Cage-shaped siloxane-containing polymer, cage-shaped siloxane, and method for producing same

Abstract

To manufacture and develop a silsesquioxane structure-containing polymeric compound having extremely high heat resistance and good mechanical properties.SOLUTION: A cage-like siloxane-containing polymer having high heat resistance and mechanical strength is obtained by polymerizing a cage-like siloxane compound whose stereo isomer ratio is controlled, and a straight chain siloxane compound. The cage-like siloxane compound whose stereo isomer ratio is controlled is manufactured by enriching an isomer by crystallizing a cage-like siloxane diol and silylating the enriched isomer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cage siloxane-containing polymer, a cage siloxane, and a method for producing the same. [Background technology]

[0002] Polysiloxanes, which have a silicon-oxygen-silicon bond as their main skeleton, are organic-inorganic hybrid compounds that have a wide range of uses, combining high heat resistance, light transmittance, excellent mechanical properties and good processability. Among them, (RSiO 1.5 ) n Polysilsesquioxanes represented by the formula (I) exhibit particularly excellent heat resistance, transparency and processability, and therefore research and development of such polysilsesquioxanes has been actively pursued in recent years. In particular, polymer compounds containing a double-decker silsesquioxane structure, which have good properties such as solubility in organic solvents, dispersion stability of organic polymers, control of refractive index and photocurability, have attracted attention. The primary structure of a polymer compound has a strong influence on its higher-order structure, and significantly changes various physical properties such as the solubility, glass transition point and crystallinity of the polymer compound. Therefore, even in polymer compounds containing a double-decker silsesquioxane structure, control of the primary structure is important in order to obtain good physical properties.

[0003] Non-Patent Document 1 reports on the synthesis of double-decker silsesquioxane-methyl-substituted linear siloxane alternating polymers and the effect of the number of silicon atoms in the linear siloxane moiety on the physical properties. Non-Patent Document 1 reports on the control of the chain length of the methyl-substituted linear siloxane moiety, but does not control the stereoisomerism of the silicon atom on the double-decker skeleton. In addition, no reports have been made on linear siloxane moieties other than methyl-substituted silicon.

[0004] Patent Document 1 discloses the synthesis and thermal properties of a double-decker silsesquioxane-linear siloxane alternating polymer in which the cis- and trans-stereoisomers of a diol having a double-decker silsesquioxane structure ring-closed with a silicon atom substituted with an isobutyl group are separated by recrystallization from a non-polar solvent, and the resulting polymer is used as a raw material to control the stereostructure. In Patent Document 1, the organic group on the silicon that ring-closes the double-decker silsesquioxane structure in the cage siloxane diol molecule is limited to an alkyl group having four carbon atoms. In addition, there is no description of the mechanical properties of this polymer.

[0005] Patent Document 2 discloses a method for producing a cage siloxane diol having a double-decker silsesquioxane structure, which is ring-closed with silicon atoms substituted with methyl and phenyl groups, which are advantageous in terms of improved heat resistance and cost, but does not disclose a method for separating these stereoisomers. Furthermore, cage siloxane diols substituted with methyl and phenyl groups have poor solubility in hydrocarbon solvents such as hexane and toluene, and the low solubility is likely to be a problem when performing a polymerization reaction using an acid catalyst in a hydrocarbon solvent as adopted in Patent Document 1. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2010-120901 A [Patent Document 2] Patent No. 4379120 [Non-patent literature]

[0007] [Non-Patent Document 1] Polymer, vol. 127, pp. 8-14, 2017. Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to produce and develop a silsesquioxane structure-containing polymer compound having extremely high heat resistance and good mechanical properties, and a membrane containing the same. [Means for solving the problem]

[0009] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have discovered that a cage siloxane-containing polymer having both high thermal stability and mechanical properties can be produced by a polymerization reaction between a cage siloxane compound enriched in trans- or cis-type stereoisomers and a linear siloxane compound, that the cage siloxane compound can be produced from a cage siloxane diol enriched in trans- or cis-type stereoisomers, and further that enrichment of the cage siloxane diol in stereoisomers can be achieved by crystallization, thereby completing the present invention.

[0010] That is, the present invention comprises the following: [1] General formula (1) [ka] (In the formula, R 1 , R 2 and R 3 R each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; a represents a real number ranging from 1 to 0.7, or a real number ranging from 0 to 0.3; n represents a real number ranging from 0 to 20; ran represents an irregular copolymer. Cage-shaped siloxane-containing polymers. In this specification, the phrase "optionally substituted with a halogen atom" means that any hydrogen atom in the alkyl group or phenyl group may be substituted with a halogen atom, and the number of substituted hydrogen atoms may be more than one. [2] A cured film comprising the cage-shaped siloxane-containing polymer according to [1], a crosslinking agent, and a crosslinking catalyst. [3] General formula (2a) [ka] (In the formula, R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and a trans-type cage siloxane compound represented by the general formula (2b): [ka] (In the formula, R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and a cage siloxane compound containing either the cis cage siloxane compound or the trans cage siloxane compound in an amount of 70 mol % or more; General formula (3) [ka] (In the formula, R 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; X represents a hydrogen atom, a methyl group, or an ethyl group; and m represents an integer of 2 to 10. Siloxane compounds, or General formula (3') [ka] (In the formula, R 4 and R 5each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; and in the presence of an acid catalyst. [4] A method for producing a cage siloxane-containing polymer represented by general formula (1), comprising the steps of: [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) is crystallized to obtain a cage-shaped siloxane diol represented by the general formula (4a) [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) or a trans-type cage siloxane diol represented by the general formula (4b): [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; The cage siloxane diol containing 70 mol % or more of the cage siloxane diol represented by the general formula (4a) or (4b) thus obtained and chlorohydrosilane R 2 R 3 HSiCl (wherein, R 2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, [ka] (In the formula, R 1 , R2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; or a trans-type cage siloxane compound represented by the general formula (2b): [ka] (In the formula, R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and The cage siloxane compound containing 70 mol % or more of the cage siloxane compound represented by the general formula (2a) or (2b) thus obtained and a cage siloxane compound represented by the general formula (3) [ka] (In the formula, R 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; X represents a hydrogen atom, a methyl group, or an ethyl group; and m represents an integer of 2 to 10. General formula (3') [ka] (In the formula, R 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; in the presence of an acid catalyst; A manufacturing method comprising the steps of: [5] General formula (4) [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) is crystallized from a polar organic solvent to obtain a cage-shaped siloxane diol represented by the general formula (4a) [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) or a trans-type cage siloxane diol represented by the general formula (4b): [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) to be enriched to 70 mol % or more. [6] The method for enriching any one of the cage-shaped siloxane diols according to [5] to 70 mol % or more, characterized in that the polar organic solvent contains at least one selected from the group consisting of tetrahydrofuran, acetone, and cyclopentyl methyl ether. [7] General formula (4a) [ka] (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) and a trans-type cage siloxane diol represented by the general formula (4b): [ka] (In the formula, R 1represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) and the cage-shaped siloxane diol is characterized in that it contains 70 mol % or more of either the cis cage-shaped siloxane diol or the trans cage-shaped siloxane diol. Effect of the Invention

[0011] The present invention can provide a siloxane polymer material having extremely high thermal stability, good visible light transmittance, and high mechanical strength. In addition, the stereoisomer-controlled monomer serving as the raw material thereof can be produced by a cost-effective method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below.

