Fluorene compound containing thioepoxy group and (meth) allyl group, and method for producing same

Abstract

Provided is a fluorene compound which is represented by formula (1) and contains a thioepoxy group and a (meth) allyl group. # imgabs0 # (In the formula, each of R1-R4 independently represents a hydrogen atom or a methyl group).

Description

Technical Field

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

[0002] Conventionally, as a fluorene compound having 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. 4873223 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 actual situation, 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] [Chemistry 1]

[0011]

[0012] (Where R 1 ~R 4 are each independently a hydrogen atom or a methyl group.)

[0013] The fluorene compound containing glycidyl group and (meth)allyl group represented by the formula (1) is reacted with thiourea or thiocyanate to obtain

[0014] [Chemistry 2]

[0015]

[0016] (Where R 1 ~R 4 are each independently a hydrogen atom or a methyl group.)

[0017] The present invention was completed by the inventors of the present invention.

[0018] That is, the present invention provides the following fluorene compound containing a thioepoxy group and a (meth)allyl group.

[0019] 1. A fluorene compound represented by the following formula (1) containing a thioepoxy group and a (meth)allyl group.

[0020] [Chemistry 3]

[0021]

[0022] (Where R 1 ~R 4 are each independently a hydrogen atom or a methyl group.)

[0023] 2. A method for producing a fluorene compound containing a thioepoxy group and a (meth)allyl group represented by the following formula (1), comprising reacting a fluorene compound containing a glycidyl group and a (meth)allyl group represented by the following formula (2) with thiourea or thiocyanate.

[0024] [Chemistry 4]

[0025]

[0026] (Where R 1 ~R 4 are each independently a hydrogen atom or a methyl group.)

[0027] [Chemistry 5]

[0028]

[0029] (Where R 1 ~R 4 are each independently a hydrogen atom or a methyl group.)

[0030] Effects of the Invention

[0031] The fluorene compound containing thioepoxy and (meth)allyl of the present invention can make it possible to form a polymer using (meth)allyl and to form a polymer using thioepoxy. In addition, it can make crosslinking and curing after forming a polymer using them possible. Since the fluorene compound containing thioepoxy and (meth)allyl of the present invention has two thioepoxy groups in one molecule and has an aromatic ring that can achieve a high refractive index, 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

[0032] The fluorene compound containing a thioepoxy group and a (meth)allyl group of the present invention is represented by the following formula (1).

[0033] [Chemistry 6]

[0034]

[0035] In formula (1), R1 ~R 4 Each is independently a hydrogen atom or a methyl group. 1 and R 2 Preferably, it is a hydrogen atom or a methyl group, R 3 and R 4 Preferred is a hydrogen atom.

[0036] Specific examples of the compound represented by formula (1) include the following compounds, but are not limited to these.

[0037] [Chemistry 7]

[0038]

[0039] [Chemistry 8]

[0040]

[0041] The compound represented by the formula (1) can be produced by reacting a fluorene compound containing a glycidyl group and a (meth)allyl group represented by the following formula (2) with thiourea or thiocyanate.

[0042] [Chemistry 9]

[0043]

[0044] (Where R 1 ~R 4 Same as above.)

[0045] Specific examples of the compound represented by formula (2) include the following compounds, but are not limited to these.

[0046] [Chemistry 10]

[0047]

[0048] [Chemistry 11]

[0049]

[0050] 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 a time for the reaction to be completed, but is usually appropriately 20 hours or less.

[0051] 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, more preferably about 0.9 to 5 mol, and more preferably about 1 to 3 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).

[0052] 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 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).

[0053] 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. can be listed. When adding the above-mentioned polymerization inhibitor, the amount 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.

[0054] As for the reaction product, by using an acidic aqueous solution for washing, the stability of the obtained compound can be improved. As specific examples of the acid used in the above-mentioned acidic aqueous solution, 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. can be listed. In addition, these can be used alone, or two or more can be mixed and used. The above-mentioned acidic aqueous solution usually exerts an effect below pH 6, but pH 0 to 3 is more effective. The above-mentioned acid can be used alone or in combination of two or more.

[0055] The fluorene compound containing a thioepoxy group and a (meth)allyl group of the present invention is a compound having two thioepoxy groups and two (meth)allyl groups in one molecule. If the reactivity of the (meth)allyl group is utilized to form a polymer by hydrosilylation reaction with a siloxane compound containing SiH, a high molecular weight organic silicon material having a structure capable of three-dimensional crosslinking containing a thioepoxy group can also be obtained. The reactivity of the thioepoxy group 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 fluorene compound 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.

[0056] Example

[0057] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the following Examples.

[0058] [Example 1]

[0059] 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):

[0060] [Chemistry 12]

[0061]

[0062] 271 g (0.5 mol) of the compound represented by the invention, 304 g (4 mol) of thiourea, 10 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 272 g of the product. 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 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 95%). In addition, the refractive index of a 70% by mass toluene solution prepared by adding 30 g of toluene to 70 g of the compound represented by formula (1-1) was measured using an Abbe refractometer NAR-1T LIQUID manufactured by Atago Co., Ltd. The result was 1.58, confirming that it was a high refractive compound.

[0063] [Chemistry 13]

[0064]

[0065] [Example 2]

[0066] Except that the compound represented by the following formula (2-2) is used instead of the compound represented by the formula (2-1):

[0067] [Chemistry 14]

[0068]

[0069] The same method as in Example 1 was used to obtain 288 g of the product except that 285 g (0.5 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 96%). In addition, using Abbe refractometer NAR-1T LIQUID manufactured by Atago Co., Ltd., the refractive index of a 70 mass % toluene solution prepared by adding 30 g of toluene to 70 g of the compound represented by formula (1-2) was measured to be 1.58, confirming that it was a high refractive compound.

[0070] [Chemistry 15]

[0071]

Claims

1. A fluorene compound containing a thioepoxy group and a (meth)allyl group represented by the following formula (1), [Chemistry 1] In the formula, R 1 ~R 4 Each is independently a hydrogen atom or a methyl group.

2. A method for producing a fluorene compound containing a thioepoxy group and a (meth)allyl group represented by the following formula (1), wherein: A fluorene compound 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 4 are each independently a hydrogen atom or a methyl group, [Chemistry 3] In the formula, R 1 ~R 4 Each is independently a hydrogen atom or a methyl group.

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