JP4542758B2 - Copolysilane and its production method - Google Patents

Description

  The present invention relates to a cyclic copolysilane (polysilane copolymer) in which the excellent properties of diarylpolysilane (such as diphenylpolysilane) are further improved, and a method for producing the same.

  Polysilane is used in various applications that take advantage of its special physical properties, such as ceramic precursors, optoelectronic materials (eg, photoelectrophotographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording such as optical memories, etc.) It is attracting attention in applications such as materials and materials for electroluminescent elements. Of the polysilanes, diphenylpolysilane has a high refractive index, high water repellency, and high flame retardancy. Therefore, in addition to the above uses, diphenylpolysilane has been studied as a raw material and an additive for various uses utilizing high refractive index, high water repellency, and high flame retardancy. In such applications, polysilane is usually used in the form of addition to a thin film or resin.

  However, a polysilane thin film having a main chain made of silicon is hard and brittle, and has low mechanical strength, and thus easily causes defects such as cracks. In particular, diphenylpolysilane has one of the highest refractive indices among polysilanes. Therefore, an application utilizing the excellent characteristics of diphenylpolysilane is conceivable. However, since diphenylpolysilane has a large structure symmetry and high crystallinity, the solvent to be dissolved is limited, and the thin film is likely to be cracked.

  Regarding addition to the resin, diphenylpolysilane has high crystallinity, and therefore has low affinity and compatibility with the resin, and cannot be added in a large amount to the resin. Therefore, the excellent physical properties of diphenylpolysilane cannot be sufficiently imparted to the additive.

Conventionally, polysilanes have been produced by using an alkali metal such as sodium metal and dilutely stirring dialkyldihalosilane or dihalotetraalkyldisilane in a toluene solvent at a temperature of 100 ° C. or higher. A method of ringing is known (Non-Patent Document 1).
J. Am. Chem. Soc., 103 (1981) 7352.

  However, this method has a large safety problem in production on an industrial scale because it is necessary to heat and strongly stir and disperse the alkali metal that ignites in the air. There are also problems with quality, such as the molecular weight distribution being multimodal. In particular, diphenyl-based polysilanes are insoluble and infusible and have physical properties that are difficult to use as optoelectronic materials.

In order to overcome these disadvantages, for example, several new methods for producing polysilanes have been proposed (Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4).
JP-A-1-23063 Japanese Patent Laid-Open No. 5-170913 Japanese Patent Publication No.7-17753 JP-A-7-309953.

  Patent Document 1 discloses a method of anionic polymerization of disilene masked with biphenyl and the like, Patent Document 2 discloses a method of ring-opening polymerization of cyclic silanes, and Patent Document 3 discloses transition of hydrosilanes. A method of dehydrogenating polycondensation with a metal complex catalyst is disclosed, and Patent Document 4 discloses a method of producing polysilane by electrode reduction of dihalosilanes at a temperature below room temperature.

  However, the methods of Patent Document 1 and Patent Document 2 involve complicated operations such as the need to synthesize complex monomers, and the total yield from monomer synthesis is not only low, but also an alkyl lithium reagent is used for polymerization. Because it is necessary, there is a difficulty in safety. The polycondensation method of Patent Document 3 still has many points to be improved regarding the molecular weight and the structure of the obtained polysilane (for example, a crosslinked structure is formed) due to its reaction mechanism. On the other hand, the electrolytic reduction method of Patent Document 4 is an excellent technique for obtaining high-molecular-weight and high-quality polysilanes safely and in a high yield, but requires an electrolytic cell which is a special reaction apparatus. Therefore, although it is suitable for the production of polysilane for high value-added applications, it is difficult to say that the method is suitable for the production of polysilane for low value-added applications.

As a method for producing polysilane, there is known a method of forming polysilane by allowing magnesium or a magnesium alloy to act on dihalosilane in an aprotic solvent in the presence of a lithium salt and a metal halide (Patent Literature). 5).
WO98 / 29476.

  Patent Document 5 also describes an example in which methylphenyldichlorosilane is reacted with dimethyldichlorosilane or n-hexylmethyldichlorosilane. In this method, polysilane can be produced safely and inexpensively without requiring complicated operations.

Furthermore, Patent Document 6 describes that the polysilane may be a linear or cyclic polysilane, and these polysilanes may be a dialkyl polysilane, an alkyl-aryl polysilane, or a diaryl polysilane.
JP 2003-162064 A (paragraph number [0035] [0038])

  Accordingly, an object of the present invention is to provide a polysilane (or oligosilane) having a high solubility or compatibility with a solvent or a resin even if it has a diphenylsilane unit, and a method for producing the same.

  Another object of the present invention is to maintain the excellent properties (high refractive index, high water repellency, high flame retardancy, etc.) of diphenylpolysilane, and also have excellent solubility in solvents, compatibility with resins and transparency. The object is to provide polysilane (or oligosilane) and a method for producing the same.

  Still another object of the present invention is to provide a method capable of easily controlling the structure and molecular weight of polysilane and imparting various characteristics to diphenylpolysilane.

  Another object of the present invention is to provide a new method capable of producing the polysilane (or oligosilane) safely and inexpensively without requiring complicated operations.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors made diphenylhalosilane and other halosilane coexist in a non-protic solvent with a lithium compound and a metal halide as required, When the components are allowed to act, the reaction can be controlled easily and accurately, and a polysilane having a structure in which a part of the structural unit of diphenylpolysilane having physical properties such as high refractive index and high water repellency is substituted with other substituents (cyclic) Copolysilane etc.) were rapidly and efficiently produced, and it was found that the excellent physical properties of diphenylpolysilane, solubility and compatibility were compatible, and the present invention was completed.

That is, the copolysilane (silane copolymer) of the present invention is a pentameric cyclic copolysilane composed of a diphenylsilane unit represented by the following formula (i) and a phenylmethylsilane unit represented by the following formula (ii). It is.
(In the formula, R ¹ is a methyl group and R ² is a phenyl group.)

  The form of the copolysilane is not particularly limited, and may be a random copolymer, a block copolymer, or a graft copolymer.

The polysilane may be a single compound, or may be a mixture with a diarylpolysilane (such as diphenylpolysilane) or another polysilane as long as it contains the cyclic copolysilane . That is, depending on the application, even if a component that replaces a part of the structural unit of diarylpolysilane (diphenylpolysilane, etc.) is contained as polysilane, it functions as a melting point depressant or compatibilizer for diarylpolysilane (diphenylpolysilane, etc.). To do. Therefore, the present invention may be a polysilane mixture as long as it contains the cyclic copolysilane . In this polysilane mixture, the ratio of the pentameric cyclic copolysilane to the whole polysilane may be 20% by weight or more.

The cyclic copolysilane or polysilane mixture includes a compound represented by the following formula (1b) and a compound represented by the following formula (2b) in an aprotic solvent in the presence of a magnesium metal component, a lithium compound, and a metal halide. Among them, it can be produced by reacting at least one of the following conditions (i) to (ii) .
(I) The metal halide is iron chloride and / or iron bromide.
(Ii) The compounds represented by (1b) and (2b) are added dropwise.

