Fluorene compound having sulfonic acid ester structure and allyl group, and method for producing same

Abstract

Provided is a fluorene compound represented by formula (1) and having a sulfonic acid ester structure and an allyl group. # imgabs0 # (In the formula, each R1 independently represents a hydrogen atom or a methyl group. Each R2 independently represents a hydrocarbon group having 1-20 carbon atoms, some or all of the hydrogen atoms thereof may be substituted by a halogen atom, a nitro group or a cyano group, and an ester bond or an ether bond may be interposed between carbon-carbon bonds thereof. ).

Description

Technical Field

[0001] The present invention relates to a fluorene compound having a sulfonate structure and an allyl group and a method for producing the same. Background Art

[0002] As a fluorene compound having an allyl group, a compound having an allyl group and an epoxy group represented by the following formula (X) described in Patent Document 1 is known as a functional epoxy resin. It is known that the introduction of a fluorene skeleton improves heat resistance and electrical properties compared to conventional epoxy resins.

[0003] [Chemistry 1]

[0004]

[0005] Therefore, the introduction of fluorene skeletons is effective in improving the heat resistance and electrical properties of resins, and is therefore important for the development of various functional resins. Among them, fluorene compounds having allyl groups are particularly important because they are not only easy to handle, but also can be synthesized into polymers using reactions based on allyl groups, such as hydrosilylation reactions.

[0006] As fluorene compounds having an allyl group, there are compounds having a phenolic hydroxyl group and compounds obtained by glycidylating the phenolic hydroxyl group (Patent Documents 1 to 3). Organosilicon compounds synthesized by hydrosilylation of these compounds have the problem of being easily oxidized and colored by light irradiation.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 4873223

[0010] Patent Document 2: Japanese Patent Application Publication No. 2014-47207

[0011] Patent Document 3: Japanese Patent Application Publication No. 2014-62055 Summary of the invention

[0012] Problems to be solved by the invention

[0013] The present invention has been made in view of the above-mentioned actual situation, and its object is to provide a fluorene compound having a sulfonate structure and an allyl group, which has high oxidation resistance by introducing a sulfonyl group as a strongly electron-withdrawing substituent, and can thus be used as a synthetic raw material for an organosilicon compound containing a fluorene skeleton having excellent light resistance, and a method for producing the same.

[0014] Means for solving problems

[0015] The present inventors have conducted extensive studies to achieve the above object and have found that the above problems can be solved by using a fluorene compound having a predetermined sulfonate structure and an allyl group, thereby completing the present invention.

[0016] That is, the present invention provides the following fluorene compound having a sulfonate structure and an allyl group and a method for producing the same.

[0017] 1. A fluorene compound having a sulfonate structure and an allyl group represented by the following formula (1).

[0018] [Chemistry 2]

[0019]

[0020] (Where R 1 are each independently a hydrogen atom or a methyl group,

[0021] R 2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, a part of or all of its hydrogen atoms may be substituted by halogen atoms, nitro groups or cyano groups, and an ester bond or ether bond may be present between its carbon-carbon bonds.

[0022] 2. The fluorene compound according to 1, wherein R 1 All are hydrogen atoms.

[0023] 3. The fluorene compound according to 1 or 2, wherein R 2 The number of carbon atoms is 1 to 8.

[0024] 4. A method for producing a fluorene compound represented by the following formula (1), comprising reacting a fluorene compound having an allyl group represented by the following formula (2) with a compound represented by the following formula (3) or (4).

[0025] [Chemistry 3]

[0026]

[0027] (Where R 1 are each independently a hydrogen atom or a methyl group.)

[0028] [Chemistry 4]

[0029]

[0030] (Where R 2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, part or all of whose hydrogen atoms may be substituted by halogen atoms, nitro groups or cyano groups, and ester bonds or ether bonds may be present between their carbon-carbon bonds. X is a fluorine atom, a chlorine atom or a bromine atom.)

