Fluorene compound having sulfonate ester structure and allyl group and method for producing same

Abstract

To provide a fluorene compound having a sulfonic acid ester structure and an allyl group which can be a synthetic raw material of a fluorene skeleton-containing organosilicon compound excellent in light resistance, and a production method of the same.SOLUTION: A fluorene compound having a sulfonic acid ester structure and an allyl group is represented by the following formula (1). In the formula, R1 is each independently a hydrogen atom or a methyl group. R2 is each independently a hydrocarbyl group having 1 to 20 carbon atoms, a part or all of the hydrogen atoms 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 carbon-carbon bonds.SELECTED DRAWING: None

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 technology]

[0002] Conventionally, 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 has been known as a functional epoxy resin, and it has been found that the introduction of a fluorene skeleton improves heat resistance and electrical properties compared to conventional epoxy resins. [ka]

[0003] Therefore, the introduction of a fluorene skeleton is effective in improving the heat resistance and electrical properties of resins, and is therefore important in 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 enable the synthesis of polymers through reactions that use the allyl groups as a foothold, such as hydrosilylation reactions.

[0004] As fluorene compounds having an allyl group, there are compounds having a phenolic hydroxy group and compounds in which the phenolic hydroxy group is glycidylated (Patent Documents 1 to 3). However, organosilicon compounds synthesized by hydrosilylation of these compounds are susceptible to oxidation and have the problem of becoming discolored when exposed to light. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4873223 [Patent Document 2] JP 2014-47207 A [Patent Document 3] JP 2014-62055 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and aims to provide a fluorene compound having a sulfonate ester structure and an allyl group, which can be used as a raw material for synthesizing an organosilicon compound containing a fluorene skeleton having excellent light resistance because it has high oxidation resistance due to the introduction of a sulfonyl group, which is a substituent with strong electron-withdrawing properties, and a method for producing the same. [Means for solving the problem]

[0007] As a result of extensive investigations to achieve the above object, the present inventors discovered that the above problems could be solved by a fluorene compound having a specific sulfonate ester structure and an allyl group, and thus completed the present invention.

[0008] That is, the present invention provides a fluorene compound having a sulfonate structure and an allyl group shown below. 1. A fluorene compound having a sulfonate structure and an allyl group, represented by the following formula (1): [ka] (In the formula, R 1 are each independently a hydrogen atom or a methyl group. R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, some or all of whose hydrogen atoms may be substituted with halogen atoms, a nitro group or a cyano group, and an ester bond or an ether bond may be present between the carbon-carbon bonds. 2.R 1 and R 1 and R 2 are both hydrogen atoms. 3.R 2 3. The fluorene compound according to 1 or 2, wherein each of the carbon numbers of 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). [ka] (In the formula, R 1 are each independently a hydrogen atom or a methyl group. [ka] (In the formula, R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, some or all of whose hydrogen atoms may be substituted with halogen atoms, a nitro group or a cyano group, and an ester bond or an ether bond may be present between the carbon-carbon bonds. X is a fluorine atom, a chlorine atom or a bromine atom. [ka] (In the formula, R 1 and R 2 is the same as above.) 5. A method for producing an organosilicon compound having a fluorene skeleton, comprising subjecting a fluorene compound according to any one of 1 to 3 above and an organosilicon compound having a Si—H group to a hydrosilylation reaction in the presence of a catalyst. Effect of the Invention

[0009] Since the sulfonyl group exhibits strong electron-withdrawing properties, the fluorene compound having a sulfonate ester structure and an allyl group of the present invention is a useful compound because the organosilicon compound obtained by hydrosilylation is less susceptible to coloration due to oxidation and is expected to have excellent light resistance compared to the case where a conventionally known fluorene compound having an allyl group is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] 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). [ka]

[0011] In formula (1), R 1 are each independently a hydrogen atom or a methyl group, with a hydrogen atom being preferred since the raw material is easily available.

