural unit selected from the structural units (A1) to (A3) is obtained. In this case, the proportion of the monomer (E) in all the monomers is preferably 30 mol% or more (for example, 50 mol% or more), and may be 100 mol%.

  The first step includes a step of polymerizing the monomer to obtain a first silicon-containing polymer, a second step of hydrogenating at least part of the unsaturated bonds of the first silicon-containing polymer, and a second step. And obtaining a silicon-containing polymer. According to these steps, a polymer containing at least one structural unit selected from the structural units (B1) to (B3) is obtained.

The first and second silicon-containing polymers can be produced from a monomer other than the monomer (E). It is also possible to produce the first and second silicon-containing polymers from the monomer (E) and a monomer other than the monomer (E). As such a monomer, for example, a compound in which the unsaturated bond of the monomer (E) is integrated into one, specifically, 2- (substituted silyl group) -1-butene, 3- ( (Substituted silyl group) -1-butene, (Substituted silyl group) -A combination of ethylene and ethylene and the like (wherein the substituted silyl group is -SiR ²⁴ R ²⁵ R ²⁶ ).

  Further, after preparing a polymer having an unsaturated bond in the main chain, the unsaturated bond of the polymer is silylated with a silylating agent, and if necessary, side chains are converted, and the first and second It is also possible to produce silicon-containing polymers. Examples of such a polymer having an unsaturated bond in the main chain include polyisoprene and polyin. Examples of the silylating agent that can react with the polymer having an unsaturated bond in the main chain to produce the first and second silicon-containing polymers include triethoxysilane, trimethoxysilane, Examples include silane compounds such as ethoxysilane and dimethylethoxysilane. In addition, for the method of converting the side chain, for example, after adding a halosilane compound such as trichlorosilane, methylchlorosilane, or dimethylchlorosilane to the polymer as a silylating agent, the side chain halosilyl group is reacted with an alcohol. And a method of converting to an alkoxysilyl group can be used.

  The monomer polymerized in the first step may further include at least one monomer selected from the above-described monomer (C) and monomer (D).

In the monomer (C), for R ¹⁹ , R ²⁰ and R ²¹ , for example, an alkyl group having about 1 to 4 carbon atoms can be used. Specific examples of the monomer (C) include, for example, 2-trimethylsilyl-1,3-butadiene, 2-triethylsilyl-1,3-butadiene, 2-tripropylsilyl-1,3-butadiene, and 2-dimethyl. Ethylsilyl-1,3-butadiene, 2-dimethylisopropylsilyl-1,3-butadiene, 2-diethylmethylsilyl-1,3-butadiene, 2-dipropylethyl-1,3-butadiene, 2-dipropylmethyl Examples include silyl-1,3-butadiene, 2-diethylpropylsilyl-1,3-butadiene, and 2-methylethylpropylsilyl-1,3-butadiene.

In the monomer (D), examples of the alkyl group used for R ²² include alkyl groups having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group. Examples of the alkoxycarbonyl group used for R ²³ include those having 2 to 8 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and an octyloxycarbonyl group. Examples of the cycloalkoxycarbonyl group include cyclohexyl. Examples thereof include those having 3 to 12 carbon atoms such as oxycarbonyl group, and examples of the alkylcarbonyl group include those having 2 to 8 carbon atoms such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group and heptylcarbonyl group. . The alkoxycarbonyl group, cycloalkoxycarbonyl group, and alkylcarbonyl group used for R ²³ may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, or an aryl group.

  Specific examples of the monomer (D) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, and chloro. Ethyl acrylate, 2-ethoxyethyl acrylate, 2,2-dimethyl-3-ethoxypropyl acrylate, 5-ethoxypentyl acrylate, 1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-methoxypropyl acrylate, 1-methyl-1 -Acrylic acid esters such as methoxyethyl acrylate, 1- (isopropoxy) ethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc. Tellurium; methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, 5-methoxypentyl Methacrylate, 2,2-dimethyl-3-ethoxypropyl methacrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, 1-methoxypropyl methacrylate, 1-methyl-1-methoxyethyl methacrylate, 1- (isopropoxy) ethyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate Methacrylic acid esters such as rate; Vinyl esters such as methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, isopropyl vinyl ketone, t-butyl vinyl ketone and isobutyl vinyl ketone; Nitriles such as acrylonitrile and methacrylonitrile Is mentioned.