[0013] First, R in the general formulas (1), (2), (2a), (2b), (3), (4), (4a), and (4b) in this specification 1 , R 2 , R 3 , R 4 , R 5 The definition of X will be explained.

[0014] R 1 , R 2 and R 3 Each of the groups represented by R is independently an alkyl group having 1 to 3 carbon atoms or a phenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. From the viewpoints of the heat resistance, processability, and economic efficiency of the cage-shaped siloxane-containing polymer of the present invention, a methyl group is preferred. 1 , R 2 and R 3 The group represented by the formula: is preferably a phenyl group.

[0015] R 4 and R 5Each of the groups represented by the formula (I) is independently an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a 3,3,3-trifluoropropyl group, and from the viewpoints of the heat resistance, processability, and economic efficiency of the cage-shaped siloxane-containing polymer of the present invention, a methyl group is preferred. 4 and R 5 is preferably a phenyl group.

[0016] X is a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of the yield of the cage-shaped siloxane-containing polymer of the present invention, a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred.

[0017] Next, the cage-shaped siloxane-containing polymer (1) of the present invention will be described. Examples of the cage-shaped siloxane polymer (1) of the present invention include the following (1a-1) to (1b-16). In the formula, Ph represents a phenyl group, Me represents a methyl group, and ran represents an irregular copolymer in which the structural units on the left and right of the notation are randomly present in the polymer.

[0018] [ka]

[0019] [ka]

[0020] [ka]

[0021] [ka]

[0022] Of these cage-shaped siloxane-containing polymers, from the viewpoints of economy, high transparency, and heat resistance, (1a-1), (1b-1), (1a-2), (1b-2), (1a-3), (1b-3), (1a-5), (1b-5), (1a-6), (1b-6), (1a-13), (1b-13), (1a-14) or (1b-14) are preferred, and (1a-1), (1b-1), (1a-2), (1b-2), (1a-5), (1b-5), (1a-13) or (1b-13) are more preferred.

[0023] Next, the cured film of the cage siloxane-containing polymer of the present invention will be described. A cured film can be obtained by adding a crosslinking agent and a crosslinking catalyst to the cage siloxane-containing polymer (1) and forming a film. The cage siloxane-containing polymer (1) is preferably (1a-1), (1b-1), (1a-2), (1b-2), (1a-3), (1b-3), (1a-5), (1b-5), (1a-6), (1b-6), (1a-13), (1b-13), (1a-14) or (1b-14), and more preferably (1a-1), (1b-1), (1a-2), (1b-2), (1a-5), (1b-5), (1a-13) or (1b-13). Examples of the crosslinking agent include alkoxy-substituted monosilanes such as tetramethoxysilane, tetraethoxysilane, trimethoxysilane, and triethoxysilane, and peralkoxyoligosiloxanes such as permethoxyoligosiloxane and perethoxyoligosiloxane. Among these, tetramethoxysilane is preferred from the viewpoints of economy and the heat resistance and mechanical strength of the cured film. The crosslinking agent is preferably silane, tetraethoxysilane or permethoxyoligosiloxane, more preferably permethoxyoligosiloxane. The content of the crosslinking agent is preferably in the range of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the cage-type siloxane-containing polymer (1).

[0024] Examples of the crosslinking catalyst include organotin crosslinking catalysts such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate, titanium alkoxide crosslinking catalysts such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetraethyl titanate, and aluminum crosslinking catalysts such as aluminum tris(acetylacetonate). The content of the crosslinking catalyst is preferably in the range of 0.005% to 20% by weight, more preferably 0.01% to 10% by weight, based on the cage-shaped siloxane-containing polymer (1).

[0025] The method for forming the cured film of the cage-type siloxane-containing polymer of the present invention is to prepare a composition containing a film-forming solvent, a cage-type siloxane-containing polymer (1), a crosslinking agent and a crosslinking catalyst, apply the composition onto a substrate to form a film, and then heat-cure the composition. Examples of the film-forming method include spin coating, spray coating, dip coating, flow coating, roll coating, applicator, screen printing, bar coater, brush coating, and sponge coating, but spin coating or applicator is preferred in terms of controlling the film thickness. There is no particular limit to the type of film-forming solvent as long as the cage-type siloxane-containing polymer (1) dissolves therein, but from the standpoint of safety and heat resistance of the cured film, hydrocarbon solvents such as toluene, xylene, heptane, and octane are preferred, and toluene is more preferred. The concentration of the cage-shaped siloxane-containing polymer (1) in the film formation can be any concentration as long as it dissolves, but from the viewpoints of film thickness and operability, it is preferably in the range of 0.1 to 80% by weight, more preferably in the range of 20 to 70% by weight. There are no particular limitations on the heat curing temperature, but it is preferably carried out at a temperature selected from the range of 50°C to 350°C, from the viewpoints of volatilizing the film-forming solvent and smoothly carrying out crosslinking.

[0026] Next, the method for producing the cage siloxane-containing polymer (1) of the present invention will be described. The cage siloxane-containing polymer (1) of the present invention is produced by a step of producing a polymeric cage siloxane-containing polymer (1) (hereinafter also referred to as a polymerization step) by reacting a cage siloxane compound containing either one or both of a trans-type cage siloxane compound (2a) and a cis-type cage siloxane compound (2b) containing 70 mol % or more of the cis-type cage siloxane compound or the trans-type cage siloxane compound with a linear siloxane compound (3).

[0027] <Polymerization process> [ka] (In the formula, Ph represents a phenyl group. R 1 , R 2 and R 3 R each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom. X represents a hydrogen atom, a methyl group, or an ethyl group. n represents a real number ranging from 0 to 20, and is preferably a real number ranging from 0 to 6. n may be an integer, but in the case of equilibrium polymerization, n is the average number of multiple integers, so it does not have to be an integer. m represents an integer from 2 to 10.