(In the formula, R ¹ is a methyl group, R ² is a phenyl group, and X ^{1 to} X ² are the same or different and are halogen atoms . )

In such a method, cyclic copolysilane can be produced efficiently. The reaction can be performed in an aprotic solvent. Furthermore, the reaction may be performed in the presence of a magnesium metal component, but may be performed in the presence of a lithium compound and / or a metal halide. Lithium halides (such as lithium chloride) can be used as the lithium compound, and iron chlorides and / or bromides can be used as the metal halide. Specifically, as the metal halide, iron chloride (II), etc. of iron (III) chloride can be used. These components can be used alone or in combination of two or more.

In the present invention, one of the compound represented by the formula ( 1b ) and the compound represented by the formula ( 2b) is reacted to form polysilane or oligosilane, and then the other component is added. And reacting to produce copolysilane. In this method, a block copolymer can be obtained.

The present invention also includes a resin composition containing the polysilane ( cyclic copolysilane, polysilane mixture). The type of resin may be a thermoplastic resin or a thermosetting resin, and the amount of polysilane used may be, for example, about 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin.

  In the present invention, since diarylpolysilane is copolymerized with other silane, solubility in a solvent and compatibility with a resin can be improved even if it has a diarylsilane (for example, diphenylsilane) unit. In addition, while maintaining the excellent properties of diarylsilanes (eg, diphenylsilane) (high refractive index, high water repellency, high flame retardancy, etc.), solubility in solvents, compatibility and transparency in resins, film formability Can be greatly improved. Furthermore, the structure and molecular weight of polysilane can be easily controlled, and various characteristics can be imparted to diarylsilane (for example, diphenylsilane). Further, the polysilane (or oligosilane) can be produced safely and inexpensively without requiring complicated operations.

  In the present invention, polysilane (copolysilane) is produced by reacting the diaryldihalosilane represented by the formula (1) with another halosilane.

[Halosilane compounds]
In the formula (1), examples of the aryl group represented by Ar ¹ and Ar ² include C _6-12 aryl groups such as a phenyl group and a naphthyl group. The aryl group may have a substituent. Examples of the substituent of the aryl group include an alkyl group (a linear or branched C _1-10 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl group), a hydroxyl group, and an alkoxy group ( Linear or branched C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, butoxy, t-butoxy group), carboxy group, linear or branched C _1-6 alkoxy-carbonyl group, linear And a branched C _1-6 alkyl-carbonyl group. Preferred substituents of the aryl group are linear or branched alkyl groups (preferably C _1-6 alkyl groups, particularly C _1-4 alkyl groups) represented by R ¹⁰ and R ¹¹ in formula (1a) or straight A chain or branched alkoxy group (preferably a C _1-6 alkoxy group, particularly a C _1-4 alkoxy group). The number of substituents for the aryl group is not particularly limited, but can usually be selected from a range of about 1 to 3.

The halogen atom represented by X ^{1 to} X ² includes F, Cl, Br, and I, and Cl and Br (particularly Cl) are preferable.

Examples of the compound represented by the formula (1) include diaryldihalosilanes (C _6-10 aryldihalosilanes such as diphenyldihalosilane and dinaphthyldihalosilane), di (alkylaryl) dihalosilanes ( Di (C _1-6 alkyl C _6-10 aryl) dihalosilanes such as ditolyl dihalosilane, dixylyl dihalosilane, especially di (C _1-4 alkyl C _6-10 aryl) dihalosilane), aryl-alkylaryl di Halosilane (C _6-10 aryl-C _1-6 alkyl C _6-10 aryl dihalosilane such as phenyltolyldihalosilane, phenylxylyldihalosilane), di (alkoxyaryl) dihalosilane (dimethoxyphenyl dihalosilane) Di (C _1-6 alkoxy C _6-10 aryl) dihalosilanes such as dimethoxyphenyldihalosilane, especially di (C _1-4 alkoxy C _6-10 aryl) dihalosilane etc.) can be exemplified. These compounds can be used alone or in combination of two or more.

  Preferred compounds (1) are compounds represented by the formula (1a) (diphenyldihalosilane, ditolyldihalosilane such as ditolyldichlorosilane, dicylyldihalosilane such as dixylyldichlorosilane), particularly the formula (1b). ) (Diphenyldihalosilane such as diphenyldichlorosilane).

The other halosilane as a copolymerization component is a compound represented by the above formulas (2) to (5) (that is, dihalosilane (2), trihalosilane (3), tetrahalosilane (4), monohalosilane (5)). These halosilanes can be used alone or in combination of two or more. In the above formulas (2) to (5), R ¹ and R ² are not simultaneously an aryl group which may have a substituent.

Examples of the organic group represented by R ^{1 to} R ⁶ include alkyl groups [linear or branched C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups (preferably C _1-6 alkyl group, especially C _1-4 alkyl group)], cycloalkyl group (C _5-8 cycloalkyl group such as cyclohexyl group, especially C _5-6 cycloalkyl group), aryl group (phenyl, naphthyl group) C _6-10 aryl groups such as aralkyl groups [C _6-10 aryl-C _1-6 alkyl groups such as benzyl and phenethyl groups (C _6-10 aryl-C _1-4 alkyl groups)]], alkoxy groups [C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and t-butoxy groups (preferably C _1-6 alkoxy groups, especially C _1-4 alkoxy groups)], amino groups, N- Substituted amino (The alkyl group, cycloalkyl group, aryl group, aralkyl group, such as substituted N- mono- or di-substituted amino group with an acyl group).

The aryl group constituting the alkyl group, cycloalkyl group, aryl group, or aralkyl group may have one or more substituents. Examples of such a substituent include the above-exemplified alkyl groups (particularly, C _1-6 alkyl groups and the like), the above-exemplified alkoxy groups and the like. Examples of the organic group having such a substituent include C _1-6 alkyl C _6-10 aryl groups such as tolyl, xylenyl, ethylphenyl, and methylnaphthyl groups (preferably mono to tri C _1-4 alkyl C _{6 -10} aryl groups, especially mono or di C _1-4 alkylphenyl groups); C _1-10 alkoxy C _6-10 aryl groups such as methoxyphenyl, ethoxyphenyl, _{methoxynaphthyl} groups (preferably C _1-6 alkoxy C) _6-10 aryl group, especially C _1-4 alkoxyphenyl group, etc.).

  The silyl group may be a substituted silyl group substituted with the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group or the like.

The halogen atom represented by X ^{1 to} X ⁴ includes F, Cl, Br, and I, and Cl and Br (particularly Cl) are preferable.

  In addition, as a dihalosilane compound represented by Formula (2), a monomer (p = 1) may be used and an oligomer or a polymer (p = 2 to about 1000) may be used. A preferable coefficient p is about 1 to 100 (for example, 1 to 50), preferably 1 to 10, and more preferably about 1 to 5 (for example, 1 to 3). When an oligomer having a large p value is used, a block copolymer is obtained, and when a monomer having a small p value is used, a random copolymer is obtained. From the viewpoint of the production efficiency of the copolymer, it is preferable to use dihalosilane (2) having p of about 1-2. Moreover, the trihalosilane compound represented by Formula (3), the tetrahalosilane compound represented by Formula (4), or the monohalosilane compound represented by Formula (5) is usually used as a monomer.