  Among these, methyl methacrylate, ethyl methacrylate, ethyl acrylate, methyl acrylate, methyl vinyl ketone, acrylonitrile and the like are preferable from the viewpoint of polymerizability with other monomers.

  The monomer polymerized in the first step may further include other monomers such as itaconic acid ester in addition to the monomer (C) and the monomer (D) described above.

  The monomer (C), monomer (D), monomer (E), and compound (I) may be commercially available or synthesized by a known method. Good. Moreover, since the compound applicable to compound (I) and its combination were 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 carried out according to a known polymerization method such as anionic polymerization, cationic polymerization, radical polymerization, etc., but is preferably carried out by radical polymerization or anionic polymerization, and the yield of the resulting polymer Therefore, it is more preferable to carry out by anionic polymerization. The first silicon-containing polymer can be obtained by anionic polymerization of the above-described monomer.

  Anionic polymerization is preferably carried out at a temperature of 0 ° C. or lower in the presence of a polymerization initiator. The polymerization initiator to be used is not particularly limited, but alkyllithium such as n-butyllithium; benzyl type initiator such as cumyl potassium, benzylsodium and dibenzylbarium; radical anion such as potassium naphthalene and lithium naphthalene; α-methyl Oligomeric dianions of non-polymerizable monomers such as styrene can be used.

  The amount of the polymerization initiator used is preferably in the range of 0.001 to 0.5 mol, more preferably 0.002 to 0.1 mol, per mol of all monomers (plural types of monomers). More preferably, it is the range of 0.01-0.05 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 with a high yield.

  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, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, n-octane, n-pentane, n-heptane and the like can be used. These solvents may be used alone or in combination of two or more.

  When the polymerization step is carried out in the presence of a solvent, a polymerizable mixture containing the monomer (E) and the organic solvent is prepared. The polymerization step is preferably performed in an inert gas atmosphere or in a high vacuum. 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 0 ° C or lower, and more preferably adjusted to -20 ° C or lower.

  The polymerization initiator may be added dropwise to the mixture of the monomer and the organic solvent, or the monomer may be added to the mixture of the polymerization initiator and the organic solvent. The total amount of the polymerization initiator may be added at once, or may be added in several divided portions. The timing for adding the polymerization initiator is not particularly limited, but it is preferable to add the polymerization initiator after the polymerization solution reaches the polymerization temperature.

  The silicon-containing polymer can be used in the form of a reaction solution after polymerization. However, if the pH of the solution becomes high due to the remaining polymerization initiator, condensation / hydrolysis of alkoxysilyl groups and the like is promoted, which causes gelation. For this reason, it is preferable to purify the polymer by precipitation. When performing reprecipitation, the poor solvent to be used varies depending on the substituent contained in the silicon polymer. For example, when the silyl group contained in the silicon polymer is an ethoxysilyl group, it is preferable to use a higher alcohol, usually methanol, as the poor solvent.

  Next, a method for obtaining a second silicon-containing polymer by hydrogenating at least a part of the unsaturated bonds of the first silicon-containing polymer will be described.

  The solvent used in the hydrogenation reaction is not particularly limited, and examples thereof include aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and decalin; aliphatic hydrocarbons such as pentane, hexane, and heptane; Ethers such as tetrahydrofuran, diethyl ether, dibutyl ether and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene and trichlorobenzene Etc. These solvents may be used alone or in combination of two or more.

  Hydrogenation to the first silicon-containing polymer can be performed by adding hydrogen to the solution containing the first silicon-containing polymer and introducing hydrogen. The hydrogenation is preferably carried out after isolating the first silicon-containing polymer from the reaction solution in which the polymerization of the monomer has been completed, and then dissolving it again in a solvent. However, hydrogenation may be performed without isolating the first silicon-containing polymer from the reaction solution.

  The hydrogenation reaction of the polymer is usually performed at a hydrogen pressure in the range of normal pressure to 300 atm, preferably 20 to 200 atm, and the reaction temperature is usually 0 to 200 ° C, preferably room temperature to 150 ° C. Temperature range. In general, the molar ratio of the polymer double bond to the hydrogenation catalyst is preferably 100: 1 to 100: 100, more preferably 100: 10 to 100: 50.

The hydrogenation rate in the hydrogenation reaction of the polymer can be controlled by the amount of catalyst added and the reaction time. The hydrogenation rate in the hydrogenation reaction of the polymer can be determined from the integrated value of olefin protons in ¹ H-NMR.