[0028] The cage siloxane compound (2) used in the polymerization step is characterized in that it is a cage siloxane compound (2) containing 70 mol % or more of a trans-type cage siloxane compound (2a) or a cage siloxane compound (2) containing 70 mol % or more of a cis-type cage siloxane compound (2b). Examples of the cage siloxane include the following.

[0029] [ka] (In the formula, Ph represents a phenyl group, and Me represents a methyl group.)

[0030] Among these, from the viewpoint of the heat resistance of the cage-shaped siloxane-containing polymer (1), (2a-1), (2b-1), (2a-2), (2b-2), (2a-4) or (2b-4) is preferred. , (2a-1), (2b-1), (2a-2) or (2b-2) are more preferred.

[0031] The cage siloxane compound (2a) containing 70 mol % or more of the trans cage siloxane compound (2a) or the cage siloxane compound (2) containing 70 mol % or more of the cis cage siloxane compound (2b) can be prepared by reacting as raw materials a cage siloxane diol (4) containing 70 mol % or more of the trans cage siloxane diol (4a) or a cage siloxane diol (4) containing 70 mol % or more of the cis cage siloxane diol (4b) and chlorohydrosilane R 2 R 3 The silylation step will be described later.

[0032] Examples of the linear siloxane compound (3) used in the polymerization step include the following compounds: In the formula, Me represents a methyl group, and Et represents an ethyl group. [ka]

[0033] These linear siloxane compounds may have a fixed chain length and may have a molecular weight distribution. From the viewpoints of stability, economy, yield, and heat resistance of the cage-shaped siloxane-containing polymer (1), the linear siloxane compound (3) used in the polymerization step is preferably (3-1), (3-2), (3-7), (3-8), (3-10), (3-11), (3-13), (3-14), (3-17), (3-18), (3-20) or (3-21), more preferably (3-2), (3-7), (3-8), (3-10), (3-14), (3-18) or (3-21). Preferably, (3-2) or (3-8) is particularly preferred. These linear siloxane compounds may be commercially available products or may be synthesized according to known production methods.

[0034] Examples of the linear siloxane compound (3') used in the polymerization step include the following compounds: In the formula, Me represents a methyl group, and Et represents an ethyl group. [ka]

[0035] The polymerization step is characterized by being carried out in the presence of an acid catalyst. The acid catalyst is preferably a Lewis acid catalyst, and examples thereof include aluminum halides such as aluminum chloride (III), aluminum bromide (III), and aluminum iodide (III); boron halides such as boron fluoride (III), boron chloride (III), boron bromide (III), and boron iodide (III); and triarylboranes such as triphenylborane, tris(4-fluorophenyl)borane, tris(3,5-bis(trifluoromethyl)phenyl)borane, and tris(pentafluorophenyl)borane. Of these, tris(pentafluorophenyl)borane is preferred from the viewpoints of yield and economy. There is no particular restriction on the equivalent of the acid catalyst, and it can be carried out at any equivalent selected from the range of 0.0001% by weight to 5% by weight relative to the cage siloxane compound (2a) or (2b).

[0036] The polymerization step is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include saturated hydrocarbon solvents such as hexane, heptane, octane, decalin, etc.; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, etc.; ether solvents such as diethyl ether, cyclopentyl methyl ether, etc.; halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,1,2,2-tetrachloroethane, etc. Among these, from the viewpoints of yield, boiling point, safety, and economical efficiency, hexane, heptane, octane, benzene, toluene, cyclopentyl methyl ether, dichloromethane, or chloroform is preferred, heptane, toluene, cyclopentyl methyl ether, dichloromethane, or chloroform is more preferred, and heptane, toluene, or dichloromethane is particularly preferred. In addition, these organic solvents can be used not only alone, but also in combination of two or more kinds as necessary. The concentration of the cage siloxane compound (2) (total of trans-type and cis-type) in the polymerization step is not particularly limited, but from the viewpoints of reactivity, economy, and solubility, the concentration of the cage siloxane compound (2) is preferably in the range of 1 to 50% by weight, more preferably in the range of 1 to 20% by weight. The reaction temperature is determined according to the progress of the reaction, but from the viewpoints of safety and operability, it is preferable to carry out the polymerization in the range of -20°C to 200°C. It is more preferably 0°C to 120°C, and particularly preferably 10°C to 80°C. The reaction time is determined according to the progress of the reaction, but from the viewpoints of safety and operability, it is preferable to carry out the polymerization in the range of 1 minute to 180 hours. It is more preferably 10 minutes to 48 hours, and particularly preferably 20 minutes to 24 hours.

[0037] In the polymerization step, by using as a raw material a cage siloxane compound (2) containing 70 mol % or more of the trans cage siloxane compound (2a), it is possible to produce a cage siloxane-containing polymer (1) containing 70 mol % or more of the trans cage siloxane-containing polymer (1a). Furthermore, by using as a raw material a cage siloxane compound (2) in which the proportion of the cis-type cage siloxane compound of general formula (2b) is 70 mol % or more, it is possible to produce a cage siloxane-containing polymer (1) containing 70 mol % or more of the cis-type cage siloxane-containing polymer (1b).

[0038] After the polymerization step, a purification step of the cage-shaped siloxane-containing polymer (1) may be included as necessary. As the purification step, a method that is usually used by those skilled in the art for purifying organosilicon polymer compounds or organic polymer compounds can be applied, and examples thereof include a reprecipitation method in which the polymer is dissolved in a good solvent and then added to a poor solvent, and a chromatographic separation using a chromatographic method such as gel permeation chromatography. From the viewpoints of economy and operability, a purification step using the reprecipitation method is preferred.

[0039] Next, a method for producing the cage siloxane compound (2) containing 70% or more of the cage siloxane compound (2a) or (2b), which is a raw material for producing the cage siloxane-containing polymer (1), will be described. The cage siloxane compound (2) containing 70% or more of the cage siloxane compound (2a) or (2b) is prepared by mixing a cage siloxane diol (4) containing 70 mol % or more of either a trans cage siloxane diol (4a) or a cis cage siloxane diol (4b), and chlorohydrosilane R 2 R 3 The silylation step will be described below.

[0040] <Silylation process> [ka]

[0041] [ka] (In the formula, Ph represents a phenyl group. R 1 , R2 and R 3 each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.

[0042] Examples of the cage-shaped siloxane compound (2) produced by the silylation step include the following. [ka] (In the formula, Ph represents a phenyl group, and Me represents a methyl group.)

[0043] Among these, (2a-1), (2b-1), (2a-2), (2b-2), (2a-4) or (2b-4) are preferred from the viewpoints of yield and heat resistance of the cage-shaped siloxane-containing polymer (1). Preferred are (2a-1), (2b-1), (2a-2) or (2b-2).

