Fluorene compound having halogen atom and allyl group, and method for producing same

Abstract

Provided is a fluorene compound represented by formula (1) and having a halogen atom and an allyl group. # imgabs0 # (In the formula, each R independently represents a hydrogen atom or a methyl group. X independently represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ).

Description

Technical Field

[0001] The present invention relates to a fluorene compound having a halogen atom 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 a fluorene skeleton is effective for improving the heat resistance and electrical properties of a resin and is therefore important for the development of various functional resins. Among them, fluorene compounds having an allyl group that can be easily synthesized into a polymer by a reaction such as hydrosilylation are particularly important.

[0006] As fluorene compounds having an allyl group, there are compounds having an epoxy group and compounds having a phenolic hydroxyl group (Patent Documents 1 to 3). In order to develop a variety of functional resins, compounds having halogen atoms that can be converted into various substituents are desired. Furthermore, for fluorene compounds having halogen atoms and allyl groups, it is expected that the halogen atoms can promote the hydrosilylation reaction and shorten the aging time of polymer synthesis using the hydrosilylation reaction.

[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 an object of the present invention is to provide a fluorene compound having a halogen atom and an allyl group which can be a precursor of various resins containing a fluorene skeleton, 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 predetermined fluorene compound having a halogen atom and an allyl group, thereby completing the present invention.

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

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

[0018] [Chemistry 2]

[0019]

[0020] (In the formula, R is independently a hydrogen atom or a methyl group. X is independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).

[0021] 2. The fluorene compound according to 1, wherein all R are hydrogen atoms.

[0022] 3. A method for producing a fluorene compound represented by the following formula (1), comprising reacting a fluorenone represented by the following formula (2) with a compound represented by the following formula (3).

[0023] [Chemistry 3]

[0024]

[0025] (In the formula, R is a hydrogen atom or a methyl group. X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)

[0026] [Chemistry 4]

[0027]

[0028] (Wherein, R and X are the same as above.)

[0029] 4. A method for producing a fluorene skeleton-containing organosilicon compound, comprising subjecting the fluorene compound according to 1 or 2 to a hydrosilylation reaction with an Si—H group-containing organosilicon compound in the presence of a catalyst.

[0030] Effects of the Invention

[0031] The fluorene compound having a halogen atom and an allyl group of the present invention can easily introduce a substituent different from the conventionally known fluorene compound having an allyl group, and is therefore expected to be a useful precursor for developing a new functional resin containing a fluorene skeleton. DETAILED DESCRIPTION

[0032] The fluorene compound having a halogen atom and an allyl group (hereinafter also simply referred to as a fluorene compound) of the present invention is represented by the following formula (1).

[0033] [Chemistry 5]

[0034]

[0035] In formula (1), each R is independently a hydrogen atom or a methyl group, and a hydrogen atom is preferred because the raw materials can be easily obtained.

[0036] In formula (1), X is independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom.

[0037] The fluorene compound of the present invention can be synthesized by reacting a fluorenone represented by the following formula (2) with a compound represented by the following formula (3).

[0038] [Chemistry 6]

[0039]

[0040] (Wherein, R and X are the same as above.)

[0041] The reaction of the compound represented by formula (2) and the compound represented by formula (3) can be carried out by methods known in the art (e.g., methods described in Japanese Patent Publication No. 2017-114947, Japanese Patent Publication No. 2020-075866, Japanese Patent Publication No. 6936544, etc.). The reaction temperature in the reaction is arbitrary, and can usually be carried out at 0 to 150° C., and the reaction time is about 2 to 30 hours.

[0042] The amount of the compound represented by formula (2) and the compound represented by formula (3) used is arbitrary, and the amount of the compound represented by formula (3) is usually 2.0 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) is preferably 2.0 to 20 moles, and more preferably 2.0 to 10 moles, per 1 mole of the compound represented by formula (2).

[0043] In the reaction, an acid may be added. The acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and the like. The amount of the acid used is preferably 0.01 to 10 mol, more preferably 0.05 to 3 mol, relative to 1 mol of the compound represented by formula (2). The acid may be used alone or in combination of two or more.

[0044] In addition, a solvent may be used in the reaction. As the solvent, a solvent selected from carbon tetrachloride, carbon disulfide, dichloromethane, chloroform and nitromethane is preferred. 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).