[0012] In formula (1), R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, some or all of whose hydrogen atoms may be substituted with halogen atoms (such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), a nitro group or a cyano group, and an ester bond or an ether bond may be present between the carbon-carbon bonds. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, or an n-decyl group; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group; and alkenyl groups having 2 to 20 carbon atoms, such as an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group. groups; alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, and 3-butynyl groups; cyclic unsaturated hydrocarbyl 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 groups; and aromatic ring-containing hydrocarbyl groups having 6 to 20 carbon atoms, such as benzyl, phenyl, orthotolyl, metatolyl, paratolyl, mesityl, 1-naphthyl, and 2-naphthyl groups.

[0013] In formula (1), R 2Since the raw materials are easily available, the alkyl group preferably has 1 to 8 carbon atoms, and is more preferably a methyl group, a trifluoromethyl group, a phenyl group, a 2-nitrophenyl group, or an orthotolyl group.

[0014] 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 compound represented by formula (3) or (4) may be used alone or in combination of two or more. [ka] (In the formula, R 1 is the same as above.) [ka] (In the formula, R 2 is the same as above.)

[0015] In formula (3), X is a fluorine atom, a chlorine atom or a bromine atom, with a chlorine atom being preferred.

[0016] The reaction between the compound represented by formula (2) and the compound represented by formula (3) or (4) can be carried out by applying a method known in the art. The reaction temperature in the reaction is optional, but the reaction is usually carried out at 0 to 120° C., and the reaction time is usually about 2 to 30 hours.

[0017] The amount of the compound represented by formula (2) and the compound represented by formula (3) or (4) used is arbitrary, but is usually 1.0 to 30 moles of the compound represented by formula (3) or (4) per mole of the compound represented by formula (2). In order to obtain the compound represented by formula (1) in good yield, the amount of the compound represented by formula (3) or (4) used is preferably 2.0 to 20 moles, more preferably 2.5 to 15 moles, per mole of the compound represented by formula (2).

[0018] In the 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, dimethylaminopyridine, etc. The amount of the base used is preferably 2 to 15 moles per mole of the compound represented by formula (2). The base may be used alone or in combination of two or more kinds.

[0019] In addition, a solvent may be used in the reaction. The solvent is not particularly limited, but it is preferable to use an aprotic polar solvent. Examples of the aprotic polar solvent include methylene chloride, tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethylsulfoxide, and 1,4-dioxane. The amount of the solvent used is usually 30 to 500 parts by mass, and preferably 50 to 300 parts by mass, based on 100 parts by mass of the compound represented by formula (2).

[0020] The reaction product of the reaction is washed with water, and then the solvent used is removed under reduced pressure with heating 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 hydrogen carbonate or potassium carbonate, or a metal hydrogen carbonate may be used.

[0021] The fluorene compound of the present invention can carry out hydrosilylation reaction with an organosilicon compound containing 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 Si-H group used is not particularly limited, but it is preferable that the organosilicon compound containing Si-H group is 0.9 to 0.99 moles per mole of the fluorene compound. This allows a polymer having a high molecular weight to be obtained.

[0022] The Si-H group-containing organosilicon compound is not particularly limited, and examples thereof include hydrosilanes such as trimethoxyhydrosilane, triethoxyhydrosilane, and triethylsilane; dimethylpolysiloxanes having Si-H groups at both ends such as 1,1,3,3-tetramethyldisiloxane, α,ω-dihydrodimethylpolysiloxane, and α,ω-dihydromethylphenylpolysiloxane; dimethylpolysiloxanes having Si-H groups at one end such as 1,1,3,3,3-pentamethyldisiloxane and 1,1,1,3,3,5,5-heptamethyltrisiloxane; Examples of such compounds include dimethylpolysiloxanes containing Si-H groups in the side chain, such as 1,1,1,5,5,5-hexamethyl-3-phenyltrisiloxane; methylphenylpolysiloxanes containing Si-H groups in the side chain, such as 1,1,1,5,5,5-hexamethyl-3-phenyltrisiloxane; cyclic polysiloxanes containing Si-H groups, such as 2,4,6-trimethylcyclotrisiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane; branched polysiloxanes containing Si-H groups; methylsilicone resins containing Si-H groups; methylphenylsilicone resins containing Si-H groups; silphenylene compounds containing Si-H groups; and silalkylene compounds containing Si-H groups.