[0044] The cis-trans mixture of cage siloxane diols represented by general formula (4), which is the raw material for the silylation step, can be produced and used according to the method described in the publicly known literature (Patent Publication No. 4379120). That is, phenyltriethoxysilane is condensed with sodium hydroxide in isopropyl alcohol-water, and the resulting tetrasodium salt is reacted with trichloroorganosilane and further hydrolyzed. The cage siloxane diol (4) includes both isomers of cis cage siloxane diol (4b) and trans cage siloxane diol (4a). In the method described in Patent Publication No. 4379120, the ratio of the stereoisomers trans cage siloxane diol (4a) / cis cage siloxane diol (4b) is in the range of 5 / 5 to 6 / 4. The isomer ratio can be determined by calculating the signal intensity ratio of the silicon-derived signal corresponding to the center of the silsesquioxane skeleton in silicon NMR, which appears as a singlet in the case of the trans isomer but splits into a doublet in the case of the cis isomer. The present invention is characterized by comprising a step of enriching a mixture of trans-type cage siloxane diol (4a) and cis-type cage siloxane diol (4b) by crystallization to enrich for isomers containing at least 70 mol% of either (4a) or (4b) (hereinafter also referred to as isomer enrichment step), and using this as a raw material for production in a silylation step to obtain a cage siloxane compound (2) containing at least 70 mol% of the cage siloxane compound (2a) or (2b). The isomer enrichment step will be described later.

[0045] Examples of chlorohydrosilanes used in the silylation step include chlorodimethylsilane, chloromethylphenylsilane, chlorodiphenylsilane, chloroethylmethylsilane, chlorodiethylsilane, chloromethylpropylsilane, and chloroisopropylmethylsilane. From the viewpoints of economy and heat resistance of the cage-shaped siloxane-containing polymer (1), chlorodimethylsilane, chloromethylphenylsilane, and chlorodiphenylsilane are preferred, and chlorodimethylsilane and chloromethylphenylsilane are more preferred. These may be commercially available products or may be synthesized by a known synthesis method.

[0046] The silylation step is preferably carried out in an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, diisopropyl ether, methyl tert-butyl ether (MTBE), cyclopentyl methyl ether, cyclopentyl ethyl ether, dioxane, ethylene glycol dimethyl ether, and tetrahydrofuran (THF). From the viewpoints of solubility, operational safety, and economic efficiency, tetrahydrofuran or cyclopentyl methyl ether is preferred, and tetrahydrofuran is more preferred. These solvents may be used alone or in combination of two or more as necessary. The raw material concentration in the silylation step is not particularly limited, but in order to increase the yield and production efficiency, it is preferable to carry out the silylation step at a concentration of 5% by weight or more of the cage siloxane compound. The reaction temperature and reaction pressure are not particularly limited, but from the viewpoints of operability and safety, the reaction temperature is preferably -80°C to 100°C, and the reaction pressure is preferably in the range of normal pressure to 1 MPa. More preferably, the reaction temperature is -20 to 80°C, and the reaction pressure is normal pressure.

[0047] The silylation step may be carried out in the presence of a base that captures hydrogen chloride produced as a by-product. Examples of the base include ammonia, as well as aliphatic secondary amines such as dimethylamine, diethylamine, and diisopropylamine, aliphatic tertiary amines such as triethylamine and diethylisopropylamine, and aromatic amines such as aniline, pyridine, 4-dimethylaminopyridine, and quinoline. From the viewpoints of yield, operability, and safety, diethylamine, triethylamine, aniline, or pyridine is preferred, and triethylamine or pyridine is more preferred.

[0048] The silylation step may be followed, if necessary, by a purification step, which can be achieved by appropriately combining common procedures commonly used by those skilled in the art, such as concentration, extraction, normal-phase or reverse-phase column chromatography, and recrystallization.

[0049] Next, the isomer enrichment step will be described. In the isomer enrichment step, the cage siloxane diol (4), which is the raw material of the cage siloxane compound (2a) or (2b), is crystallized in a polar organic solvent, and the isomer enrichment step is carried out to obtain an isomer of either the trans cage siloxane diol (4a) or the cis cage siloxane diol (4b) at a content of 70 mol% or more. The mixture of the trans cage siloxane diol (4a) and the cis cage siloxane diol (4b) can be crystallized preferentially by crystallizing it from a polar organic solvent, and the proportion of the cis cage siloxane diol (4b) in the solution after crystallization increases. The polar solvent may be any polar organic solvent capable of coordinating with a hydroxyl group, and examples thereof include ketones such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether, tetrahydrofuran, dioxane and cyclopentyl methyl ether, and halogen-containing solvents such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dibromoethane. Among these polar organic solvents, acetone, tetrahydrofuran, dioxane, or cyclopentyl methyl ether is preferred, and acetone or tetrahydrofuran is more preferred, in terms of solubility, isomer ratio in crystallization, and not inhibiting the subsequent reaction.

[0050] Examples of the trans cage siloxane diol (4a) or cis cage siloxane diol (4b) that can be enriched by the isomer enrichment step include the following.

[0051] [ka]

[0052] Among these, from the viewpoints of yield and economy, (4a-1), (4b-1), (4a-2) or (4b-2) is preferred, and (4a-1) or (4b-1) is more preferred.

[0053] In the isomer enrichment step, a supersaturated solution of an isomer mixture of cage siloxane diol (4) (the molar ratio of trans cage siloxane diol (4a) / cis cage siloxane diol (4b) is 70 / 30 or less) in a polar organic solvent is prepared, and the trans cage siloxane diol (4a) is preferentially crystallized from the solution. The method for preparing the supersaturated solution is as follows: Methods that are commonly used by those skilled in the art for crystallization of organic silicon compounds or organic compounds can be applied, including a thermal crystallization method in which the solvent is heated to a temperature below the boiling point and then cooled to become supersaturated, a method in which a poor solvent is added to a polar organic solvent solution of cage-shaped siloxane diol (4), and an evaporation method in which the solvent is slowly evaporated. There are no particular limitations on the poor solvent, so long as it is miscible with the polar organic solvent and has low solubility for cage-shaped siloxane diol compound (4), and examples of such poor solvents include hydrocarbon solvents such as pentane, hexane, and octane; and alcohol solvents such as methanol and ethanol. The crystallization temperature is not particularly limited, but is usually preferably in the range of -80°C to 80°C, more preferably 0°C to 50°C. EXAMPLES

[0054] The present invention will be described in more detail below with reference to examples and comparative examples. However, the scope of the present invention should not be construed as being limited to the specific examples shown below.

