WO2017170094A1 - Nouveau composé dihydroxy - Google Patents

Nouveau composé dihydroxy Download PDF

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Publication number
WO2017170094A1
WO2017170094A1 PCT/JP2017/011625 JP2017011625W WO2017170094A1 WO 2017170094 A1 WO2017170094 A1 WO 2017170094A1 JP 2017011625 W JP2017011625 W JP 2017011625W WO 2017170094 A1 WO2017170094 A1 WO 2017170094A1
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group
reaction
phenyl
general formula
carbon atoms
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Japanese (ja)
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隼 溝口
緒旺 路
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Honshu Chemical Industry Co Ltd
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Honshu Chemical Industry Co Ltd
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Priority to JP2018509158A priority Critical patent/JP7267008B2/ja
Priority to KR1020187029622A priority patent/KR102263143B1/ko
Priority to CN201780022066.2A priority patent/CN108884040A/zh
Publication of WO2017170094A1 publication Critical patent/WO2017170094A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/12—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing nitrogen

Definitions

  • the present invention relates to a novel dihydroxy compound. Specifically, the present invention relates to a dihydroxy compound having an indoline skeleton, which is suitable as a raw material for aromatic polycarbonate oligomers and resins.
  • bisphenoxy alcohols compounds in which the hydrogen atom of the hydroxy group of bisphenol is substituted with a hydroxyalkyl group
  • thermoplastic synthetic resin raw materials such as polycarbonate resins, thermosetting resin raw materials such as epoxy resins, and antioxidant raw materials.
  • thermosetting resin raw materials such as epoxy resins
  • antioxidant raw materials such as antioxidant raw materials.
  • the performance required for these bisphenoxy alcohols has become increasingly sophisticated.
  • bisphenoxy alcohols 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine having an isoindoline skeleton is known (Non-patent Document 1).
  • the compound has insufficient heat resistance and optical characteristics, and further improvement is required.
  • the present invention has been made against the background described above, and an object of the present invention is to provide a novel dihydroxy compound having an indoline skeleton having high heat resistance and high refractive index.
  • a dihydroxy compound represented by the following general formula (1) (In the formula, each R independently represents an alkylene group having 2 to 6 carbon atoms, and each R 1 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, phenyl, R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R 3 represents 1 to 8 carbon atoms.
  • each R independently represents an alkylene group having 2 to 6 carbon atoms
  • each R 1 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, phenyl
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom
  • R 3 represents 1 to 8 carbon atoms.
  • the dihydroxy compound according to the present invention Since the dihydroxy compound according to the present invention has high heat resistance and a high refractive index, it can be expected to have excellent effects as a resin raw material such as polycarbonate, polyester, epoxy resin, and acrylic resin for optical materials. Furthermore, the polycarbonate using the dihydroxy compound according to the present invention as a raw material monomer is expected to have high purity, high heat resistance, and high refractive index, and in particular, an excellent effect can be expected in polycarbonate for optical materials.
  • each R independently represents an alkylene group having 2 to 6 carbon atoms
  • each R 1 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, phenyl
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom
  • R 3 represents 1 to 8 carbon atoms.
  • each R is independently an alkylene group having 2 to 6 carbon atoms.
  • alkylene group examples include 1,2-ethylenediyl group, 1,2- Examples thereof include a propanediyl group, a 1,3-propanediyl group, a pentamethylene group, and a hexamethylene group, preferably a linear or branched alkylene group having 2 to 4 carbon atoms, particularly preferably.
  • the hydroxyalkoxy group represented by “—O—R—OH” in the general formula (1) will be described.
  • the bonding position of the hydroxy group bonded to the alkylene group R is alkylene bonded directly to the ether group. It is not bonded to the carbon atom constituting the group R (the 1st carbon atom).
  • R is an alkylene group having 3 or more carbon atoms
  • the bonding position of the hydroxy group is preferably the 2- or 3-position of the alkylene group “R”, and more preferably the 2-position. Specific examples include 2-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxy-1-methylethoxy group, 3-hydroxypropoxy group and the like.
