Organosilicon compound having fluorenyl group containing thioepoxy group and (meth) allyl group, and method for producing same

Abstract

Provided is an organosilicon compound represented by formula (1) and having a fluorenyl group containing a thioepoxy group and a (meth) allyl group. # imgabs0 # (In the formula, each of R1-R8 independently represents a hydrogen atom or a methyl group. And each of R9 to R12 independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. And R13 represents a hydrocarbylene group having 1-10 carbon atoms).

Description

Technical Field

[0001] The present invention relates to an organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group, and a method for producing the same. Background Art

[0002] Conventionally, as an organosilicon compound having a fluorenyl group containing a (meth)allyl group and a glycidyl group, there is known a compound described in Patent Document 1. The refractive index of this compound is not high enough to be used as a raw material for a high refractive index optical material.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent No. 5890288 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a compound capable of increasing the refractive index of a polymer and useful as a raw material for a high-refractive-index optical material.

[0008] Means for solving problems

[0009] The present inventors have repeatedly studied to achieve the above-mentioned object and found that:

[0010]

[0011] (Where R 1 ~R 8 Each is independently a hydrogen atom or a methyl group. 9 ~R 12 Each R is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 13 is a hydrocarbon group having 1 to 10 carbon atoms. An organosilicon compound having a fluorenyl group containing a glycidyl group and a (meth)allyl group represented by ) is reacted with thiourea or thiocyanate to obtain a compound represented by the following formula (1):

[0012]

[0013] (Where R 1 ~R 8 Each is independently a hydrogen atom or a methyl group. 9 ~R 12 Each R is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 13The present invention has been accomplished by an organosilicon compound represented by ) having a fluorenyl group containing a thioepoxy group and a (meth)allyl group in one molecule.

[0014] That is, the present invention provides the following organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group.

[0015] 1. An organosilicon compound represented by the following formula (1) having a fluorenyl group containing a thioepoxy group and a (meth)allyl group.

[0016] [Chemistry 1]

[0017]

[0018] (Where R 1 ~R 8 Each is independently a hydrogen atom or a methyl group. 9 ~R 12 Each R is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 13 It is an alkylene group having 1 to 10 carbon atoms.

[0019] 2. The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group according to claim 1, wherein R 9 ~R 12 It is methyl.

[0020] 3. A method for producing an organosilicon compound represented by the following formula (1) having a fluorenyl group containing a thioepoxy group and a (meth)allyl group, wherein an organosilicon compound represented by the following formula (2) having a fluorenyl group containing a glycidyl group and a (meth)allyl group is reacted with thiourea or thiocyanate.

[0021] [Chemistry 2]

[0022]

[0023] (Where R 1 ~R 13 Same as above.)

[0024] [Chemistry 3]

[0025]

[0026] (Where R 1 ~R 13 Same as above.)

[0027] Effects of the Invention

[0028] The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group of the present invention enables both polymerization using a (meth)allyl group and polymer formation using a thioepoxy group. In addition, crosslinking and curing after polymerization using these groups are possible. The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group of the present invention has four thioepoxy groups in one molecule and an aromatic ring capable of high refractive index, so the polymer obtained therefrom can be expected to have a high refractive index and can be used as a raw material for a high refractive index optical material. DETAILED DESCRIPTION

[0029] The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group of the present invention is represented by the following formula (1).

[0030] [Chemistry 4]

[0031]

[0032] In formula (1), R 1 ~R 8 Each is independently a hydrogen atom or a methyl group. 1 ~R 4 Preferably, it is a hydrogen atom or a methyl group, R 5 ~R 8 Preferred is a hydrogen atom.

[0033] In formula (1), R 9 ~R 12 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. Specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and octyl; cyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as cyclohexyl; and aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, and naphthyl. Among these, methyl is preferred in terms of raw material availability.

[0034] In formula (1), R 13 It is a hydrocarbon group having 1 to 10 carbon atoms. The above hydrocarbon group may be saturated or unsaturated, and may be any of linear, branched, and cyclic. Specific examples thereof include alkylene groups having 1 to 10 carbon atoms, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene; cyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as cyclohexylene; and arylene groups having 6 to 10 carbon atoms, such as phenylene, tolylene, and naphthylene. Among these, phenylene is preferred from the aspect of raw material availability.