[0031] [Chemistry 5]

[0032]

[0033] (Where R 1 and R 2 Same as above.)

[0034] 5. A method for producing a fluorene skeleton-containing organosilicon compound, comprising subjecting the fluorene compound according to any one of 1 to 3 to a hydrosilylation reaction with an Si—H group-containing organosilicon compound in the presence of a catalyst.

[0035] Effects of the Invention

[0036] Since the sulfonyl group exhibits strong electron-withdrawing properties, the organosilicon compound containing a fluorene skeleton obtained by hydrosilylation of the fluorene compound having a sulfonate structure and an allyl group of the present invention is less susceptible to coloration due to oxidation than the case of using a conventionally known fluorene compound having an allyl group, and can be expected to have excellent light resistance, so it is a useful compound. DETAILED DESCRIPTION

[0037] The fluorene compound having a sulfonate structure and an allyl group (hereinafter also simply referred to as a fluorene compound) of the present invention is represented by the following formula (1).

[0038] [Chemistry 6]

[0039]

[0040] In formula (1), R 1 Each independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferred from the viewpoint of easy availability of raw materials.

[0041] In formula (1), R 2Each is independently a hydrocarbon group having 1 to 20 carbon atoms, and a part or all of its hydrogen atoms may be substituted by halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), nitro or cyano groups, and ester bonds or ether bonds may be interposed between its carbon-carbon bonds. The hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, and 3-butenyl; Alkyl groups having 2 to 20 carbon atoms, such as alkynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl and 3-butynyl; cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, such as 1-cycloallyl, 1-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl; aromatic ring-containing hydrocarbon groups having 6 to 20 carbon atoms, such as benzyl, phenyl, o-tolyl, m-tolyl, p-tolyl, mesityl, 1-naphthyl and 2-naphthyl; and the like.

[0042] In formula (1), R 2 Preferred is a hydrocarbon group having 1 to 8 carbon atoms, and more preferred is a methyl group, a trifluoromethyl group, a phenyl group, a 2-nitrophenyl group, or an o-tolyl group.

[0043] The fluorene compound of the present invention can be synthesized by reacting a bisphenol fluorene compound having an allyl group represented by the following formula (2) with a compound represented by the following formula (3) or (4). The compounds represented by the formula (3) or (4) may be used alone or in combination of two or more.

[0044] [Chemistry 7]

[0045]

[0046] (Where R 1 Same as above.)

[0047] [Chemistry 8]

[0048]

[0049] (Where R 2 Same as above.)

[0050] In formula (3), X is a fluorine atom, a chlorine atom or a bromine atom, and is preferably a chlorine atom.

[0051] The reaction of the compound represented by formula (2) with the compound represented by formula (3) or (4) can be carried out by a method known in the art. The reaction temperature in the above reaction is arbitrary, and it can be carried out at 0 to 120°C, and the reaction time is usually about 2 to 30 hours.

[0052] The amount of the compound represented by formula (2) and the compound represented by formula (3) or (4) used is arbitrary, and the amount of the compound represented by formula (3) or (4) is usually 1.0 to 30 moles per 1 mole of the compound represented by formula (2). From the aspect of being able to obtain the compound represented by formula (1) in high yield, the amount of the compound represented by formula (3) or (4) is preferably 2.0 to 20 moles, more preferably 2.5 to 15 moles, per 1 mole of the compound represented by formula (2).

[0053] In the above reaction, a base may be added. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, secondary or tertiary amines such as diethylamine, triethylamine and diisopropylethylamine, pyridine, and dimethylaminopyridine. The amount of the base used is preferably 2 to 15 moles relative to 1 mole of the compound represented by formula (2). The base may be used alone or in combination of two or more.