  The hydrogenation catalyst is not particularly limited, and a known catalyst that can hydrogenate a double bond can be used. Specifically, a solid catalyst in which a noble metal such as nickel, palladium, platinum, cobalt, ruthenium or rhodium or a compound such as an oxide, salt or complex thereof is supported on a porous carrier such as carbon, alumina, silica, silica / alumina diatomaceous earth, etc. Is mentioned. Among these, those in which palladium is supported on carbon are preferable.

  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 hydrolysis condensation of compound (I) may occur with some functional groups or with all functional groups. The hydrolyzate and hydrolysis condensate of compound (I) can be prepared by a known method, for example, a method used in a sol-gel method. An example of a method for producing the hydrolyzate and hydrolyzed 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) undergoes hydrolytic condensation to obtain a solution composed of the component (I) and a solvent (hereinafter sometimes referred to as “solution (Sa)”). 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. When a compound containing a metal atom (M) to which an alkoxy group is bonded is used as the compound (I), the compound (I) is contained. Alcohol having the same molecular structure (alkoxy component) as the alkoxy group 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 the hydrolysis and / or hydrolysis condensation of compound (I) varies depending on the type of compound (I) and the desired hydrolysis condensate, but usually the compound (I) ) Is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 4 mol, relative to 1 mol of the alkoxy group or halogen atom (the total when both are present). Preferably, it is in the range of 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. 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.

As the catalyst used for the hydrolysis of the compound (I), an acid catalyst or a basic catalyst can be used, but an acid catalyst is preferably used. 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 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 the metal 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.

  Although there is no limitation in particular in the temperature of the reaction solution at the time of producing a hydrolysis condensation reaction, it is the range of 2-100 degreeC normally, Preferably it is the range of 4-60 degreeC, More preferably, it is the range of 6-50 degreeC It is. 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 ethanol and isopropanol; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, etc. Glycerol derivatives; glycerin; acetonitrile; dimethylformamide; dimethyl sulfoxide; sulfolane and the like can be used alone or in combination. Among these, alcohols such as ethanol and isopropanol 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. Further, 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, etc., but is usually preferably in the range of 1 × 10 ⁻⁵ to 10 moles, more preferably relative to 1 mole of the metal 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.

  Especially in the concentration of solids contained in the mixture (S) obtained in the second step of the present invention (the total concentration of the compound (I) component, the silicon-containing polymer, and other components that can be added in the following cases) Although there is no limitation, Preferably it is the range of 1-50 weight%, More preferably, it is the range of 2-30 weight% (for example, the range of 3-15 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 the metal atom (M) in the compound (I) component to the weight of the silicon-containing polymer Is preferably in the range of 0.001 to 1.0, more preferably in the range of 0.005 to 0.7, and still more preferably in the range of 0.01 to 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 is 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, it is possible to obtain a lump of at least 0.3 cm square or more. 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 degree of polymerization, number average molecular weight and weight average molecular weight A silicon-containing polymer was dissolved in tetrahydrofuran so that the concentration was 0.25 wt%, 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 a polymethyl methacrylate standard (polymethyl methacrylate standard sample manufactured by Sowa Co., Ltd.). That is, polymethyl methacrylate 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, it was confirmed that at least a part of the structural units constituting the silicon-containing polymer was condensed and / or hydrolyzed. .

<Synthesis of 2-triethoxysilyl-1,3-butadiene>
2-Triethoxysilyl-1,3-butadiene used in the examples was synthesized by the following method.

A two-necked eggplant flask was equipped with a dropping funnel and a Dimroth condenser and replaced with nitrogen for 5 minutes or more. To this eggplant flask, 25 g (0.20 mol) of 1,4-dichloro-2-butyne and a catalyst were added. As a catalyst, 3 drops of 0.05 N isopropanol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added. Subsequently, 27.35 g (0.20 mol) of trichlorosilane was dropped into the flask while heating the flask with a drier. Although the trichlorosilane was refluxed by heating the dryer, the heating was continued until the reaction continued to the extent that the reflux continued even if the heating was stopped. If the reaction did not continue, a solid catalyst was added directly to the reaction system. If the reaction was too intense, the flask was cooled. After completion of the dropwise addition of trichlorosilane, disappearance of 1,4-dichloro-2-butyne was confirmed by gas chromatography. The product was then purified by vacuum distillation (665 Pa (5 mm Hg), 60 ° C.). As a result, 38.53 g (yield 74%) of 1,4-dichloro-2-trichlorosilyl-2-butene was obtained.