In the dihalosilane compound represented by the formula (2) and the formula (2a), the combination of R ¹ and R ² is not particularly limited, and is an alkyl group (preferably a linear or branched C ₁ such as a methyl group). _-10 alkyl group) and an alkyl group (preferably a linear or branched C _1-10 alkyl group such as a methyl group), the alkyl group and a cycloalkyl group (C ₅ such as a cyclohexyl group). _{A -10} cycloalkyl group), a combination of the alkyl group and an aryl group (such as a C _6-12 aryl group _optionally having a substituent such as a phenyl group, a tolyl group), and the alkyl group Examples thereof include a combination with an aralkyl group and a combination of the cycloalkyl group and the aryl group. Preferred combinations are an alkyl group and an alkyl group, an alkyl group and a cycloalkyl group, and an alkyl group and an aryl group.

Examples of such compounds include diC _1-6 alkyldihalosilanes (dimethyldihalosilane, ethylmethyldihalosilane, diethyldihalosilane, dibutyldihalosilane, di-t-butyldihalosilane, and the like). C _1-4 alkyldihalosilane, etc.), C _1-6 alkyl-C _5-10 cycloalkyldihalosilane (methyl cyclohexyl dihalosilane, ethylcyclohexyl dihalosilane, butylcyclohexyl dihalosilane, etc. C _1-4 Alkyl-C _5-8 cycloalkyldihalosilane, etc.), C _1-6 alkyl-C _6-12 aryl dihalosilane (methylphenyldihalosilane, ethylphenyldihalosilane, butylphenyldihalosilane, t-butyl) Phenyldihalosilane, methyltolyldihalosilane, ethyltolyldihalosilane, butyltolyldihalosilane, methyl C _1-4 alkyl-C _6-10 aryl dihalosilane such as ruxyldihalosilane). These compounds can be used alone or in combination of two or more. Preferred dihalosilane compounds (2) include alkyl-aryl dihalosilanes (eg, methylphenyl dihalosilane, methyltolyl dihalosilane, etc.) and alkyl-cycloalkyl dihalosilanes (eg, methylcyclohexyl dihalosilane). It can be illustrated.

In the trihalosilane compound represented by the formula (3), R ³ is usually an alkyl group (preferably a linear or branched C _1-6 alkyl group such as a methyl group), a cycloalkyl group (cycloto C _5-8 cycloalkyl group such as xyl group), aryl group (C _6-12 aryl group _optionally having substituent such as phenyl group, tolyl group), aralkyl group (C such as benzyl group) _6-12 aryl C _1-4 alkyl groups, etc.). R ³ is usually a linear or branched C _1-4 alkyl group such as a methyl group, a C _5-8 cycloalkyl group such as a cyclohexyl group), a substituent such as a phenyl group or a tolyl group. In many cases, it may be a C _6-10 aryl group. Examples of trihalosilane compounds include C _1-6 alkyltrihalosilanes (such as methyltrichlorosilane, butyltrichlorosilane, t-butyltrichlorosilane, and hexyltrichlorosilane), C _6-10 cycloalkyltrihalosilanes (such as cyclohexyltrihalosilane), and C. Examples thereof include _6-10 aryltrihalosilane (phenyltrichlorosilane, tolyldichlorosilane, xylyltrichlorosilane, etc.).

In the formula (5), the combination of R ⁴ , R ⁵ and R ⁶ is not particularly limited. Examples of the monohalosilane compound represented by the formula (5) include a trialkylhalosilane in which an alkyl group is a linear or branched C _1-6 alkyl group such as a methyl group, and a cycloalkyl group is a cyclohexyl group. A tricycloalkylhalosilane which is a C _5-10 cycloalkyl group such as a triarylhalosilane whose aryl group is a C _6-12 aryl group which may have a substituent such as a phenyl group or a tolyl group, mono C _1-6 alkyl di C _5-10 cycloalkyl halosilanes, mono- C _1-6 alkyl di C _6-12 aryl halosilane, di-C _1-6 alkyl mono- C _5-10 cycloalkyl halo silane, di-C _1-6 alkyl Examples thereof include mono C _{6-12 arylhalosilane} . More specifically, examples of the compound (5) include tri-C _1-6 alkylhalosilane (trimethylhalosilane, tributylhalosilane, etc.), di-C _{1-6 alkylC 6-10} arylhalosilane (dimethylphenyl). Halosilanes, etc.), mono C _1-6 alkyldiC _6-10 arylhalosilanes (methyldiphenylhalosilanes, etc.), tri C _6-10 arylhalosilanes (triphenylchlorosilanes, tolylchlorosilanes, trixylylchlorosilanes, etc.) It can be illustrated.

  These halosilane compounds (2) to (5) can be used alone or in combination of two or more. The proportion of these halosilane compounds used can be appropriately selected according to the desired structure, molecular weight, physical properties, etc. of the polysilane. Of these halosilane compounds (2) to (5), at least one or both selected from dihalosilane compound (2) and trihalosilane compound (3) (particularly at least dihalosilane compound (2)) are often used. The usage-amount of the dihalosilane compound (2) and / or trihalosilane (3) is 30-100 mol% with respect to the whole halosilane compounds (2)-(5), Preferably it is 50-100 mol%, Furthermore, About 70-100 mol% (for example, 80-100 mol%) may be sufficient. The ratio of the dihalosilane compound (2) and the trihalosilane compound (3) can usually be selected from the range of the former / the latter = 100/0 to 0/100 (molar ratio), for example, 95/5 to 5/95. (Molar ratio), preferably 90/10 to 10/90 (molar ratio).

  The diaryldihalosilane compound (1) and at least one halosilane selected from halosilane compounds (2) to (5) can be used in any combination. Usually, the amount of at least one halosilane selected from halosilane compounds (2) to (5) (particularly a dihalosilane compound represented by formula (2) or a trihalosilane compound represented by formula (3)) is halosilane. 1 mol% or more (for example, 2 to 70 mol%), preferably 3 mol% or more (for example, 3 to 65 mol%), more preferably 5 mol% or more with respect to the total of compounds (1) to (5) ( For example, 5 to 60 mol%).

  The ratio of the diaryldihalosilane compound (1) and at least one halosilane selected from the halosilane compounds (2) to (5) is, for example, the former / the latter = 99/1 to 10/90 (molar ratio), The ratio is preferably 97/3 to 20/80 (molar ratio), more preferably about 95/5 to 30/70 (molar ratio), and may be about 90/10 to 50/50 (molar ratio).

  The halosilane compound is preferably a compound having as high purity as possible. For example, a liquid halosilane compound is preferably dried using a desiccant such as calcium hydride and distilled, and a solid halosilane compound is purified and used by a recrystallization method or the like. Is preferred.

  By combining the diaryldihalosilane compound (1) and at least one halosilane selected from halosilane compounds (2) to (5), even a halosilane having low reactivity alone can be selected as a starting material, The structure of the halosilane can be easily incorporated into the structure of the diaryl copolymer polysilane rather than polymerizing alone. Therefore, various characteristics can be imparted to the diarylpolysilane. Furthermore, polysilane (chain or cyclic copolysilane) having various structures can be produced by selecting reaction components. In particular, a copolysilane having a cyclic structure (copolymerized polysilane) can be easily obtained by a combination of the diaryldihalosilane compound (1) and the halosilane compounds (2) to (5).