[0054] In addition, a solvent may be used in the reaction. The solvent is not particularly limited, and preferably an aprotic polar solvent is used. Examples of aprotic polar solvents include dichloromethane, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and the like. The amount of the solvent used is generally 30 to 500 parts by mass, preferably 50 to 300 parts by mass, relative to 100 parts by mass of the compound represented by formula (2).

[0055] After washing the reaction product obtained by the above reaction, the solvent used is removed under heating and reduced pressure to obtain the fluorene compound of the present invention. When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, a metal carbonate such as sodium carbonate, sodium bicarbonate, or potassium carbonate or a metal bicarbonate can be used arbitrarily.

[0056] The fluorene compound of the present invention can be subjected to a hydrosilylation reaction with an organosilicon compound containing a Si-H group by utilizing an allyl group. In the hydrosilylation reaction, the amount of the fluorene compound of the present invention and the organosilicon compound containing a Si-H group is not particularly limited, and the organosilicon compound containing a Si-H group is preferably 0.9 to 0.99 moles relative to 1 mole of the fluorene compound. Thus, a high molecular weight polymer is obtained.

[0057] The organosilicon compound containing Si-H groups is not particularly limited, and examples thereof include hydrosilanes such as trimethoxyhydrogensilane, triethoxyhydrogensilane, and triethylsilane; dimethylpolysiloxanes containing Si-H groups at both ends such as 1,1,3,3-tetramethyldisiloxane, α,ω-dihydrodimethylpolysiloxane, and α,ω-dihydromethylphenylpolysiloxane; dimethylpolysiloxanes containing Si-H groups at one end such as 1,1,3,3,3-pentamethyldisiloxane and 1,1,1,3,3,5,5-heptamethyltrisiloxane; and 1,1,1,3,5,5,5-heptamethyltrisiloxane. Dimethylpolysiloxane containing side chain Si-H groups such as siloxane; methylphenylpolysiloxane containing side chain Si-H groups such as 1,1,1,5,5,5-hexamethyl-3-phenyltrisiloxane; cyclic polysiloxane containing Si-H groups such as 2,4,6-trimethylcyclotrisiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane; branched polysiloxane containing Si-H groups; methyl silicone resin containing Si-H groups; methylphenyl silicone resin containing Si-H groups; silylene compounds containing Si-H groups; silylene compounds containing Si-H groups, etc.

[0058] When the compound of the present invention and an organosilicon compound containing a Si—H group are subjected to a hydrosilylation reaction, a co-reaction with other vinyl group-containing compounds is also optional. Examples of other vinyl compounds include dimethylpolysiloxanes containing vinyl groups at both ends, such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, α,ω-divinyldimethylpolysiloxane, and α,ω-divinylmethylphenylpolysiloxane; dimethylpolysiloxanes containing side chain vinyl groups, such as 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane; methylvinylphenylpolysiloxanes containing side chain vinyl groups, such as 1,1,1,5,5,5-hexamethyl-3-vinyl-3-phenyltrisiloxane; cyclic polysiloxanes containing vinyl groups, such as 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane; branched polysiloxanes containing vinyl groups, methylvinyl silicone resins, and methylvinylphenyl silicone resins.

[0059] The hydrosilylation reaction is carried out in the presence of a catalyst. As the catalyst, platinum group metal single substances such as platinum (including platinum black), rhodium, palladium, etc. can be used; platinum chloride, chloroplatinic acid and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6.); alcohol-modified chloroplatinic acid (for example, U.S. Patent No. 3220972) 3159601, the specification of U.S. Patent No. 3159662 and the specification of U.S. Patent No. 3775452); a catalyst in which a platinum group metal such as platinum black or palladium is supported on a carrier such as alumina, silica, carbon, etc.; a rhodium-olefin complex; tris(triphenylphosphine)rhodium chloride (the so-called Wilkinson catalyst); a metal catalyst such as a complex of platinum chloride, chloroplatinic acid or chloroplatinate and a vinyl-containing siloxane (especially a vinyl-containing cyclic siloxane).