  A nitrogen inlet tube and a dropping funnel were attached to a three-necked flask, and a mechanical stirrer was installed. Into this flask, 38.5 g (0.15 mol) of 1,4-dichloro-2-trichlorosilyl-2-butene and 200 ml of tetrahydrofuran were added and cooled to 0 ° C. Here, a mixture of 29.52 g (0.64 mol) of ethanol and 53.6 g (0.53 mol) of triethylamine, which was distilled to remove water, was added dropwise over 1 hour. Simultaneously with the dropwise addition, a large amount of triethylamine hydrochloride began to precipitate. After completion of the dropwise addition, the reaction solution was stirred for 2 hours at room temperature and 1 hour at 60 ° C. to complete the reaction. After the reaction solution was cooled to room temperature, 200 ml of hexane was added to precipitate a salt. The salt was separated by suction filtration. Next, after distilling off the solvent from the reaction solution with a rotary evaporator, the product was purified by distillation under reduced pressure (13.3 Pa (0.1 mmHg), 80 ° C.). As a result, 32.1 g (yield 75%) of 1,4-dichloro-2-triethoxysilyl-2-butene was obtained.

  A 200 ml two-necked eggplant flask was equipped with a dropping funnel and a Dimroth condenser, and purged with nitrogen for 5 minutes or more. This flask was charged with 10.98 g (0.17 mol) of zinc powder and 30 ml of tetrahydrofuran. The zinc powder was washed with 2N hydrochloric acid, water, and acetone and then dried under reduced pressure at room temperature. Next, 32.1 g (0.12 mol) of 1,4-dichloro-2-triethoxysilyl-2-butene was added dropwise together with 16 ml of tetrahydrofuran over about 30 minutes while heating and refluxing the solution in the flask. After completion of dropping, the reaction was further refluxed for 2 hours to complete the reaction. Next, the reaction solution was cooled to room temperature, and pentane was added to precipitate zinc chloride as a by-product. The zinc chloride was separated by suction filtration. Next, after distilling off the solvent from the reaction solution with a rotary evaporator, calcium hydride powder was added, and the mixture was stirred for about 10 hours under a nitrogen stream. Finally, the product was purified by vacuum distillation (266 Pa (2 mm Hg), 40 ° C.). Thus, 12 g (yield 50%) of 2-triethoxysilyl-1,3-butadiene was obtained.

<Example 1>
A silicon-containing polymer was prepared by the following method. First, the Schlenk tube was dried by heating under reduced pressure. To this Schlenk tube, 0.2 g of metallic potassium and 0.2 g of naphthalene were added, 10 ml of tetrahydrofuran was added in a high purity argon atmosphere, and the mixture was stirred at room temperature for about 10 hours. This potassium naphthalene solution was used as a polymerization initiator.

  46 mmol of 2-triethoxysilyl-1,3-butadiene (monomer (E)) and 10 ml of tetrahydrofuran were added to a dry Schlenk tube under a high purity argon atmosphere. The Schlenk tube was cooled to -78 ° C with a dry ice-methanol bath. A polymerization initiator was added dropwise to the Schlenk tube in a high purity argon atmosphere so that the molar ratio of the monomer (E) and potassium naphthalene was 60: 1, and polymerization was performed at -78 ° C for 12 hours. . After 12 hours, 1 drop of ethanol was added to the polymerization solution to stop the polymerization. The polymerization solution was dropped into methanol and allowed to stand to obtain a precipitated oily polymer.

  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 58,000, a weight average molecular weight of 87,000, and a molecular weight distribution of 1.5.

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, the peak derived from the structural unit (A1); the peak corresponding to the methyl proton of the ethoxysilyl group (1.2 ppm), the peak corresponding to the main chain methylene proton (2.3 ppm), the methylene proton of the ethoxysilyl group A peak corresponding to (3.8 ppm) and a peak corresponding to a proton bonded to a double bond carbon of the main chain (6.2 ppm) are observed, and the silicon-containing polymer is substantially composed of a structural unit (A1). confirmed.

  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, 337 parts by weight of the solution (Sb1) was added while stirring the solution (Sa1), and then stirred at room temperature for 30 minutes to obtain a mixture (S1).

  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. The mixture (S1) gelled after 5 days at room temperature. 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 3.5 mm × 3.5 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 300 MPa, and very good results were obtained.