[0055] In the instrumental analysis of compounds, 1 H-NMR (proton nuclear magnetic resonance spectrum), 13 C-NMR (Carbon-13 Nuclear Magnetic Resonance Spectrum) and 29 The Si-NMR (silicon-29 nuclear magnetic resonance spectrum) was measured using a Bruker-Avance Ascend 400 nuclear magnetic resonance spectrometer, deuterated chloroform was used as the solvent, and tetramethylsilane was used as the standard substance. The IR (infrared absorption) spectrum was measured using a Horiba Ltd. FT-720 spectrophotometer and a SensIRtechnologies DuraSamplIRII (reflection type) measurement cell.

[0056] (Example 1) Synthesis of cage-shaped siloxane-containing polymer (1a-1) Under an argon atmosphere, 25 mg of tris(pentafluorophenyl)borane was dissolved in 54.2 g of dichloromethane, and 7.0 g of a cage siloxane compound with a trans-type cage siloxane compound (2a-1) / cis-type cage siloxane compound (2b-1) ratio of 9 / 1 and 0.91 g of 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane in 24.1 g of dichloromethane were slowly added dropwise. 30 minutes after the end of the dropwise addition, the solution foamed. After 3.5 hours, a small amount of triethylamine was added to stop the reaction. The reaction mixture was slowly added to a large amount of methanol, and the precipitate was filtered to obtain a crude polymer. This was dissolved again in THF, slowly added to a large amount of methanol, and the reprecipitated polymer was filtered and dried under reduced pressure to obtain 6.6 g of a cage siloxane-containing polymer (1a-1) as a white powder. The molecular weight of the cage-type siloxane-containing polymer (1a-1) (1a-1 / 1b-1=9 / 1) was measured by gel permeation chromatography in terms of PMMA, and the weight average molecular weight was 161,000. , and the number average molecular weight was 53,000.

[0057] In thermogravimetric analysis (in an air stream), the cage-shaped siloxane-containing polymer (1a-1) had a 1% weight loss temperature of 426°C and a 5% weight loss temperature of 486°C.

[0058] This cage-shaped siloxane-containing polymer (1a-1) was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilaurate tin as a crosslinking catalyst were added, and the mixture was applied to a Teflon-coated stainless steel plate using an applicator to form a film. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and then peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film in thermogravimetric analysis (in air flow) was 454°C, and the 5% weight loss temperature was 504°C. The glass transition point of the thin film was determined by dynamic viscoelasticity measurement to be 51°C. When this thin film was cut out and subjected to a tensile strength test at room temperature, it showed clear elastic deformation and a strength of 22 MPa at the yield point.

[0059] By using a cage siloxane compound with a high proportion of trans-type as the raw material, it was possible to obtain a cage siloxane-containing polymer with excellent thermal stability and mechanical strength.

[0060] (Example 2) Synthesis of cage-shaped siloxane-containing polymer (1b-1) Under an argon atmosphere, 25 mg of tris(pentafluorophenyl)borane was dissolved in 54.2 g of dichloromethane, and 7.0 g of a cage siloxane compound with a trans isomer (2a-1) / cis isomer (2b-1) ratio of 2 / 8 and 0.91 g of 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane in 24.1 g of dichloromethane were slowly added dropwise. 30 minutes after the end of the dropwise addition, the solution foamed. After 3.5 hours, a small amount of triethylamine was added to stop the reaction. The reaction mixture was slowly added to a large amount of methanol, and the precipitate was filtered to obtain a crude polymer. This was dissolved again in THF, slowly added to a large amount of methanol, and the reprecipitated polymer was filtered and dried under reduced pressure to obtain 6.6 g of a cage siloxane-containing polymer (1b-1) (1a-1 / 1b-1=2 / 8) as a white powder. The molecular weight of the cage-type siloxane-containing polymer (1b-1) was measured by gel permeation chromatography in terms of PMMA, and the weight average molecular weight was 345,000 and the number average molecular weight was 175,000. .

[0061] In thermogravimetric analysis (in an air stream) of the cage-shaped siloxane-containing polymer (1b-1), the 1% weight loss temperature was 431°C, and the 5% weight loss temperature was 491°C.

[0062] This polymer was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilaurate tin as a crosslinking catalyst were added, and the mixture was applied to a Teflon-coated stainless steel plate using an applicator to form a film. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and then peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film in thermogravimetric analysis (in air flow) was 454°C, and the 5% weight loss temperature was 510°C. The glass transition point of the thin film was determined to be 50°C by dynamic viscoelasticity measurement. When this thin film was cut out and subjected to a tensile strength test at room temperature, it showed clear elastic deformation and a strength of 17 MPa at the yield point.

[0063] By using a cage siloxane compound with a high proportion of cis-isomer as a raw material, it was possible to obtain a cage siloxane-containing polymer with excellent thermal stability and mechanical strength.

[0064] (Comparative Example 1) Synthesis of cage-shaped siloxane-containing polymer (1c) Under an argon atmosphere, 25 mg of tris(pentafluorophenyl)borane was dissolved in 54.2 g of dichloromethane, and 7.0 g of a cage-shaped siloxane compound (2-1) with a trans isomer (2a-1) / cis isomer (2b-1) ratio of 5 / 5 and 0.91 g of 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane in 24.1 g of dichloromethane were slowly added dropwise. 30 minutes after the end of the dropwise addition, the solution foamed. After 3.5 hours, a small amount of triethylamine was added to stop the reaction. The reaction mixture was slowly added to a large amount of methanol, and the precipitate was filtered to obtain a crude polymer. This was dissolved again in THF, slowly added to a large amount of methanol, and the reprecipitated polymer was filtered and dried under reduced pressure to obtain 6.6 g of a cage-shaped siloxane-containing polymer (1c) (1a-1 / 1b-1=5 / 5) as a white powder. The molecular weight of this polymer was measured by gel permeation chromatography using PMMA conversion and found to be 188,000 in weight average molecular weight and 66,000 in number average molecular weight.

[0065] This polymer had a 1% weight loss temperature of 405° C. and a 5% weight loss temperature of 451° C., both of which were lower than those of the cage siloxane-containing polymers (1a-1) and (1b-1) of Examples 1 and 2.

[0066] This polymer was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilaurate tin as a crosslinking catalyst were added. A film was formed by coating the mixture on a Teflon-coated stainless steel plate using a caterer. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and then peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film was 438°C, and the 5% weight loss temperature was 485°C. The glass transition point of the thin film was determined by DMA to be 32°C. A cut-out piece of this thin film was subjected to a tensile strength test at room temperature, which showed stress elongation due to plastic deformation, and the stress at the breaking point was 13 MPa.