[0060] The amount of the catalyst used is a catalytic amount. Generally, as a platinum group metal, it is preferably 0.001 to 0.1% by mass relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent can be used as needed. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferred. The amount of the solvent used is not particularly limited. It is preferably 0.3 to 10 times 30 to 1000 parts by mass relative to 100 parts by mass of the total of the fluorene compound and the organosilicon compound containing the Si-H group. As the polymerization conditions, from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150°C, and particularly preferably 60 to 120°C. The polymerization time also depends on the type and amount of the polymer. In order to prevent the intervention of moisture in the polymerization system, it is preferably completed in about 0.5 to 100 hours, and particularly preferably in 0.5 to 30 hours. After the polymerization reaction is completed, if a solvent is used, it can be distilled off to obtain a silicon-containing fluorene compound.

[0061] Since the fluorene compound of the present invention has an electron-withdrawing substituent, it has higher oxidation resistance and excellent light resistance than conventional fluorene compounds having an allyl group, and is useful for the synthesis of an organosilicon compound containing a fluorene skeleton.

[0062] Example

[0063] The following examples and comparative examples are shown to further illustrate the present invention, but the present invention is not limited to the following examples. In the following examples and comparative examples, Mw is measured by gel permeation chromatography (GPC) using TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column, under the analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of tetrahydrofuran, and a column temperature of 40°C with monodisperse polystyrene as a standard.

[0064] The compounds used in the synthesis are shown below.

[0065] [Chemistry 9]

[0066]

[0067] [Chemistry 10]

[0068]

[0069] [Chemistry 11]

[0070]

[0071] [Chemistry 12]

[0072]

[0073] [Example 1]

[0074] After adding 215.3 g (0.50 mole) of the compound represented by formula (S-1) and 202.4 g (2.0 moles) of triethylamine to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 350 g of dichloromethane was added, stirred and cooled to 0°C. Then, using a dropping funnel, 229.1 g (2.0 moles) of the compound represented by formula (S-3) was added dropwise over a period of 1 hour. After the addition was completed, the mixture was heated to 70°C and stirred for 8 hours. The reaction solution was then washed with an aqueous sodium carbonate solution and pure water, and the solvent was removed under reduced pressure to obtain a solid. The obtained solid was analyzed by UV-visible absorption spectroscopy and 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (5).

[0075] 1H-NMR (CDCl3): δ=3.02(6H,s),3.25(4H,d,J=6.3),4.75-4.90(4H,m),5.76(2H,ddt,J=17.1,10.6,6.3Hz),6.55(2H,d,J=1.2Hz) ,6.92(2H,d,J=8.3Hz),7.12(2H,dd,J=8.3,1.2Hz),7.31-7.45(4H,m),7.65(2H,dd,J=8.1,1.4Hz),7.85(2H,dd,J=8.5,1.5Hz).

[0076] [Chemistry 13]

[0077]

[0078] [Example 2]

[0079] After adding 215.3 g (0.50 mole) of the compound represented by the formula (S-1) and 237.3 g (3.0 moles) of pyridine to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 350 g of tetrahydrofuran was added, stirred and cooled to 0°C. Then, using a dropping funnel, a solution of 476.6 g (2.5 moles) of the compound represented by the formula (S-4) dissolved in 200 g of tetrahydrofuran was dropped over a period of 1 hour. After the addition was completed, the mixture was heated to 90°C and stirred for 7 hours. The reaction solution was washed with an aqueous sodium hydroxide solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was analyzed by UV-visible absorption spectroscopy and 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (6).

[0080] 1 H-NMR (CDCl3): δ=2.34(6H,s),3.23(4H,d,J=6.3Hz),4.76-4.91(4H,m),5.76(2H,ddt,J=17.1,10.6,6.3Hz),6.55(2H,d,J=1 .2Hz),6.87(2H,d,J=8.4Hz),7.11(2H,dd,J=8.4,1.2Hz),7.28-7.45(8H,m),7.59-7.72(6H,m),7.85(2H,dd,J=8.5,1.5Hz).