<Example 2>
1 g of the silicon-containing polymer obtained in the same manner as in Example 1 was dissolved in 100 ml of dry cyclohexane. To this, 1.5 g of palladium carbon (10% supported) was added, and maintained in an autoclave at a hydrogen pressure of 80 atm and 100 to 110 ° C. for 90 hours. After completion of the reaction, the remaining catalyst was removed by filtration, and the solvent was distilled off. A hydrogenated silicon-containing polymer was thus obtained. When ¹ H-NMR of the polymer was measured, the peak intensity of protons bonded to the double bond carbon of the main chain in the silicon-containing polymer before hydrogenation was greatly reduced. The structural units contained in the hydrogenated silicon-containing polymer were confirmed to be 99% structural units (B1) and 1% structural units (A1).

  Next, a lump made of a composite was obtained in the same manner as in Example 1 except that the hydrogenated silicon-containing polymer was used. The three-point bending strength of the lump was 350 MPa, and a very good result was obtained. Moreover, the lump without coloring compared with Example 1 was obtained.

<Example 3>
A hydrogenated silicon-containing polymer was obtained in the same manner as in Example 2 except that the amount of hydrogenation was changed. That is, in Example 3, 0.5 g of palladium carbon (10% supported) was added at the time of hydrogenation, and kept in an autoclave at a hydrogen pressure of 80 atm and 100 to 110 ° C. for 44 hours. Except for this, a hydrogenated silicon-containing polymer was produced under the same conditions as in Example 2. When ¹ H-NMR of the obtained polymer was measured, a decrease was observed in the peak intensity of protons bonded to the double bond carbon of the main chain as compared with the silicon-containing polymer before hydrogenation. It was confirmed that the structural units contained in the hydrogenated silicon-containing polymer were 52% structural units (B1) and 48% structural units (A1).

  Except using this hydrogenated polymer, the lump which consists of a composite_body | complex was obtained by the method similar to Example 1. FIG. The three-point bending strength of the mass was 330 MPa, and very good results were obtained. Moreover, the lump without coloring compared with Example 1 was obtained.

<Example 4>
The molar ratio of monomer (E) to 2,2′-azobisisobutyronitrile in 46 mmol of 2-triethoxysilyl-1,3-butadiene (monomer (E)) and 10 ml of tetrahydrofuran 2,2′-azobisisobutyronitrile was added so as to be 100: 1 and heated at 80 ° C. for 10 hours. In this way, a silicon-containing polymer was obtained. When ¹ H-NMR of the obtained silicon-containing polymer was measured, a peak derived from the structural unit (A1); a peak corresponding to the methyl proton of the ethoxysilyl group (1.2 ppm), corresponding to a methylene proton of the main chain (2.3 ppm), a peak corresponding to the methylene proton of the ethoxysilyl group (3.8 ppm), and a peak corresponding to the proton bonded to the double bond carbon of the main chain (6.2 ppm) were observed. From this result, it was confirmed that the silicon-containing polymer substantially consists of the structural unit (A1).

  When the GPC of the silicon-containing polymer was measured, the number average molecular weight was 29,000, the weight average molecular weight was 67,000, and the molecular weight distribution was 2.3. Except that the silicon-containing polymer was used, a mass composed of the composite was obtained in the same manner as in Example 1. The three-point bending strength of the lump was 110 MPa.

<Example 5>
As a monomer, a mixture of 27.6 mmol of 2-triethoxysilyl-1,3-butadiene (monomer (E)) and 18.4 mmol of methyl methacrylate was used, and a silicon-containing polymer (number average) In the same manner as in Example 1 except that a molecular weight: 43,000, a weight average molecular weight: 69,000, and a molecular weight distribution: 1.6) were obtained, a mass comprising a complex was obtained. The three-point bending strength of the lump was 250 MPa, and good results were obtained.

<Comparative Example 1>
2000 mmol of trimethoxyvinylsilane was added to a flask fitted with a reflux tube under a nitrogen atmosphere. Trimethoxyvinylsilane 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 silicon-containing 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 polymer thus obtained was dissolved in ethanol to obtain a silicon-containing polymer solution 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, 304 parts by weight of the silicon-containing polymer solution was added while stirring the solution (Sa1), and then stirred at room temperature for 30 minutes to obtain a mixture (SC1).