[Aprotic solvent]
The reaction is usually performed in the presence of a solvent inert to the reaction. As the solvent, aprotic solvents (inert solvents) can be widely used. For example, ethers (cyclic C _4-6 ethers such as 1,4-dioxane, tetrahydrofuran and tetrahydropyran, diethyl ether, diisopropyl ether, 1, Chain C _4-6 ethers such as 2-dimethoxyethane and bis (2-methoxyethyl) ether), carbonates (ethylene carbonate, propylene carbonate, etc.), nitriles (acetonitrile, benzonitrile, etc.), amides (dimethylformamide) , Dimethylacetamide, etc.), sulfoxides (dimethylsulfoxide, etc.), halogen-containing compounds (halogenated hydrocarbons, such as methylene chloride, chloroform, bromoform, chlorobenzene, bromobenzene), aromatic hydrocarbons (benzene, Toluene, xylene), aliphatic hydrocarbons (hexane, cyclohexane, octane, linear or cyclic hydrocarbons such as cyclooctane), and the like, these solvents may be used as a mixed solvent. As the solvent, a polar solvent alone (tetrahydrofuran, 1,2-dimethoxyethane, etc.), a mixture of two or more polar solvents, a mixture of a polar solvent and a nonpolar solvent, and the like are preferable. When a mixture of a polar solvent and a nonpolar solvent is used, the ratio between the two is the former / the latter (weight ratio) = 1 / 0.01 to 1/20.

  If the concentration of the halosilane compound in the solvent (reaction solution) is too high, the solubility of the metal halide may decrease or polysilane having a narrow molecular weight distribution may not be generated. Accordingly, the concentration of the halosilane compound in the solvent (reaction solution) is usually 20 mol / L or less (for example, 0.05 to 20 mol / L), preferably 10 mol / L or less (for example, 0.2 to 10). Mol / L), particularly about 5 mol / L or less (for example, 0.3 to 5 mol / L).

[Magnesium metal component]
The reaction between the diaryldihalosilane compound (1) and at least one halosilane selected from the halosilane compounds (2) to (5) can be carried out in the presence of a magnesium metal component, and the magnesium metal component is allowed to act. As a result, copolysilane can be produced efficiently.

  The magnesium metal component only needs to contain at least magnesium, and may be a magnesium metal alone or a magnesium alloy, or a mixture containing the magnesium metal or alloy. The kind of magnesium alloy is not particularly limited, and examples thereof include conventional magnesium alloys such as magnesium alloys containing components such as aluminum, zinc, rare earth elements (scandium, yttrium, etc.). These magnesium metal components can be used alone or in combination of two or more.

  The shape of the magnesium metal component is not particularly limited as long as it does not impair the reaction of the halosilane compound, but examples thereof include powder particles (powder, granules, etc.), ribbons, cut pieces, lumps, rods, flat plates, etc. In particular, a shape having a large surface area (powder, granule, ribbon, cut piece, etc.) is preferable. When the magnesium metal component is granular, the average particle size is about 1 to 10,000 μm, preferably about 10 to 5000 μm, and more preferably about 20 to 1000 μm.

  Depending on the storage status of the magnesium metal component, a film (such as an oxide film) may be formed on the metal surface. Since this coating may adversely affect the reaction, it may be removed by an appropriate method such as cutting or elution (pickling such as hydrochloric acid cleaning) as necessary.

  The amount of magnesium metal component used is usually 1 to 20 equivalents, preferably 1.1 to 14 equivalents, more preferably 1.2 to 10 equivalents (for example, in terms of magnesium) with respect to the halogen of the halosilane compound. 1.2 to 5 equivalents). Moreover, the usage-amount of a magnesium metal component is 1-20 times as magnesium normally with respect to a halosilane compound as a magnesium number, Preferably it is 1.1-14 times, More preferably, it is 1.2-10 times ( For example, about 1.2 to 5 times.

  The magnesium metal component reduces the compounds represented by the above formulas (1) to (5) to form polysilane, and magnesium itself is oxidized to form a halide.

  The reaction may be performed at least in the presence of the magnesium metal component. In order to promote polymerization of the halosilane, the reaction may be performed in the presence of at least one selected from a lithium compound and a metal halide (promoter or catalyst), particularly a lithium compound. And in the presence of both metal halides.

[Lithium compounds]
The lithium compound functions as a catalyst for promoting the polymerization of halosilane. Lithium compounds include lithium halides (lithium chloride, lithium bromide, lithium iodide, etc.), inorganic acid salts (lithium nitrate, lithium carbonate, lithium hydrogen carbonate, lithium hydrochloride, lithium sulfate, lithium perchlorate, lithium phosphate Etc.) can be used. These lithium compounds can be used alone or in combination of two or more. A preferred lithium compound is lithium halide (especially lithium chloride).

  If the concentration of the lithium compound in the solvent (or reaction mixture) is too low, the reaction rate may decrease. If it is too high, the polarity of the reaction solution will change, resulting in a decrease in the reaction rate or the desired formation. The Si—Si main chain bond of polysilane, which is a product, is cleaved, and the molecular weight of the product may decrease. Therefore, the concentration of the lithium compound in the solvent (reaction solution) is usually 0.05 to 5 mol / L, preferably 0.1 to 4 mol / L, particularly about 0.15 to 3 mol / L.

  The proportion of the lithium compound is 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 5 to 100 parts by weight (for example, 5 to 75 parts by weight) based on 100 parts by weight of the total amount of the halosilane compound. Usually, it is about 10 to 80 parts by weight.

[Metal halogen compounds]
Like lithium compounds, metal halides also function as catalysts that promote the polymerization of halosilanes. Examples of the metal halide include polyvalent metal halides such as transition metals (for example, periodic table group 3A elements such as samarium, periodic table group 4A elements such as titanium, periodic table group 5A elements such as vanadium, iron, nickel, Periodic table group 8 elements such as cobalt and palladium, periodic table group 1B elements such as copper, periodic table group 2B elements such as zinc), periodic table group 3B metals (such as aluminum), periodic table group 4B metals (such as tin) Metal halides such as chloride, bromide or iodide. Although the valence of the metal constituting the metal halide is not particularly limited, it is preferably 2 to 4 valence, particularly 2 or 3 valence. These metal halides can be used alone or in combination of two or more.

  The metal halide is preferably a chloride or bromide of at least one metal selected from iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium and the like.

Examples of such metal halides include chlorides (iron chlorides such as FeCl ₂ and FeCl ₃ ; AlCl ₃ , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VCl ₂ , TiCl ₄ , PdCl ₂ , SmCl _2, etc.), Examples thereof include bromides (such as iron bromide such as FeBr ₂ and FeBr ₃ ) and iodides (such as SmI ₂ ). Of these metal halides, chlorides (for example, iron chlorides such as iron (II) chloride and iron (III), zinc chloride) and bromides are preferred. Usually, iron chloride and / or zinc chloride is used.