[0081] [Chemistry 14]

[0082]

[0083] [Example 3]

[0084] After adding 183.4 g (0.40 mole) of the compound represented by formula (S-2) and 94.9 g (1.2 moles) of pyridine to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 200 g of dichloromethane was added, stirred and cooled to 0°C. Then, using a dropping funnel, a solution of 221.6 g (1.0 mole) of the compound represented by formula (S-5) dissolved in 100 g of dichloromethane was dropped over a period of 1 hour. After the addition was completed, the mixture was heated to 60°C and stirred for 12 hours. The reaction solution was then washed with an aqueous potassium carbonate solution and pure water, and the solvent was removed under reduced pressure to obtain a solid. The obtained solid was analyzed by UV-visible absorption spectroscopy and 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (7).

[0085] 1 H-NMR (CDCl3): δ=2.31(6H,s),3.26(4H,d,J=6.9Hz),4.75-4.90(4H,m),5.80(2H,ddt,J=16.4,10 .6,6.9Hz),6.80-6.91(4H,m),7.27-7.45(4H,m),7.65(2H,dd,J=8.1,1.4Hz),7.78-8.22(10H,m).

[0086] [Chemistry 15]

[0087]

[0088] [Example 4]

[0089] After adding 183.4 g (0.40 mole) of the compound represented by formula (S-2) and 242.9 g (2.4 moles) of triethylamine to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 400 g of tetrahydrofuran was added, stirred and cooled to 0°C. Then, using a dropping funnel, 338.6 g (1.2 moles) of the compound represented by formula (S-6) was added dropwise over a period of 1 hour. After the addition was completed, the mixture was heated to 100°C and stirred for 15 hours. The reaction solution was then washed with an aqueous sodium carbonate solution and pure water, and the solvent was removed under reduced pressure to obtain a solid. The obtained solid was analyzed by UV-visible absorption spectroscopy and 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (8).

[0090] 1H-NMR (CDCl3): δ=2.31(6H,s),3.25(4H,d,J=6.9Hz),4.76-4.90(4H,m),5.78(2H,ddt,J=17.1,10.6,6 .9Hz),6.81-6.91(4H,m),7.27-7.45(4H,m),7.65(2H,dd,J=8.1,1.4Hz),7.85(2H,dd,J=8.5,1.5Hz).

[0091] [Chemistry 16]

[0092]

[0093] [Example 5]

[0094] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 587g (1.00 mol) of the compound represented by formula (5) and 1500g of toluene were added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 133g (0.99 mol) of the compound represented by formula (S-8) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 8 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain resin 1. The Mw of resin 1 is 32,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that the resin 1 was a polymer represented by the following formula (9).

[0095] [Chemistry 17]

[0096]

[0097] [Example 6]

[0098] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 739g (1.00 mol) of the compound represented by formula (6) and 1500g of toluene were added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-7) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 8 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain resin 2. The Mw of resin 2 is 35,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that the resin 2 was a polymer represented by the following formula (10).

[0099] [Chemistry 18]

[0100]

[0101] [Example 7]

[0102] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 580 g (0.70 mol) of the compound represented by the formula (7), 55.9 g (0.30 mol) of the compound represented by the formula (S-9) and 1500 g of toluene were added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192 g (0.99 mol) of the compound represented by the formula (S-7) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 8 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain resin 3. The Mw of resin 3 is 29000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that the resin 3 was a polymer represented by the following formula (11) (a=0.7, b=0.3).

[0103] [Chemistry 19]

[0104]

[0105] [Example 8]

[0106] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 578g (0.80 mol) of the compound represented by the formula (8), 37.3g (0.20 mol) of the compound represented by the formula (S-9) and 1500g of toluene were added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 133g (0.99 mol) of the compound represented by the formula (S-8) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain resin 4. The Mw of resin 4 is 26000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that the resin 4 was a polymer represented by the following formula (12) (a=0.8, b=0.2).