  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. Moreover, as a result of measuring solid NMR of the lump, it was confirmed that the functional groups of the structural units constituting the silicon-containing polymer were 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 (16)

A composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer,
The weight ratio of the hydrolysis condensate to the silicon-containing polymer is in the range of 1:99 to 85:15;
The compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded,
The silicon-containing polymer includes at least one selected from the following structural unit (A1), structural unit (A2), structural unit (A3), structural unit (B1), structural unit (B2), and structural unit (B3). A composite comprising a structural unit.
[Wherein R ¹ , R ² and R ³ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹ , R ² and R ³ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
[Wherein R ⁴ , R ⁵ and R ⁶ are each independently one atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ⁴ , R ⁵ and R ⁶ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
[Wherein R ⁷ , R ⁸ and R ⁹ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ⁷ , R ⁸ and R ⁹ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
[Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently one atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹⁰ , R ¹¹ and R ¹² One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
[Wherein, R ¹³ , R ¹⁴ and R ¹⁵ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹³ , R ¹⁴ and R ¹⁵ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]
[Wherein R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ¹⁶ , R ¹⁷ and R ¹⁸ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]   2. The composite according to claim 1, wherein a ratio of the at least one structural unit in all the structural units of the silicon-containing polymer is 50 mol% or more. The silicon-containing polymer further includes at least one structural unit selected from structural units derived from the following monomer (C) and structural units derived from the following monomer (D). Or the complex according to 2.
[Wherein, R ¹⁹ , R ²⁰ and R ²¹ each independently represents an alkyl group. ]
[Wherein, R ²² represents a hydrogen atom or an alkyl group, and R ²³ represents a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyl group or a cyano group. ]   The composite according to any one of claims 1 to 3, wherein at least a part of the substituted silyl group having the atomic group (G) contained in the silicon-containing polymer is condensed and / or hydrolyzed. .   The composite according to any one of claims 1 to 3, wherein the silicon-containing polymer has a number average molecular weight of 10,000 or more.   The composite according to any one of claims 1 to 3, wherein the silicon-containing polymer has a weight average molecular weight / number average molecular weight ratio in the range of 1 to 5.   The composite according to any one of claims 1 to 6, wherein the metal atom (M) is at least one selected from Si, Al, Ti, and Zr. A first step of obtaining at least one silicon-containing polymer selected from a first silicon-containing polymer and a second silicon-containing polymer;
A mixture comprising at least one selected from Compound (I), a hydrolyzate of Compound (I), and a hydrolysis condensate of Compound (I), at least one silicon-containing polymer, and a solvent. A second step of preparing,
The compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded,
The first silicon-containing polymer is a polymer obtained by polymerizing a monomer containing the following monomer (E):
The method for producing a composite, wherein the second silicon-containing polymer is a polymer obtained by hydrogenating at least part of unsaturated bonds of the first silicon-containing polymer.
[Wherein R ²⁴ , R ²⁵ and R ²⁶ are each independently an atomic group selected from an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group, and at least selected from R ²⁴ , R ²⁵ and R ²⁶ One atomic group (G) is an alkoxy group, a halogen atom, or a hydroxyl group. ]   The method for producing a composite according to claim 8, wherein the first step includes a step of polymerizing the monomer to obtain the first silicon-containing polymer.   The method for producing a composite according to claim 9, wherein a ratio of the monomer (E) to the monomer is 50 mol% or more.   The first step includes a step of polymerizing the monomer to obtain the first silicon-containing polymer, and hydrogenation to at least a part of the unsaturated bond of the first silicon-containing polymer. The method for producing a composite according to claim 8, comprising a step of obtaining a silicon-containing polymer of 2.   The method for producing a complex according to any one of claims 8 to 11, further comprising a step of removing the solvent from the mixture.   The method for producing a composite according to any one of claims 8 to 12, wherein the first step includes a step of obtaining the first silicon-containing polymer by anionic polymerization of the monomer. The composite according to any one of claims 8 to 13, wherein the monomer further includes at least one monomer selected from the following monomers (C) and the following monomers (D). Body manufacturing method.
[Wherein, R ¹⁹ , R ²⁰ and R ²¹ each independently represents an alkyl group. ]
[Wherein, R ²² represents a hydrogen atom or an alkyl group, and R ²³ represents a carboxyl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyl group or a cyano group. ]   The composite_body | complex manufactured with the manufacturing method of any one of Claims 8-14.   The lump which consists of a composite_body | complex of any one of Claims 1-7 and Claim 15.