[0067] When a cage siloxane compound having approximately the same ratio of trans- and cis-isomers was used as the raw material, the thermal stability and mechanical strength were inferior to those of Examples 1 and 2.

[0068] (Example 3) Synthesis of cage-shaped siloxane-containing polymer (1a-5) Under an argon atmosphere, 25 mg of tris(pentafluorophenyl)borane was dissolved in 54.2 g of dichloromethane, and 7.0 g of a cage siloxane compound with a trans isomer (2a-2) / cis isomer (2b-2) ratio of 9 / 1 and 0.91 g of 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane in 24.1 g of dichloromethane were slowly added dropwise. 30 minutes after the end of the dropwise addition, the solution foamed. After 3.5 hours, a small amount of triethylamine was added to stop the reaction. The reaction mixture was slowly added to a large amount of methanol, and the precipitate was filtered to obtain a crude polymer. This was dissolved again in THF, slowly added to a large amount of methanol, and the reprecipitated polymer was filtered and dried under reduced pressure to obtain 6.6 g of a cage siloxane-containing polymer (1a-5) (1a-5 / 1b-5=9 / 1) as a white powder. The molecular weight of this polymer was measured by gel permeation chromatography using PMMA conversion and found to be 32,000 in weight average molecular weight and 18,000 in number average molecular weight.

[0069] (Example 4) Isomer Enrichment of Cage Siloxane Diols (4a-1) and (4b-1) 20.0 g of cage siloxane diol (4-1) (a 1:1 isomer mixture of (4a-1) and (4b-1)) prepared according to the method described in Japanese Patent No. 4379120 was completely dissolved in 177 mL of boiling THF. The temperature was lowered to room temperature and the mixture was allowed to stand for 14 hours to crystallize. The precipitated crystals were filtered to obtain 6.8 g of trans-type cage siloxane diol. The trans isomer (4a-1) / cis isomer (4b-1) ratio was determined to be 9.5 / 0.5 by silicon NMR. After concentrating the solution, the same procedure was repeated to obtain 1.1 g of a trans-type cage siloxane diol (2a-1) with a trans isomer (4a-1) / cis isomer (4b-1) ratio of 9 / 1 as a white crystalline powder. The mother liquor was concentrated to obtain 11.5 g of a crystalline powder of a cis-type cage siloxane diol having a trans isomer (4a-1) / cis isomer (4b-1) ratio of 2 / 8.

[0070] (Example 5) Synthesis of cage-shaped siloxane compound (2a-1) A 200mL three-neck flask equipped with a magnetic stirrer, a Dimroth condenser, and a three-way cock was charged with 42.6g (35.9mmol) of a cage siloxane diol with a ratio of trans-type cage siloxane diol (4a-1) / cis-type cage siloxane diol (4b-1) of 9 / 1, and the atmosphere in the apparatus was replaced with argon. 11.36g (143.7mmol) of pyridine and 360mL of dehydrated THF were charged in the flask, and 13.6g (144mmol) of chlorodimethylsilane was added dropwise from a syringe over 30 minutes. After the dropwise addition, the mixture was heated to reflux for 1 hour. The reaction mixture was transferred to a separatory funnel, extracted with 300mL of hexane, and washed three times with 200mL of distilled water. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated using a rotary evaporator and dried under reduced pressure to obtain 46.0 g (yield 98%) of a cage siloxane compound (2a-1) (2a-1 / 2b-1=9 / 1) as a white solid.

[0071] 1 H-NMR (400MHz, CDCl 3 ), δ(ppm): 0.1017(d, J=2 .8Hz,12H), 0.2706(s,6H), 4.7056(sep,J=2.8Hz,2H), 7.1780(t,J=7.54Hz,9H), 7.2534(t,J=7.5Hz,overlap), 7.30-7.45(18H,overlap), 7.52-7.58(m,9H,overlap). 13 C-NMR (101MHz, CDCl 3 ),δ(ppm):-3.53,-0.41,127.17,127.35,129. 90, 129.97, 130.55, 131.42, 133.58, 133.68. 29 Si-NMR (79MHz, CDCl 3 ), δ(ppm):-79.52,-79.21,-63.39,-4.48. IR spectrum (solid, cm -1):3072,3053,3006,2960,2133,1595,1429,1275,1250,1109,1065,1053,1030,997,904,833,814,783,737,729,719,694,671,627,619,613.

[0072] (Example 6) Synthesis of cage-shaped siloxane compound (2a-2) A 200 mL three-neck flask equipped with a magnetic stirrer, a Dimroth condenser, and a three-way cock was charged with 10.0 g (8.43 mmol) of a cage siloxane diol with a trans cage siloxane diol (4a-1) / cis cage siloxane diol (4b-1) ratio of 9 / 1, and the apparatus was purged with argon. 2.68 g (33.9 mmol) of pyridine and 80 mL of dehydrated THF were charged into the flask, and 3.15 g (20. 1 mmol) was added dropwise from a syringe over 10 minutes. After the addition, the mixture was heated under reflux for 1 hour. The reaction mixture was transferred to a separatory funnel, extracted with 100 mL of chloroform, and washed three times with 150 mL of distilled water. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated on a rotary evaporator and dried under reduced pressure to obtain 13.4 g of a crystalline solid. This was dissolved in a minimum amount of THF, and methanol was slowly added in an amount three times the amount of THF to obtain 11.1 g (yield 92.7%) of a powdery white solid, trans-type cage siloxane compound (2a-2) (2a-2 / 2b-2=9 / 1).

[0073] IR spectrum (solid, cm -1 ):3072,3051,3006,2131,1593,1429,1115,1107,1059,1028,997,891,868,814,783,727,694; 1 H-NMR (400MHz, CDCl 3 ), δ(ppm):0.27(s,6H),0.34(d,J=2.80Hz),5.12(q,2H,J=2.84Hz),7.08‐7.55(m,50H); 13 C-NMR (101MHz, CDCl 3),δ(ppm):-3.11,-0.73,127.51,127.60,127.69,127.75,127.79,129.74,130.25,130.33, 130.37,130.85,130.88,130.92,131.68,133.34,133.99,134.00,134.10,134.18,136.77; 29 Si-NMR (79MHz, CDCl 3 ),δ(ppm):-79.44,-79.12,-63.22,-13.08.