[0023] In addition, when carrying out the hydrosilylation reaction between the compound of the present invention and an organosilicon compound containing a Si-H group, it is also possible to co-react with another vinyl group-containing compound. Examples of other vinyl group 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 vinyl groups at the side chain, such as 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane; methylvinylphenylpolysiloxanes containing vinyl groups at the side chain, 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, methylvinylsilicone resins, and methylvinylphenylsilicone resins.

[0024] The hydrosilylation reaction is carried out in the presence of a catalyst. Examples of the catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (for example, as described in U.S. Pat. No. 3,220,972). complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); and complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes).

[0025] The amount of the catalyst used is a catalytic amount, and is preferably 0.001 to 0.1 mass% as platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable. The amount of the solvent used is not particularly limited, but is preferably 30 to 1000 mass parts, which is 0.3 to 10 times the total of 100 mass parts of the fluorene compound and the Si-H group-containing organosilicon compound. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is, for example, 40 to 150°C, particularly 60 to 120°C. The polymerization time depends on the type and amount of the polymer, but is preferably completed within about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is completed, if a solvent is used, it can be distilled off to obtain a silicon-containing fluorene compound.

[0026] The fluorene compound of the present invention has higher oxidation resistance and light resistance than conventional fluorene compounds having an allyl group because it has an electron-withdrawing substituent, and is therefore useful for the synthesis of organosilicon compounds having a fluorene skeleton. EXAMPLES

[0027] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by gel permeation chromatography (GPC) using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analysis conditions of a flow rate of 0.6 mL / min, tetrahydrofuran as an elution solvent, and a column temperature of 40° C., with monodisperse polystyrene as a standard.

[0028] The compounds used in the synthesis are shown below. [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [Example 1] A 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel was charged with 215.3 g (0.50 mol) of the compound represented by formula (S-1) and 202.4 g (2.0 mol) of triethylamine, and then 350 g of methylene chloride was added, stirred, and cooled to 0°C. Then, using the dropping funnel, 229.1 g (2.0 mol) of the compound represented by formula (S-3) was dropped over 1 hour. After the dropwise addition was completed, the mixture was heated to 70°C and stirred for 8 hours, after which the reaction solution was washed with an aqueous sodium carbonate solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was subjected to ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (5). 1 H-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). [ka]

[0033] [Example 2] A 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel was charged with 215.3 g (0.50 mol) of the compound represented by formula (S-1) and 237.3 g (3.0 mol) of pyridine, and then 350 g of tetrahydrofuran was added and stirred, and cooled to 0°C. Then, using the dropping funnel, a solution in which 476.6 g (2.5 mol) of the compound represented by formula (S-4) was dissolved in 200 g of tetrahydrofuran was dropped over 1 hour. After the dropwise addition was completed, the mixture was heated to 90°C and stirred for 7 hours, after which 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 subjected to ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (6). 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). [ka]

[0034] [Example 3] A 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel was charged with 183.4g (0.40 mol) of the compound represented by formula (S-2) and 94.9g (1.2 mol) of pyridine, and then 200g of methylene chloride was added and stirred, and cooled to 0°C. Then, using the dropping funnel, a solution of 221.6g (1.0 mol) of the compound represented by formula (S-5) dissolved in 100g of methylene chloride was dropped over 1 hour. After the dropping was completed, the mixture was heated to 60°C and stirred for 12 hours, after which the reaction solution was washed with an aqueous potassium carbonate solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was subjected to ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (7). 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). [ka]

[0035] [Example 4] In a 2L flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel, 183.4g (0.40 mol) of the compound represented by formula (S-2) and 242.9g (2.4 mol) of triethylamine were added, and then 400g of tetrahydrofuran was added, stirred, and cooled to 0°C. Then, using the dropping funnel, 338.6g (1.2 mol) of the compound represented by formula (S-6) was dropped over 1 hour. After the dropping was completed, the mixture was heated to 100°C and stirred for 15 hours, after which the reaction solution was washed with an aqueous sodium carbonate solution and pure water, and the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was analyzed by ultraviolet-visible absorption spectroscopy and 1H-NMR spectrum analysis (Bruker) confirmed that the compound was the compound represented by the following formula (8). 1 H-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). [ka]