[0035] Specific examples of the compound represented by formula (1) include the following compounds, but are not limited to these.

[0036] [Chemistry 5]

[0037]

[0038] [Chemistry 6]

[0039]

[0040] [Chemistry 7]

[0041]

[0042] [Chemistry 8]

[0043]

[0044] The compound represented by the formula (1) can be produced by reacting an organosilicon compound represented by the following formula (2) having a fluorenyl group containing a glycidyl group and a (meth)allyl group with thiourea or thiocyanate.

[0045] [Chemistry 9]

[0046]

[0047] (Where R 1 ~R 13 Same as above.)

[0048] Specific examples of the compound represented by formula (2) include the following compounds, but are not limited to these.

[0049] [Chemistry 10]

[0050]

[0051] [Chemistry 11]

[0052]

[0053] [Chemistry 12]

[0054]

[0055] [Chemistry 13]

[0056]

[0057] The reaction temperature of the compound represented by formula (2) and thiocyanate or thiourea is arbitrary, but is usually 0 to 100° C., preferably 20 to 70° C. The reaction time is not particularly limited as long as it is the time required for the reaction to be completed, but is usually appropriately 20 hours or less.

[0058] As for thiocyanate and thiourea, the amount of the substance corresponding to the amount of the substance of the epoxy group of the epoxy compound in stoichiometry is used. If the purity of the product, reaction rate, economic efficiency, etc. are important, an amount below or above this amount may be used. In the present invention, preferably, more than 0 mol and less than 5 mol of thiocyanate and thiourea are used for the reaction with respect to 1 mol of the epoxy group of the compound represented by formula (2), more preferably, about 0.9 to 5 mol are used, and more preferably, about 1 to 3 mol are used.

[0059] The reaction can be carried out without a solvent or in a solvent. When a solvent is used, it is preferred to use a solvent in which any one of the thiocyanate or thiourea and the compound represented by formula (2) is soluble. Specific examples include alcohols such as water, methanol, and ethanol; ethers such as diethyl ether, tetrahydrofuran, and dioxane; hydroxy ethers such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloroethane, chloroform, and chlorobenzene. In addition, a mixed solvent of these solvents, such as a mixed solvent of alcohols and water, ethers, hydroxy ethers, halogenated hydrocarbons, or a mixed solvent of aromatic hydrocarbons and alcohols, is sometimes effective. When the above solvents are used, the amount used is preferably 0.1 to 500 parts by mass, and more preferably 1 to 400 parts by mass, relative to 100 parts by mass of the compound represented by formula (2).

[0060] In addition, adding a polymerization inhibitor to the reaction solution is effective in terms of improving the reaction effect. As the above-mentioned polymerization inhibitor, acids, anhydrides, etc. can be listed. As specific examples of the above-mentioned acids and anhydrides, nitric acid, hydrochloric acid, sulfuric acid, oleum, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, maleic acid, benzoic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, silica gel, silica alumina, aluminum chloride, etc. When adding the above-mentioned polymerization inhibitor, the amount thereof added is usually in the total amount of the reaction solution, preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The above-mentioned polymerization inhibitor can be used alone or in combination of two or more.

[0061] As for the reaction product, the stability of the obtained compound can be improved by washing with an acidic aqueous solution. Specific examples of the acid used in the above-mentioned acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, maleic acid, etc. In addition, these can be used alone or in combination of two or more. The above-mentioned acidic aqueous solution usually works below pH 6, but is more effective at pH 0 to 3. The above-mentioned acid can be used alone or in combination of two or more.

[0062] The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group of the present invention is a compound having 4 thioepoxy groups and 2 (meth)allyl groups in one molecule. If the reactivity of the (meth)allyl group is used to perform a hydrosilylation reaction with a siloxane compound containing Si-H to polymerize, a high molecular weight organosilicon material having a thioepoxy group and a structure capable of three-dimensional crosslinking can also be obtained. Using the reactivity of the thioepoxy group, it can also be used as a curable material having a structure capable of three-dimensional crosslinking. By utilizing these groups, after polymerization, the remaining functional groups can be used for crosslinking and curing. Therefore, the organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group of the present invention is a compound that can be used as a macromolecular monomer for a heat-resistant resin material having a high refractive index.