[0074] (Example 7) Synthesis of cage-shaped siloxane compound (2a-3) A 100mL three-neck flask equipped with a magnetic stirrer, a 10mL dropping funnel, a Dimroth condenser, and a three-way cock was charged with 5.00g (3.84mmol) of a cage siloxane diol with a trans cage siloxane diol (4a-1) / cis cage siloxane diol (4b-1) ratio of 9 / 1, and purged with argon. 1.54g (15.2mmol) of triethylamine and 40mL of dehydrated THF were charged in the three-neck flask. 2.83g (9.22mmol) of chlorodiphenylsilane was charged in the dropping funnel and dropped over 10 minutes. After dropping, the mixture was heated to reflux for 1 hour. The reaction mixture was transferred to a separatory funnel, 150mL of diethyl ether was added, and the mixture was washed three times with 100mL of distilled water. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated on a rotary evaporator to obtain a pale yellow solid. This was washed with hexane, suction filtered, and dried under reduced pressure to obtain 5.57 g of a white solid. The obtained white solid was dissolved in a minimum amount of THF, and 5 times the amount of methanol was added. By recrystallization, 3.71 g (yield 62.2%) of the trans-type cage siloxane compound (2a-3) (2a-3 / 2b-3=9 / 1) was obtained as colorless crystals.

[0075] 29 Si-NMR (79MHz, CDCl 3 ),δ(ppm):-79.34,-78.98,-63.05,-21.87.

[0076] (Example 8) Synthesis of cage-shaped siloxane compound (2b-1) In a 500mL three-neck flask equipped with a magnetic stirrer, a Dimroth condenser, and a three-way cock, 30.0g (25.3mmol) of a cage siloxane diol with a trans cage siloxane diol (4a-1) / cis cage siloxane diol (4b-1) ratio of 2 / 8 was placed, and the apparatus was replaced with argon. 8.03g (102mmol) of pyridine and 250mL of dehydrated THF were placed in the flask, and 9.61g (102mmol) of chlorodimethylsilane was added dropwise from a syringe over 30 minutes. After the dropwise addition, the mixture was heated to reflux for 1 hour. The reaction mixture was transferred to a separatory funnel, extracted with 300mL of hexane, and washed three times with 200mL of distilled water. The organic layer was dried over magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated using a rotary evaporator and dried under reduced pressure to obtain 31.1 g (yield 94.4%) of a cis-type cage siloxane compound (2b-1) (2a-1 / 2b-1=2 / 8) as a powdery white solid.

[0077] IR spectrum (solid, cm -1 ):3072,3053,3028,3006,2121,2017,1431,1273,1252,1105,1065,1030,997,904,827,812,785,735,717,694,640,627,619. 1 H-NMR (400MHz, CDCl 3 ), δ(ppm):0.1033(d,J=2.8Hz,12.0H),0.2705(s,6.0H),4.7073(sep,J=2.8,1.9H),7.13-7.22(m,10.0H),7.23-7.29( m),7.30-7.46(m,19.6H),7.53-7.58(m,9.7H). 13 C-NMR (101MHz, CDCl 3),δ(ppm):-3.5291(SiMe2),-0.4094(SiMe),127.0726(ortho),127.2616(ortho),127.3486(ortho),129.8418(para),129.96 34(para,overlap),130.5359(ipso),130.5777(ipso),131.4261(ipso),133.5760(meta),133.6049(meta),133.7439(meta). 29 Si-NMR (79MHz, CDCl 3 ), δ(ppm):-79.67,-79.38,-79.21,-63.41,-4.46.

[0078] (Example 9) Synthesis of cage-shaped siloxane-containing polymer (1a-2) 10 g of cage-type siloxane diol isomer mixture ((4a-1) / (4b-1) = 92 / 8) and octamethylcyclotetrasiloxane (D 4 ) 2.3 g, toluene (16.8 g) was added to a 100 mL four-neck round-bottom flask, and a reflux condenser, magnetic stirrer, and oil bath were set up, with nitrogen flowing through. While stirring, 0.31 g of sulfuric acid and 2.0 g of toluene were added, and the mixture was refluxed for 1 hour. The mixture was then aged at 80°C for 5 hours. Heating was stopped, and water was added. After separation, the aqueous layer was removed. After washing with water several times, the organic layer was concentrated and reprecipitated with heptane. The precipitate was washed several times with heptane and then dried under reduced pressure at 80°C to obtain 8.6 g of a white solid. The molecular weight of the cage-shaped siloxane-containing polymer (1a-2) ((1a-2 / 1b-2=11.5 / 1)) was measured by gel permeation chromatography in terms of PMMA, and the weight average molecular weight was 142,000 and the number average molecular weight was 57,000. 1 H-NMR revealed that n was 3.0 on average. [ka]

[0079] This polymer was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilauryl tin as a crosslinking catalyst were added, and the mixture was applied to a Teflon-coated stainless steel plate using an applicator to form a film. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film was 436°C, and the 5% weight loss temperature was 484°C. The glass transition point of the thin film was determined by DMA to be 81°C. When this thin film was cut out and subjected to a tensile strength test at room temperature, it showed stress elongation due to plastic deformation, and the stress at the breaking point was 20 MPa. In this way, by using a cage siloxane compound with a high proportion of cis-type as a raw material, a cage siloxane-containing polymer with excellent thermal stability and mechanical strength was obtained.

[0080] (Example 10) Synthesis of cage-shaped siloxane-containing polymer (1b-2) A mixture of cage-shaped siloxane diol isomers ((4a-1) / (4b-1) = 25 / 75) was added to 1 0 g, Octamethylcyclotetrasiloxane (D 4 ) 2.3 g, toluene (18. 8 g) into a 100 mL four-neck round-bottom flask and attach a reflux condenser, magnetic stirrer, An oil bath was set and nitrogen was flowed. 0.31 g of sulfuric acid and 2.0 g of toluene were added while stirring, and the mixture was refluxed for 1 hour. Then, the mixture was aged at 80°C for 5 hours. Heating was stopped, and Water was added, and after separation, the aqueous layer was removed. After washing with water several times, the organic layer was concentrated and reprecipitated with heptane. The precipitate was washed several times with heptane and then dried under reduced pressure at 80°C to obtain 8.6 g of a white solid. The molecular weight of the cage-shaped siloxane-containing polymer (1b-2) ((1a-2 / 1b-2=1 / 3)) was measured by gel permeation chromatography in terms of PMMA, and the weight average molecular weight was 146,000 and the number average molecular weight was 45,000. 1 H-NMR revealed that n was 3.2 on average. [ka]

[0081] This polymer was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilauryl tin as a crosslinking catalyst were added, and the mixture was applied to a Teflon-coated stainless steel plate using an applicator to form a film. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film was 411°C, and the 5% weight loss temperature was 466°C. The glass transition point of the thin film was determined by DMA to be 78°C. When this thin film was cut out and subjected to a tensile strength test at room temperature, it showed stress elongation due to plastic deformation, and the stress at the breaking point was 20 MPa. In this way, by using a cage siloxane compound with a high proportion of trans-type as a raw material, a cage siloxane-containing polymer with excellent thermal stability and mechanical strength was obtained.