  If the concentration of the metal halide in the solvent (reaction solution) is too low, the reaction rate may decrease. If it is too high, the polarity of the reaction solution will change and decrease at the reaction rate, or activated magnesium may be halogenated. There is a risk of oxidation as a chemical. Therefore, the concentration of the metal halide in the solvent is usually about 0.001 to 6 mol / L, preferably about 0.005 to 4 mol / L, more preferably 0.01 to 3 mol / L. About L.

  The ratio of the metal halide is about 0.1 to 50 parts by weight, preferably about 1 to 30 parts by weight, and more preferably about 2 to 20 parts by weight with respect to 100 parts by weight of the total amount of the halosilane compound.

[Reaction method or production method]
In the production method of the present invention, for example, in a sealable reaction vessel, reaction components [diaryldihalosilane compound (1) and halosilane compound selected from compounds (2) to (5)], magnesium metal component, and If necessary, the lithium compound and / or metal halide may be accommodated together with a solvent, and the reaction may be carried out preferably with mechanical or magnetic stirring. The raw material halosilane compound may be used in advance as a mixture of a plurality of halosilane compounds, or a plurality of halosilane compounds may be added in parallel or intermittently, or may be added in time series (for example, the first One halosilane component may be added to the reaction system to allow the reaction to proceed to produce polysilane or oligosilane, and then the second halosilane component may be added to react. The former method used as a mixture of a plurality of halosilane compounds is suitable for obtaining a random copolymer (random copolysilane). The latter method, in which the second halosilane component is added during the reaction of the first halosilane component, is suitable for obtaining a block copolymer. In the latter method, it is sufficient that at least one of the first halosilane component and the second halosilane component contains the diaryldihalosilane represented by the formula (1). That is, one of the compounds represented by the above formula (1) and at least one compound selected from the compounds represented by the above formulas (2) to (5) is reacted to produce polysilane or oligosilane. After the production, the other component may be added to the reaction system and reacted to produce polysilane. For example, after reacting the compound represented by the formula (1) to produce polysilane or oligosilane, at least one halosilane compound among the compounds represented by the formulas (2) to (5) is used as a reaction system. After adding at least one halosilane compound among the compounds represented by the formulas (2) to (5) to produce polysilane or oligosilane, at least the formula (1) A compound represented may be added to the reaction system and reacted to form polysilane.

  As long as the reaction vessel can be sealed, there is no particular limitation on the shape and structure. The reaction vessel may have a dry atmosphere, but a dry inert gas (eg, nitrogen gas, helium gas, argon gas) atmosphere, particularly a deoxygenated and dried argon gas atmosphere is preferable.

  The reaction time varies depending on the amount of the halosilane compound, the magnesium metal component and the catalyst component (lithium compound, metal halide), etc., but is 5 minutes or longer, and is usually about 30 minutes to 100 hours. By adjusting the reaction time, the amount of magnesium metal component, and the type and amount of catalyst, the molecular weight and structure of polysilane can be controlled.

  The reaction temperature is usually in the temperature range from −20 ° C. to the boiling point of the solvent used, preferably 0 to 80 ° C., more preferably about 20 to 70 ° C. The produced copolymer may be purified by a conventional method such as a reprecipitation method using a good solvent and a poor solvent, or an extraction method.

  In such a method, polysilane having a uniform molecular weight can be produced in a high yield by a simple method in which a stirring operation is performed at a temperature near room temperature. In addition, since a commercially available raw material is used without using an expensive reagent and a special apparatus such as a light irradiator, an ultrasonic irradiation apparatus, or an electrode reaction apparatus is not used, the polysilane can be produced at a low cost. Furthermore, the said polysilane which has a desired structure can be manufactured only by adjusting a monomer concentration, the kind of catalyst, quantity, and reaction time.

[Structure of polysilane]
The copolysilane (polysilane copolymer) obtained by the above-described method is a diarylsilane unit corresponding to the diaryldihalosilane compound represented by the formula (1) and other halosilane compounds [represented by the formulas (2) to (5). And a silane unit corresponding to the halosilane compound]. The structure of the copolysilane may be linear, branched, or cyclic. That is, the copolysilane (polysilane copolymer) of the present invention has at least one structural unit selected from structural units represented by the following formula (6) and structural units represented by the following formulas (7) to (10). It consists of.

(In the formula, Ar ¹ , Ar ² , R ^{1 to} R ⁶ are the same as described above. R, s, t and u represent the number of each structural unit, and the total of r, s, t and u is an integer of 2 to 1000. Is).

  Specifically, using the diaryldihalosilane represented by the formula (1) and the dihalosilane compound represented by the formula (2), the structural unit (6) and the structural unit ( A copolymer composed of 7) is obtained.

(In the formula, Ar ¹ , Ar ² , R ¹ and R ² are the same as described above. R and s represent the number of each structural unit, r is an integer of 1 to 1000, and s is an integer of 1 to 1000).

  In addition, by using the diaryldihalosilane represented by the formula (1) and the dihalosilane compound represented by the formula (3), the structural unit (6) and the structural unit (8) represented by the following formula: A copolymer composed of

(In the formula, Ar ¹ , Ar ² , and R ³ are the same as described above. R and t represent the number of each structural unit, r is an integer of 1 to 1000, and t is an integer of 1 to 1000).

  In addition, using the diaryldihalosilane represented by the formula (1) and the monohalosilane compound represented by the formula (4), the structural unit (6) and the structural unit (10) represented by the following formula: A copolymer composed of can also be obtained. In this case, the structural unit (10) is necessarily the end of the copolymer.

(In the formula, Ar ¹ , Ar ² and R ^{4 to} R ⁶ are the same as described above. R represents the number of each structural unit, and r is an integer of about 2 to 100).

  The weight average molecular weight of polysilane is about 300 to 100,000, preferably about 400 to 10,000, and more preferably about 500 to 5,000. The average degree of polymerization is about 3 to 1000, preferably about 4 to 100, and more preferably about 5 to 50. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is Mw / Mn = 1 to 2, preferably about 1.1 to 1.5. In the present invention, polysilane copolymers having various molecular weights and structures can be arbitrarily obtained by combining silane compounds.

  Regarding polysilanes, diaryl polysilanes (such as diphenyl polysilane) are particularly high in refractive index and water repellency, but have insufficient solubility in solvents and compatibility with resins. On the other hand, the copolysilane of the present invention has a higher solubility in a solvent, a lower melting point, and improved compatibility with a resin as compared with decaphenylcyclopentasilane (a cyclic pentamer of diphenylpolysilane). .

  In order to effectively exhibit the characteristics of the polydiarylsilane, it is advantageous that the diaryldihalosilane compound (1) has a cyclic structure since it is easily cyclized in the reaction.

  A preferable cyclic copolysilane can be represented by the following formula, for example.