[0063] Example

[0064] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the following Examples.

[0065] [Example 1]

[0066] A 3 L separable flask including a nitrogen inlet tube, a thermometer, a Dimroth type condenser, a vacuum controller and an aspirator was charged with the following formula (2-1):

[0067] [Chemistry 14]

[0068]

[0069] 255.6 g (0.2 mol) of the compound represented by the invention, 152 g (2 mol) of thiourea, 5 g of acetic anhydride, and 1000 g of toluene and 1000 g of methanol as solvents were reacted at 50°C for 8 hours. After the reaction, the mixture was extracted with toluene, washed with a 1% by mass aqueous sulfuric acid solution, and then washed with water. The excess solvent was distilled off to obtain 249 g of the product. The elemental analysis was performed using a fully automatic elemental analyzer 2400II CHNS / O manufactured by Perkin Elmer, a GC-MS mass analysis was performed using a 7890A manufactured by Agilent, and a Bruker AV400M was used for analysis.1 H-NMR analysis and FT-IR analysis using Nicolet 6700 manufactured by Thermo Fisher SCIENTIFIC confirmed that the product was a compound represented by the following formula (1-1) (yield 93%). In addition, 30 g of toluene was added to 70 g of the compound represented by formula (1-1), and the refractive index of the prepared 70% by mass toluene solution was measured using Abbe refractometer NAR-1T LIQUID manufactured by Atago Co., Ltd. The result was 1.58, confirming that it was a high refractive compound.

[0070] [Chemistry 15]

[0071]

[0072] [Example 2]

[0073] Except that the compound represented by the following formula (2-2) is used instead of the compound represented by the formula (2-1):

[0074] [Chemistry 16]

[0075]

[0076] The same method as in Example 1 was used to obtain 282 g of the product except that 301.2 g (0.2 mol) of the compound represented was used. Elemental analysis was performed using a fully automatic elemental analyzer 2400II CHNS / O manufactured by Perkin Elmer, GC-MS mass analysis was performed using a 7890A manufactured by Agilent, and AV400M manufactured by Bruker was used for mass spectrometry. 1 H-NMR analysis and FT-IR analysis using Nicolet 6700 manufactured by Thermo Fisher SCIENTIFIC confirmed that the product was a compound represented by the following formula (1-2) (yield 90%). In addition, 30 g of toluene was added to 70 g of the compound represented by formula (1-2), and the refractive index of the prepared 70% by mass toluene solution was measured using Abbe refractometer NAR-1T LIQUID manufactured by Atago Co., Ltd. The result was 1.58, confirming that it was a high refractive compound.

[0077] [Chemistry 17]

[0078]

Claims

1. An organosilicon compound represented by the following formula (1) having a fluorenyl group containing a thioepoxy group and a (meth)allyl group, [Chemistry 1] In the formula, R 1 ~R 8 are each independently a hydrogen atom or a methyl group, R 9 ~R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 13 It is a hydrocarbylene group having 1 to 10 carbon atoms.

2. The organosilicon compound having a fluorenyl group containing a thioepoxy group and a (meth)allyl group according to claim 1, wherein R 9 ~R 12 It is methyl.

3. A method for producing an organosilicon compound represented by the following formula (1) having a fluorenyl group containing a thioepoxy group and a (meth)allyl group, wherein: An organosilicon compound having a fluorenyl group containing a glycidyl group and a (meth)allyl group represented by the following formula (2) is reacted with thiourea or thiocyanate. [Chemistry 2] In the formula, R 1 ~R 8 are each independently a hydrogen atom or a methyl group, R 9 ~R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 13 is an alkylene group having 1 to 10 carbon atoms, [Chemistry 3] In the formula, R 1 ~R 8 are each independently a hydrogen atom or a methyl group, R 9 ~R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 13 It is a hydrocarbylene group having 1 to 10 carbon atoms.

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