[0036] [Example 5] 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 toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 133g (0.99 mol) of the compound represented by formula (S-8) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of 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, after which toluene was distilled off from the reaction solution under reduced pressure to obtain resin 1. The Mw of resin 1 was 32000. Note that resin 1 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was the polymer represented by the following formula (9). [ka]

[0037] [Example 6] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen purge 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 toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 192g (0.99 mol) of the compound represented by formula (S-7) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of 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, after which toluene was distilled off under reduced pressure from the reaction solution to obtain resin 2. The Mw of resin 2 was 35,000. Note that resin 2 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was the polymer represented by the following formula (10). [ka]

[0038] [Example 7] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 580g (0.70 mol) of the compound represented by formula (7), 55.9g (0.30 mol) of the compound represented by formula (S-9), 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 formula (S-7) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain resin 3. The Mw of resin 3 was 29000. Note that resin 3 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was a polymer represented by the following formula (11) (a=0.7, b=0.3). [ka]

[0039] [Example 8] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 578 g (0.80 mol) of the compound represented by formula (8), 37.3 g (0.20 mol) of the compound represented by 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 133 g (0.99 mol) of the compound represented by formula (S-8) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain resin 4. The Mw of resin 4 was 26,000. Note that resin 4 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was a polymer represented by the following formula (12) (a=0.8, b=0.2). [ka]

[0040] [Comparative Example 1] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen purge device and a reflux condenser, 431g (1.00 mol) of the compound represented by formula (S-1) 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% by mass) was added, and 133g (0.99 mol) of the compound represented by formula (S-8) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, after which toluene was distilled off under reduced pressure from the reaction solution to obtain comparative resin 1. The Mw of comparative resin 1 was 29000. The comparative resin 1 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was the polymer represented by the following formula (13). [ka]

[0041] [Comparative Example 2] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 543 g (1.00 mol) of the compound represented by formula (S-10) and 1500 g of toluene were added and heated to 70°C. Then, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration 0.5 mass%) was added, and 192 g (0.99 mol) of the compound represented by formula (S-7) was added dropwise over 1 hour (total number of moles of hydrosilyl groups / total number of moles of alkenyl groups = 0.99 / 1). After the dropwise addition, the mixture was heated to 100°C and aged for 9 hours, after which toluene was distilled off from the reaction solution under reduced pressure to obtain comparative resin 2. The Mw of comparative resin 2 was 33,000. The comparative resin 2 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer was the polymer represented by the following formula (14). [ka]

[0042] [Light transmission test 1] Resins 1 to 4 and comparative resins 1 and 2 were each dissolved in cyclopentanone to a concentration of 50% by mass to prepare a resin solution. Each resin solution was applied onto a glass substrate, heated at 60°C for 30 minutes, and then heated at 190°C for 2 hours in a nitrogen atmosphere to prepare a resin film (thickness 10 μm). The transmittance of light with a wavelength of 400 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Corporation). The results are shown in Table 1.

[0043] [Table 1]

[0044] [Light transmission test 2] A sample consisting of the coating 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 measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Corp.). The results are shown in Table 2.

[0045] [Table 2]

[0046] From the above results, according to the present invention, a fluorene compound having a sulfonate ester structure and an allyl group can be synthesized. Furthermore, by using this compound, a fluorene-containing polymer having a sulfonate ester structure such as resins 1 to 4 can be synthesized and provided. In addition, the film can be provided as a highly light-resistant film without oxidation for a long time.

Claims

1. A fluorene compound having a sulfonate structure and an allyl group, represented by the following formula (1): 【Chemistry 1】 (In the formula, R 1 are each independently a hydrogen atom or a methyl group. R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, some or all of whose hydrogen atoms may be substituted with halogen atoms, nitro groups or cyano groups, and an ester bond or ether bond may be present between the carbon-carbon bonds.

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

3. R 2 The fluorene compound according to claim 1, wherein each of the carbon numbers of the following is 1 to 8:

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). 【Chemistry 2】 (In the formula, R 1 are each independently a hydrogen atom or a methyl group. 【Chemistry 3】 (In the formula, R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, some or all of whose hydrogen atoms may be substituted with halogen atoms, nitro groups or cyano groups, and an ester bond or ether bond may be present between the 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 is the same as above.)

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

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