(In the formula, Ar ¹ and Ar ² represent an aryl group which may have a substituent, and R ¹ and R ² are the same or different, and represent a hydrogen atom, a silyl group, an alkyl group, a cycloalkyl group or an aryl group. A silyl group, an alkyl group, a cycloalkyl group, or an aryl group may have a substituent, provided that R ¹ and R ² are not an aryl group at the same time, and m and n are each 1 And m + n is an integer greater than or equal to 4. p is the same as above)

Ar ¹ , Ar ² , R ¹ and R ² are as described above. Preferable Ar ¹ and Ar ² are C _6-10 aryl groups [phenyl group, C _1-4 alkylphenyl group (tolyl group, xylyl group, etc.)], and are usually phenyl groups. Preferred R ¹ and R ² are C _1-4 alkyl groups (such as methyl groups), C _5-8 cycloalkyl groups (such as cyclohexyl groups), C _6-10 aryl groups (such as phenyl groups), or C _1-4 alkyl groups. A C _6-10 aryl group (tolyl group, xylyl group, etc.), and the combination of R ¹ and R ² is usually a combination of a C _1-4 alkyl group and a C _1-4 alkyl group, C _1-4 A combination of an alkyl group and a C _5-8 cycloalkyl group, or a combination of a C _1-4 alkyl group and a C _6-10 aryl group.

  m and n are each about 1 to 100, preferably 1 to 50, more preferably about 1 to 10 (for example, 1 to 5), and m + n is 4 to 200, preferably 4 to 100, Preferably, it may be about 4-50. In the main polysilane produced by the reaction, m + n is usually 4 to 25 (for example, 4 to 20), preferably about 4 to 10 (for example, 4 to 8, particularly 4 to 6).

  For example, when preparing polysilane using diphenyldihalosilane and another dihalosilane, the main component is a cyclic pentamer corresponding to the charged ratio of dihalosilane by appropriately selecting the type, amount and reaction temperature of the catalyst. Can be generated as As apparent from the structure, this cyclic polysilane has a feature that it does not contain an oxygen atom in the structure, like decaphenylcyclopentasilane. Furthermore, with respect to the by-product generated by the above reaction, most of the cyclic polysilane or the linear polysilane having a terminal hydrogen atom is present, and the oxygen content relative to the entire product is also small. Therefore, there is little absorption in the visible light region (especially in the short wavelength region) due to the Si-O-Si structure or Si-OH group, and not only the product but also the transparency of the solution in which the product is dissolved in various solvents is very high. It is characterized by being high.

  More specifically, methylnonaphenylcyclopentasilane represented by the following formula (11) can be synthesized by reacting diphenyldichlorosilane and methylphenyldichlorosilane at a molar ratio of 4: 1. When diphenyldichlorosilane and methylphenyldichlorosilane are reacted at a molar ratio of 1: 1, dimethyloctaphenylcyclopentasilane represented by the following formula (12) and trimethylheptaphenyl represented by the following formula (13) Mixtures with cyclopentasilane can be made 1: 1.

  Regarding the cyclic copolysilanes represented by the above formulas (11) to (13), compared with decaphenylcyclopentasilane, it exhibits higher solubility in various solvents and film formation is also easy. In addition, since it contains almost no oxygen, including by-products, it is less colored even when dissolved in an organic solvent, and exhibits high transparency. Furthermore, the melting point of decaphenylcyclopentasilane is as high as 192 ° C., whereas the cyclic copolysilane represented by the formulas (11) to (13) has a low melting point of 100 ° C. or less (for example, about 60 to 100 ° C.). On the other hand, the cyclic copolysilanes represented by the formulas (11) to (13) are solid at room temperature, have high fluidity, and are non-adhesive, so that they are very easy to handle in handling, for example, addition to a resin. Is easy.

  In addition, in the said method of this invention, the polysilane mixture containing the polysilane (cyclic polysilane) which has a cyclic structure is also produced | generated. Therefore, the present invention also includes a polysilane mixture containing cyclic polysilane (cyclic co or homopolysilane).

  Examples of the cyclic homopolysilane include diaryl polysilane (such as diphenyl polysilane), alkyl-aryl polysilane, alkyl-cycloalkyl polysilane, dialkyl polysilane, and dicycloalkyl polysilane corresponding to the compound represented by the formula (1). The content of the cyclic polysilane (cyclic co or homopolysilane) is, for example, 40% by weight or more (for example, 40 to 100% by weight), preferably 50% by weight or more (for example, 50 to 100% by weight) with respect to the entire polysilane mixture. %), More preferably 60% by weight or more (for example, 60 to 100% by weight).

  Furthermore, the ratio of the pentameric cyclic polysilane (homo or copolysilane) to the whole polysilane mixture is, for example, 20% by weight or more (for example, 2 to 100% by weight), preferably 30% by weight or more (for example, 30 to 30%). 90% by weight), more preferably 40% by weight or more (for example, 40 to 90% by weight).

[Resin composition]
The resin composition of the present invention is composed of the polysilane and the resin, and polysilane (copolysilane or a polysilane mixture) is usually added as an additive. The kind of resin is not specifically limited, Any of a thermoplastic resin and a thermosetting resin may be sufficient.

  Examples of thermoplastic resins include olefin resins [polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.], halogen-containing resins [polyvinyl chloride, fluororesins, etc.], styrene resins [polystyrene, acrylonitrile-styrene. Resin], acrylic resin [polymethyl methacrylate, etc.], polycarbonate resin [bisphenol A type polycarbonate resin, etc.], polyester resin [polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polyarylate , Liquid crystal polyester, etc.], polyacetal resin, polyamide resin [nylon 6, nylon 66, nylon 46, nylon 6T, nylon MXD, etc.], poly Ren ether resins [modified polyphenylene ether, etc.], polysulfone resins [polysulfone, polyethersulfone, etc.], polyimide resins [polyetherimide, polyamideimide, etc.], maleimide resins [polyamino bismaleimide, bismaleimide triazine resins, etc.] Examples thereof include thermoplastic elastomers.

  Thermosetting resins include phenolic resin, furan resin, amino resin [urea resin, melamine resin, etc.], unsaturated polyester resin, diallyl phthalate resin, epoxy resin, vinyl ester resin, polyurethane resin, silicone resin, polyimide resin, etc. It can be illustrated. The thermosetting resin may be an initial condensate.

  These resins can be used alone or in combination of two or more. When using a plurality of resins, a polymer alloy may be formed.

  The amount of polysilane added varies depending on the type and application of the resin and polysilane, but is generally 0.01 to 50 parts by weight (for example, 0.5 to 50 parts by weight), preferably 0.1 to 100 parts by weight of the resin. It may be about 30 parts by weight. If the addition amount is small, properties such as flame retardancy and water repellency cannot be imparted, and if it is too large, the properties of the resin may be impaired.

  The resin composition of the present invention has various additives such as a solvent, a filler, a reinforcing agent, a plasticizer, a curing agent, a polymerization initiator, a catalyst, a stabilizer (an antioxidant, an ultraviolet absorber, etc.) depending on the application. ), Release agents, antistatic agents, colorants, vulcanizing agents, antifoaming agents, leveling agents, dispersing agents, flow control agents, and the like.

  The method of adding and mixing polysilane to the resin is not particularly limited, and usually, resin pellets, polysilane, and if necessary, additives are often melt-mixed. For example, after premixing resin pellets and components such as a stabilizer, polysilane may be melt-mixed in a kneading apparatus together with additives such as reinforcing agents and fillers as necessary. The melt-mixed resin composition is usually pelletized and subjected to molding. There are two types of kneaders: a batch type and a continuous type. Examples of the batch-type kneader include a mixing roll, a kneader, and an intensive mixer. Examples of the continuous kneader include a single screw extruder, a meshing twin screw extruder, and a non-meshing twin screw extruder.