[0045] The fluorene compound of the present invention can be obtained by washing the reaction product with water and then removing the solvent used under heating and reduced pressure. When washing with water, an aqueous solution of a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a metal carbonate or metal bicarbonate such as sodium carbonate, sodium bicarbonate or potassium carbonate can be used arbitrarily.

[0046] 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.

[0047] 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.

[0048] 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 compounds containing a vinyl group 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.

[0049] The hydrosilylation reaction is carried out in the presence of a catalyst. As the catalyst, platinum group metals such as platinum (including platinum black), rhodium, and palladium can be used; platinum chlorides, chloroplatinic acid, and chloroplatinates such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, described in U.S. Patent No. 3,220,972) The invention also includes alcohol-modified chloroplatinic acid described in the book); complexes of chloroplatinic acid and olefins (for example, complexes of chloroplatinic acid and olefins described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662 and U.S. Patent No. 3,775,452); catalysts prepared by loading platinum group metals such as platinum black or palladium on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); metal catalysts such as complexes of platinum chloride, chloroplatinic acid or chloroplatinates and vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes).

[0050] 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.

[0051] By having a halogen atom that can be easily converted to another substituent, the fluorene compound of the present invention becomes a synthetic precursor of a fluorene compound having a substituent different from a conventional fluorene compound having an allyl group and an allyl group, and can be used for the development of a resin material containing a fluorene skeleton.

[0052] Furthermore, since a fluorene compound having a halogen atom and an allyl group exhibits good reactivity in hydrosilylation, the reaction time for polymer synthesis by hydrosilylation can be shortened compared to the case of using an allyl group-containing fluorene compound having no halogen atom.

[0053] Example

[0054] 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 eluent of tetrahydrofuran, and a column temperature of 40°C with monodisperse polystyrene as a standard.

[0055] The compounds used in the synthesis are shown below.

[0056] [Chemistry 7]

[0057]

[0058] [Example 1]

[0059] After adding 180.2 g (1.00 mole) of the compound represented by formula (S-1) and 335.8 g (2.20 moles) of the compound represented by formula (S-2) to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 500 g of chloroform was added and stirred. After the compounds represented by formula (S-1) and formula (S-2) were dissolved, 17.2 g (0.10 mole) of p-toluenesulfonic acid was added, and the mixture was heated to 90°C and stirred for 12 hours. 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 analyzed by ultraviolet-visible absorption spectroscopy and 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (4).

[0060] 1 H-NMR (CDCl3): δ = 3.27 (4H, d, J = 6.3Hz), 4.76-4.91 (4H, m), 5.78 (2H, ddt, J = 17.1, 10.6, 6.3Hz), 6.53 (2H, d, J=1.2Hz),7.22-7.45(6H,m),7.52(2H,d,J=8.3Hz),7.64(2H,dd,J=8.1,1.4Hz),7.85(2H,dd,J=8.5,1.5Hz).

[0061] [Chemistry 8]

[0062]

[0063] [Example 2]

[0064] After adding 180.2 g (1.00 mole) of the compound represented by formula (S-1) and 512.4 g (2.60 mole) of the compound represented by formula (S-3) to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 500 g of chloroform was added and stirred. After the compounds represented by formula (S-1) and formula (S-3) were dissolved, 12.0 g (0.20 mole) of acetic acid was added, and the mixture was heated to 120°C and stirred for 10 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 ultraviolet-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).

[0065] 1H-NMR (CDCl3): δ = 3.22 (4H, d, J = 6.3Hz), 4.80-4.95 (4H, m), 5.73 (2H, ddt, J = 17.1, 10.6, 6.3Hz), 6.51 (2H, d, J = 1 .3Hz),7.09(2H,dd,J=8.4,1.3Hz),7.31-7.45(6H,m),7.64(2H,dd,J=8.1,1.4Hz),7.85(2H,dd,J=8.5,1.5Hz).