[0107] [Chemistry 20]

[0108]

[0109] [Comparative Example 1]

[0110] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 431g (1.00 mol) of the compound represented by the formula (S-1) and 1500g of toluene were added and heated to 70°C. Then, 1.0g of a chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 133g (0.99 mol) of the compound represented by the formula (S-8) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 8 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain a comparative resin 1. The Mw of the comparative resin 1 was 29000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that Comparative Resin 1 was a polymer represented by the following formula (13).

[0111] [Chemistry 21]

[0112]

[0113] [Comparative Example 2]

[0114] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 543g (1.00 mol) of the compound represented by the formula (S-10) and 1500g of toluene were added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by the formula (S-7) was dropped over a period of 1 hour (total moles of hydrosilyl groups / total moles of alkenyl groups = 0.99 / 1). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 9 hours. Then, toluene was removed from the reaction solution under reduced pressure to obtain a comparative resin 2. The Mw of the comparative resin 2 was 33,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that Comparative Resin 2 was a polymer represented by the following formula (14).

[0115] [Chemistry 22]

[0116]

[0117] [Light transmittance test 1]

[0118] Resins 1 to 4 and comparative resins 1 and 2 were dissolved in cyclopentanone to prepare resin solutions at a concentration of 50% by mass. Each resin solution was coated on a glass substrate, heated at 60°C for 30 minutes, and then heated at 190°C for 2 hours under a nitrogen atmosphere to prepare a resin film (10 μm thick). The transmittance of light with a wavelength of 400 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech). The results are shown in Table 1.

[0119] [Table 1]

[0120]

[0121] [Light transmittance test 2]

[0122] The sample consisting of the film on the glass wafer obtained by the above method was continuously irradiated with a 400 nm, 1 W laser in an oven at 50°C, and the light transmittance at a wavelength of 400 nm after 100 hours and 1000 hours was examined using a spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 2.

[0123] [Table 2]

[0124]

[0125] From the above results, according to the present invention, a fluorene compound having a sulfonate structure and an allyl group can be synthesized. Furthermore, by using this compound, an organosilicon compound having a sulfonate structure and containing a fluorene skeleton as a polymer such as resins 1 to 4 can be synthesized and provided. In addition, the film does not oxidize for a long time and can be provided as a film with high light resistance.

Claims

1. A fluorene compound represented by the following formula (1) having a sulfonate structure and an allyl group, [Chemistry 1] In the formula, R 1 are each independently a hydrogen atom or a methyl group, R 2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, a part of or all of the hydrogen atoms thereof may be substituted with a halogen atom, a nitro group or a cyano group, and an ester bond or an ether bond may be interposed between the carbon-carbon bonds thereof.

2. The fluorene compound according to claim 1, wherein R 1 All are hydrogen atoms.

3. The fluorene compound according to claim 1 or 2, wherein R 2 The number of carbon atoms is 1 to 8.

4. A method for producing a fluorene compound represented by the following formula (1), wherein: A fluorene compound having an allyl group represented by the following formula (2) is reacted with a compound represented by the following formula (3) or (4), [Chemistry 2] In the formula, R 1 are each independently a hydrogen atom or a methyl group, In the formula, R 2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, a part or all of its hydrogen atoms may be substituted by a halogen atom, a nitro group or a cyano group, an ester bond or an ether bond may be present between its carbon-carbon bonds, X is a fluorine atom, a chlorine atom or a bromine atom, [Chemistry 4] In the formula, R 1 and R 2 Same as above.

5. A method for producing an organosilicon compound containing a fluorene skeleton, wherein: The fluorene compound according to any one of claims 1 to 3 is subjected to a hydrosilylation reaction with an organosilicon compound containing a Si—H group in the presence of a catalyst.

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