  In a thermosetting resin, generally, a curable composition is prepared by mixing polysilane and a resin initial condensate together with various resin additives such as a curing agent. In addition, the polysilane and the resin initial condensate are mixed or mixed in a dissolution tank, and if necessary, kneaded with an additive such as a reinforcing agent to prepare a curable composition, and this curable composition is used as a base cloth or the like. It may be impregnated, dried and cured.

  The molding method of the resin composition varies depending on the type and use of the resin. In the case of a thermoplastic resin, methods such as extrusion molding, injection molding, blow molding, stretched film molding, compression molding, calendar molding, RIM molding, etc. It can be illustrated. In the case of a thermosetting resin, methods such as compression molding, transfer molding, laminate molding, cast molding, and RIM molding can be exemplified.

  The present invention can improve the affinity for solvents and resins while maintaining the characteristics of diarylpolysilane. Therefore, the characteristics of diarylpolysilane, such as flame retardancy, water repellency, releasability, and slipperiness, can be effectively imparted to resins and substrates. Therefore, various uses, for example, ceramic precursors, optoelectronic materials (for example, photoelectrophotographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, electroluminescent element materials, etc. ), Flame retardants, water repellents, release agents and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The molecular weight of polysilane was measured by gel permeation chromatography. Further, FD-MS (Field Desorption-Mass Spectrometry) uses “JMS-700” manufactured by JEOL Ltd., ionization method: FD (Electrolytic Desorption Field Desorption), emitter: carbon, emitter current: 0-40 mA. (2 mA / min), acceleration voltage: 8 kV, counter voltage: 2 kV.

Example 1
In a 1000 mL round flask equipped with a three-way cock, 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), and anhydrous iron (II) chloride (FeCl ₂ ) 20. 0 g was charged, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), dried argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and about 30 minutes at room temperature. Stir. To this reaction mixture, a mixture of 60.8 g (0.24 mol) of diphenyldichlorosilane previously purified by distillation and 11.5 g (0.06 mol) of methylphenyldichlorosilane previously purified by distillation was added with a dropping funnel, and the mixture was added at 50 ° C. For about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain a white solid of cyclic diphenyldichlorosilane-methylphenyldichlorosilane copolymer. (Weight average molecular weight 1200, yield 85%).

FD-MS: 724,786,848,910,1151,1212,1395
From this analysis result, the product has two distributions in the molecular weight distribution: a distribution having a molecular weight of 848 as a vertex and a distribution having a molecular weight of 1212 as a vertex.

Reference example 1
A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), and 15.0 g of anhydrous zinc chloride (ZnCl ₂ ). After drying at 50 ° C. by heating to 1 mmHg (= 133 kPa) under reduced pressure, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature for about 30 minutes. To this reaction mixture, a mixture of 60.8 g (0.24 mol) of diphenyldichlorosilane previously purified by distillation and 11.5 g (0.06 mol) of methylphenyldichlorosilane previously purified by distillation was added with a dropping funnel, and the mixture was added at 50 ° C. For about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain a white solid of cyclic diphenyldichlorosilane-methylphenyldichlorosilane copolymer. (Weight average molecular weight 3500, yield 80%).

  The diphenyldichlorosilane-methylphenyldichlorosilane copolymer was reprecipitated using 200 ml of good solvent tetrahydrofuran and 1000 ml of poor solvent methanol to obtain a cyclic diphenyldichlorosilane-methylphenyldichlorosilane copolymer having a weight average molecular weight of 3200.

Example 3
In a 1000 ml round flask equipped with a three-way cock, 65.9 g of granular (particle size 20 to 1000 μm) magnesium, 30.0 g of anhydrous lithium chloride (LiCl), anhydrous iron (III) chloride (FeCl ₃ ) 15. 0 g was accommodated and heated to 50 ° C. under reduced pressure to 1 mmHg (= 133 kPa) to dry the reaction mixture. Then, dry argon gas was introduced into the reactor, and 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added. Stir at room temperature for about 30 minutes. To this reaction mixture, a mixture of 50.6 g (0.20 mol) of diphenyldichlorosilane purified in advance by distillation and 38.2 g (0.20 mol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe, and the mixture was mixed at 50 ° C. Stir for about 24 hours. To the reaction mixture, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain a white solid of cyclic diphenyldichlorosilane-methylphenyldichlorosilane copolymer. (Weight average molecular weight 1000, yield 90%).

  The diphenyldichlorosilane-methylphenyldichlorosilane copolymer was reprecipitated using 200 ml of good solvent toluene and 800 ml of poor solvent 2-propanol to obtain a cyclic diphenyldichlorosilane-methylphenyldichlorosilane copolymer having a weight average molecular weight of 1100. .

    FD-MS: 662, 724, 786, 848, 906

Reference example 2
In a 1000 mL round flask equipped with a three-way cock, 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), anhydrous iron (III) chloride (FeCl ₃ ) 20. 0 g was charged, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), dried argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and about 30 minutes at room temperature. Stir. To this reaction mixture, a mixture of 101.3 g (0.40 mol) of diphenyldichlorosilane purified in advance by distillation and 21.2 g (0.10 mol) of phenyltrichlorosilane purified in advance by distillation was added with a dropping funnel at 60 ° C. Stir for about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain a light yellow solid of diphenyldichlorosilane-phenyltrichlorosilane copolymer (weight) Average molecular weight 1300, yield 90%).

Reference example 3
In a 1000 mL round flask equipped with a three-way cock, 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), anhydrous iron (III) chloride (FeCl ₃ ) 20. 0 g was charged, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), dried argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and about 30 minutes at room temperature. Stir. To this reaction mixture, a mixture of 101.3 g (0.40 mol) of diphenyldichlorosilane purified in advance by distillation and 12.9 g (0.10 mol) of dimethyldichlorosilane purified in advance by distillation was added with a dropping funnel at 60 ° C. Stir for about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain a light yellow solid of diphenyldichlorosilane-dimethyltrichlorosilane copolymer (weight) Average molecular weight 1000, yield 90%).

Reference example 4
In a 1000 mL round flask equipped with a three-way cock, 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), anhydrous iron (III) chloride (FeCl ₃ ) 20. 0 g was charged, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), dried argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and about 30 minutes at room temperature. Stir. To this reaction mixture, a mixture of 101.3 g (0.40 mol) of diphenyldichlorosilane purified beforehand by distillation and 19.7 g (0.10 mol) of cyclohexylmethyldichlorosilane purified beforehand by distillation was added with a dropping funnel, and the mixture was added at 60 ° C. For about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain a white solid of a cyclic diphenyldichlorosilane-cyclohexylmethyldichlorosilane copolymer. (Weight average molecular weight 1100, yield 85%).

Reference Example 5
A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 30.0 g of granular (particle size 20 to 1000 μm) magnesium, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), and then dried argon gas Was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature for about 30 minutes. To this reaction mixture, a mixture of 101.3 g (0.40 mol) of diphenyldichlorosilane purified in advance by distillation and 21.2 g (0.10 mol) of phenyltrichlorosilane purified in advance by distillation was added with a dropping funnel at 60 ° C. Stir for about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain a light yellow solid of diphenyldichlorosilane-methyltrichlorosilane copolymer (weight) (Average molecular weight 900, yield 70%).