[0066] [Chemistry 9]

[0067]

[0068] [Example 3]

[0069] After adding 180.2 g (1.00 mole) of the compound represented by formula (S-1) and 516.2 g (2.00 mole) of the compound represented by formula (S-4) to a 2L flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel, 500 g of chloroform was added and stirred. After the compounds represented by formula (S-1) and formula (S-4) were dissolved, 8.61 g (0.05 mole) of p-toluenesulfonic acid was added, and the mixture was heated to 130°C and stirred for 9 hours. 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 1 H-NMR spectrum analysis (manufactured by Bruker) confirmed that the product was a compound represented by the following formula (6).

[0070] 1 H-NMR (CDCl3): δ = 2.35 (6H, s), 3.27 (4H, d, J = 6.3Hz), 4.75-4.90 (4H, m), 5.82 (2H, ddt, J = 16.5, 10.6, 6.3Hz), 6.79 ( 2H,d,J=1.2Hz), 6.99(2H,d,J=1.2Hz), 7.27-7.45(4H,m), 7.64(2H,dd,J=8.1,1.4Hz), 7.85(2H,dd,J=8.5,1.5Hz).

[0071] [Chemistry 10]

[0072]

[0073] [Example 4]

[0074] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 280 g (0.60 mole) of the compound represented by formula (4) and 74.6 g (0.40 mole) of the compound represented by formula (S-7) were added, and then 700 g of toluene was 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 mole) of the compound represented by formula (S-5) 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 4 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 (7) (a=0.6, b=0.4).

[0075] [Chemistry 11]

[0076]

[0077] [Example 5]

[0078] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 278g (0.50 mol) of the compound represented by the formula (5) and 93.2g (0.50 mol) of the compound represented by the formula (S-7) were added, and then 700g of toluene was 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 the formula (S-6) 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 2. The Mw of resin 2 is 34,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that the resin 2 was a polymer represented by the following formula (8) (a=0.5, b=0.5).

[0079] [Chemistry 12]

[0080]

[0081] [Comparative Example 1]

[0082] In a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 215g (0.50 mole) of the compound represented by the formula (S-8) and 93.2g (0.50 mole) of the compound represented by the formula (S-7) were added, and then 700g of toluene was 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 mole) of the compound represented by the formula (S-6) 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 14 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain a comparative resin 1. The Mw of the comparative resin 1 is 30,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that Comparative Resin 1 was a polymer represented by the following formula (9) (a=0.5, b=0.5).

[0083] [Chemistry 13]

[0084]

[0085] [Comparative Example 2]

[0086] After adding 217 g (0.40 mole) of the compound represented by the formula (S-9) and 112 g (0.60 mole) of the compound represented by the formula (S-7) to a 5L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 700 g of toluene was 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 mole) of the compound represented by the formula (S-5) 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 16 hours. Then, the toluene was removed from the reaction solution under reduced pressure to obtain a comparative resin 2. The Mw of the comparative resin 2 is 31,000. In addition, using 1 H-NMR (manufactured by Bruker Corporation) confirmed that Comparative Resin 2 was a polymer represented by the following formula (10) (a=0.4, b=0.6).

[0087] [Chemistry 14]

[0088]

[0089] [Comparison of aging time]

[0090] When synthesizing resins 1 and 2 and comparative resins 1 and 2, Mw was measured every 2 hours during aging until Mw became 30000 or more.

[0091] [Table 1]

[0092]

[0093] From the above results, according to the present invention, it is possible to synthesize a fluorene compound having a halogen atom and an allyl group, and to provide it. The halogen atom can be easily converted to other substituents, so the fluorene compound can be used as a precursor of various functional materials containing fluorene. Furthermore, the fluorene compound having a halogen atom and an allyl group shows good reactivity in hydrosilylation, and can shorten the reaction time of polymer synthesis.

Claims

1. A fluorene compound having a halogen atom and an allyl group represented by the following formula (1), [Chemistry 1] In the formula, each R is independently a hydrogen atom or a methyl group, and each X is independently a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

2. The fluorene compound according to claim 1, wherein R is a hydrogen atom.

3. A method for producing a fluorene compound represented by the following formula (1), wherein: A fluorenone represented by the following formula (2) is reacted with a compound represented by the following formula (3), [Chemistry 2] In the formula, R is a hydrogen atom or a methyl group, and X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. [Chemistry 3] Wherein, R and X are the same as above.

4. A method for producing an organosilicon compound containing a fluorene skeleton, wherein: The fluorene compound according to claim 1 or 2 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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