[0082] (Comparative Example 2) Synthesis of Cage-type Siloxane-containing Polymer (1C') A mixture of cage-shaped siloxane diol isomers ((4a-1) / (4b-1) = 50 / 50) was added to 1 0 g, Octamethylcyclotetrasiloxane (D 4 ) 2.3 g, toluene (16. 8 g) into a 100 mL four-neck round-bottom flask and attach a reflux condenser, magnetic stirrer, An oil bath was set and nitrogen was flowed. 0.31 g of sulfuric acid and 2.0 g of toluene were added while stirring, and the mixture was refluxed for 1 hour. Then, the mixture was aged at 80°C for 7 hours. Heating was stopped, and Water was added, and after separation, the aqueous layer was removed. After washing with water several times, the organic layer was concentrated and reprecipitated with heptane. The precipitate was washed several times with heptane and then dried under reduced pressure at 80°C to obtain 8.3 g of a white solid. The molecular weight of the cage-shaped siloxane-containing polymer (1C') was measured by gel permeation chromatography in terms of PMMA, and the weight average molecular weight was 73,000 and the number average molecular weight was 310. It was 00.1 H-NMR revealed that n was 3.2 on average. [ka]

[0083] This polymer was dissolved in a small amount of toluene, and a crosslinking agent MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) and a small amount of dibutyl dilauryl tin as a crosslinking catalyst were added, and the mixture was applied to a Teflon (trademark)-coated stainless steel plate using an applicator to form a film. This was dried by heating at 40°C for 30 minutes, 70°C for 30 minutes, 100°C for 1 hour, and 200°C for 2 hours, and peeled off from the stainless steel plate to prepare a transparent thin film. The 1% weight loss temperature of this thin film was 397°C, and the 5% weight loss temperature was 465°C. The glass transition point of the thin film was determined by DMA to be 66°C. When this thin film was cut out and subjected to a tensile strength test at room temperature, it showed stress elongation due to plastic deformation, and the stress at the breaking point was 17MPa. When a cage siloxane compound with the same ratio of trans-type and cis-type was used as the raw material, the thermal stability and mechanical strength were inferior to those of Examples 9 and 10. [Industrial Applicability]

[0084] The cage siloxane-containing polymer of the present invention is expected to be able to control extremely high thermal properties such as heat resistance, processability, solvent resistance, and mechanical and dynamic properties by the trans or cis isomer content ratio, and is expected to be a material applicable to applications such as heat-resistant optical materials, heat-resistant ceramic and metal surface coating materials, resist and pattern forming materials, and insulating materials. In addition, since the cage siloxane compound has reactive hydrogen atoms on silicon atoms at the terminals and has excellent solubility, it is expected to be a useful raw material for producing not only all-siloxane type polymers, but also alternating polymers with various organic molecules by using reactions such as hydrosilylation. Furthermore, cage siloxane diols with a trans or cis isomer ratio increased to 70% or more are expected to be a useful raw material for producing various siloxane structure-containing polymers.

Claims

1. General formula (1) 【Chemistry 1】 (In the formula, R １ , R ２ and R ３ R each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; a represents a real number ranging from 1 to 0.7, or a real number ranging from 0 to 0.3; n represents a real number ranging from 2 to 20; r a n represents an irregular copolymer. Cage-shaped siloxane-containing polymers.

2. A cured film obtained by thermally curing a composition comprising the cage-shaped siloxane-containing polymer according to claim 1, a crosslinking agent, and a crosslinking catalyst, The cured film, wherein the crosslinker is an alkoxy-substituted monosilane or peralkoxyoligosiloxane.

3. General formula (2a) 【Chemistry 2】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and a trans-type cage siloxane compound represented by the general formula (2b): 【Chemistry 3】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group or a phenyl group having 1 to 3 carbon atoms; and a cage siloxane compound containing either the cis cage siloxane compound or the trans cage siloxane compound in an amount of 70 mol % or more, and a cage siloxane compound represented by the general formula (3): 【Chemistry 4】 (In the formula, R ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; X represents a hydrogen atom, a methyl group, or an ethyl group; and m represents an integer of 2 to 10. 【Chemistry 5】 (In the formula, R ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; and a compound represented by the general formula (1) in the presence of an acid catalyst. 【Chemistry 6】 (In the formula, R １ , R ２ and R ３ R each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; a represents a real number ranging from 1 to 0.7, or a real number ranging from 0 to 0.3; n represents a real number ranging from 2 to 20; r a n represents an irregular copolymer. Method for producing cage siloxane-containing polymers.

4. General formula (1) 【Chemistry 7】 (In the formula, R １ , R ２ and R ３ R each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group. ４ and R ５ each independently represents a group having 1 carbon atom which may be substituted by a halogen atom represents a phenyl group which may be substituted with an alkyl group having a molecular weight of from 1 to 3 or a halogen atom; a represents a real number ranging from 1 to 0.7, or a real number ranging from 0 to 0.3; n represents a real number ranging from 2 to 20; r a n represents an irregular copolymer. A method for producing a cage siloxane-containing polymer, comprising the steps of: 【Chemistry 8】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, 【Chemistry 9】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; 【Chemistry 10】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; a cage siloxane diol containing 70 mol % or more of the cage siloxane diol represented by the general formula (4a) or (4b) obtained in the above step, and a chlorohydrosilane R ２ R ３ HSiCl (wherein R ２ and R ３ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, 【Chemistry 11】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; 【Chemistry 12】 (In the formula, R １ , R ２ and R ３ each independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; and The cage siloxane compound containing 70 mol % or more of the cage siloxane compound represented by the general formula (2a) or (2b) obtained in the above step and a cage siloxane compound represented by the general formula (3) 【Chemistry 13】 (In the formula, R ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; X represents a hydrogen atom, a methyl group, or an ethyl group; and m represents an integer of 2 to 10. General formula (3') 【Chemistry 14】 (In the formula, R ４ and R ５ each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom; in the presence of an acid catalyst; A method comprising:

5. General formula (4) 【Chemistry 15】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.) is crystallized from a ketone or ether solvent to obtain a cage siloxane diol represented by the general formula (4a): 【Chemistry 16】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group; 【Chemistry 17】 (In the formula, R １ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group.

6. A method for enriching any of the cage siloxane diols of claim 5 to 70 mole % or more, wherein the ketone is acetone and the ether solvent is tetrahydrofuran or cyclopentyl methyl ether.

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