Reference Example 6
In a 1000 mL round flask equipped with a three-way cock, 30.0 g of granular (particle size 20 to 1000 μm) magnesium, 40.0 g of anhydrous lithium chloride (LiCl), anhydrous iron (III) chloride (FeCl ₃ ) 20. 0 g was charged, dried at 50 ° C. under reduced pressure by heating to 1 mmHg (= 133 kPa), dried argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and about 30 minutes at room temperature. Stir. To this reaction mixture, a mixture of 101.3 g (0.40 mol) of diphenyldichlorosilane previously purified by distillation and 15.0 g (0.10 mol) of methyltrichlorosilane previously purified by distillation was added with a dropping funnel at 60 ° C. Stir for about 24 hours. After completion of the reaction, 250 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, followed by extraction with 1000 ml of toluene. The toluene layer was washed with 200 ml of pure water three times, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain a light yellow solid of diphenyldichlorosilane-phenyltrichlorosilane copolymer (weight) Average molecular weight 1600, yield 70%).

Reference Example 7
Except for using a mixture of 50.6 g (0.2 mol) of diphenyldichlorosilane, 4.8 g (0.025 mmol) of methylphenyldichlorosilane and 3.2 g (0.025 mmol) of dimethyldichlorosilane, which has been purified by distillation as halosilane, Reaction was carried out in the same manner as in Example 1 to obtain a diphenyldichlorosilane-methylphenyldichlorosilane-dimethyldichlorosilane copolymer having a weight average molecular weight of 1000 (yield 80%).

Reference Example 8
The reaction was carried out in the same manner as in Example 1 except that the reaction time was 6 hours to obtain a diphenyldichlorosilane-methylphenyldichlorosilane copolymer having a cyclic main component (weight average molecular weight 800, yield 60%). .

Reference Example 9
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 30 ° C., and a diphenyldichlorosilane-methylphenyldichlorosilane copolymer having a cyclic main component was obtained (weight average molecular weight 1700, yield 50%). ).

Reference Example 10
After adding 22.9 g (0.12 mol) of methylphenyldichlorosilane and stirring at room temperature for 2 hours to produce low molecular weight polysilane, 121.5 g (0.48 mol) of diphenyldichlorosilane purified in advance by distillation was added. A reaction was carried out in the same manner as in Example 3 except for adding to obtain a polymethylphenylsilane-polyphenylsilin copolymer (block copolymer) having a weight average molecular weight of 1100 (yield 60%).

Reference Example 11
The reaction was carried out in the same manner as in Example 2 except that 10.0 g of anhydrous nickel chloride (NiCl ₂ ) was used instead of 15.0 g of anhydrous zinc chloride (ZnCl ₂ ), and the main component was diphenyldichlorosilane-methylphenyldicyclic. A chlorosilane copolymer was obtained (weight average molecular weight 1900, yield 80%).

Reference Example 12
A reaction was carried out in the same manner as in Example 2 except that 7.5 g of anhydrous aluminum chloride (AlCl ₃ ) was used instead of 15.0 g of anhydrous zinc chloride (ZnCl ₂ ), and diphenyldichlorosilane-methylphenyldi having a weight average molecular weight of 2100. A chlorosilane copolymer was obtained (yield 75%).

Reference Example 13
The reaction is carried out in the same manner as in Example 3 except that 15.0 g of anhydrous lithium perchlorate (LiClO ₄ ) is used instead of 30.0 g of anhydrous lithium chloride (LiCl), and the main component is cyclic diphenyldichlorosilane-methylphenyl. A dichlorosilane copolymer was obtained (weight average molecular weight 1600, yield 65%).

Reference Example 14
The same procedure as in Example 3 was conducted except that 101.3 g (0.40 mol) of diphenyldichlorosilane purified in advance by distillation and 38.2 g (0.20 mol) of methylphenyldichlorosilane purified in advance by distillation were used. The reaction was carried out to obtain a diphenyldichlorosilane-methylphenyldichlorosilane copolymer having a cyclic main component (weight average molecular weight 1500, yield 55%).

Comparative Example 1
A reaction was carried out in the same manner as in Example 2 except that 114.7 g (600 mmol) of methylphenyldichlorosilane purified in advance by distillation as halosilane to obtain polymethylphenylsilane (yield 80%).

Comparative Example 2
A reaction was carried out in the same manner as in Example 2 except that 126.9 g (600 mmol) of phenyltrichlorosilane purified by distillation in advance was used as halosilane to obtain polyphenylsilin (yield 82%).

Comparative Example 3
A reaction was carried out in the same manner as in Example 1 except that 151.9 g (600 mmol) of diphenyldichlorosilane purified in advance by distillation as halosilane to obtain polydiphenylsilane (yield 85%).

The polysilane copolymer obtained in Examples 1 and 3 and Reference Example 2 and the polysilane obtained in Comparative Examples 1, 2 and 3 were mixed with equal amounts of various solvents to prepare a mixed solution having a concentration of 50% by weight. did. Then, the liquid mixture was visually observed, and the solubility of the polysilane copolymer was evaluated according to the following criteria. The results shown in Table 1 were obtained. In the table, THF represents tetrahydrofuran, and PGMEA represents propylene glycol monomethyl ether acetate.

○: Completely dissolved and transparent Δ: Dissolved but turbid ×: Some insoluble.

The polysilane copolymer obtained in Examples 1 and 3 and Reference Example 2 and the polysilane obtained in Comparative Examples 1 and 2 and 3 were mixed with an equal amount of toluene, respectively, to prepare a 50 wt% toluene mixed solution, The transmittance of visible light (600 nm) was measured. The results are shown in Table 2.

  The polysilane copolymer can be dissolved in various solvents and has high transparency of the solution as compared with the polysilane homopolymer. Therefore, it is considered that it can be developed for various uses, for example, for optoelectronic materials.

The polysilane copolymers obtained in Examples 1 and 3 and Reference Example 2 and the polysilanes obtained in Comparative Examples 1, 2 and 3 were added to polycarbonate resins with different addition amounts, and extruded. When the transparency of the molded product (thickness 3 mm) was visually observed, the results shown in Table 3 were obtained.

  Since the polysilane copolymer has higher compatibility with the resin than the polysilane homopolymer, it can be added more to the resin. Furthermore, a transparent resin can be added without impairing transparency. Therefore, excellent physical properties such as water repellency and flame retardancy of polysilane can be imparted to the resin.

Claims (1)

A resin composition comprising a cyclic copolysilane and a thermoplastic resin,
The cyclic copolysilane is a pentameric cyclic copolysilane composed of a diphenylsilane unit represented by the following formula (i) and a phenylmethylsilane unit represented by the following formula (ii) :
(In the formula, R ¹ is a methyl group and R ² is a phenyl group.)
The thermoplastic resin is composed of a polycarbonate resin,
The resin composition whose addition amount of the said cyclic copolysilane is 0.01-50 weight part with respect to 100 weight part of said resin .