  • R 1 is each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and R 1 is an alkyl group having 1 to 8 carbon atoms
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • R 1 is an alkoxy group having 1 to 8 carbon atoms
  • the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like.
  • Such an alkoxy group may have a substituent such as a phenyl group or an alkoxy group, for example, within a range not impairing the effects of the present application.
  • R 1 when R 1 is a phenyl group, the phenyl group may have a substituent such as an alkyl group or an alkoxy group, as long as the effects of the present application are not impaired. preferable.
  • R 1 is a halogen atom
  • specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 is preferably a methyl group or a phenyl group.
  • R 2 is each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom
  • R 3 is an alkyl group having 1 to 8 carbon atoms or a carbon atom
  • R 2 and R 3 are alkyl groups having 1 to 8 carbon atoms
  • preferred groups and specific examples are the same as those for R 1 , and R 2 , R 3
  • preferred groups and specific examples are the same as those for R 1 .
  • R 2 is preferably a hydrogen atom or a methyl group
  • R 3 is preferably a methyl group.
  • m is 0, 1 or 2, preferably 0 or 1, particularly preferably 0, and n is 0, 1 or 2, preferably 0 or 1. And particularly preferably 0.
  • the “—O—R—OH” group and the phenyl group that are substituted with the phenyl group directly bonded to the 3-position carbon atom of the indoline skeleton, and the substitution position of R 1 are as follows.
  • the “—O—R—OH” group is preferably substituted at the 4-position or 2-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton. More preferably.
  • the phenyl group is preferably substituted at the o-position or p-position with respect to the “—O—R—OH” group, and the “—O—R—OH” group is a carbon at the 3-position of the indoline skeleton.
  • substitution at the 4-position with respect to the phenyl carbon atom directly bonded to the atom substitution at the 3-position or 5-position is preferred, and the “—O—R—OH” group is substituted at the 2-position. If it is, it is preferable to substitute at the 3-position or 5-position.
  • R 1 is preferably substituted at the o-position or the p-position with respect to the “—O—R—OH” group, and the carbon atom at the 3-position of the indoline skeleton.
  • the “—O—R—OH” group When the “—O—R—OH” group is substituted at the 4-position and the phenyl group is substituted at the 3-position with respect to the phenyl carbon atom directly bonded to the carbon atom, it is preferably substituted at the 5-position.
  • the “O—R—OH” group When the “O—R—OH” group is substituted at the 2-position and the phenyl group is substituted at the 3-position, the 5-position is preferably substituted, and the “—O—R—OH” group is substituted at the 2-position and the phenyl group is 5 When substituted at the position, substitution at the 3-position is preferred.
  • the substitution position of R 1 is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton,
  • the phenyl group is substituted at the 3-position and R 1 is substituted at the 5-position and the 6-position, or the “—O—R—OH” group is substituted at the 4-position, the phenyl group is substituted at the 3-position, and the R 1 is substituted at the 2-position and 5-position.
  • the substitution position of R 1 is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton
  • the phenyl group is substituted at the 3-position and R 1 is substituted at the 5-position and the 6-position, or the “—O—R—OH” group is substituted at the 4-position, the phenyl group is substituted at the 3-position, and the R 1 is substituted at
  • the dihydroxy compound represented by the general formula (1) is preferably represented by the following general formula (3).
  • R 1 , R 2 , R 3 , m, and n are the same as those in formula (1), and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that The total number of carbon atoms of R 4 substituted on each hydroxyethoxy group is 4 or less.
  • R 4 is an alkyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, and an n-propyl group.
  • R 4 is preferably a hydrogen atom or a methyl group.
  • the substitution position of R 1 is the 5-position relative to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton.
  • the substitution position of R 1 is preferably the 5-position and the 6-position or the 2-position and the 5-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton.
  • dihydroxy compound represented by the general formula (1) of the present invention examples include 3,3-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -1-phenyl-1H- Indole-2-on 3,3-bis (4- (2-hydroxy-2-methylethoxy) -3-phenylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxy-1) -Methylethoxy) -3-phenylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -5-methyl-3-phenylphenyl) -1-phenyl -1H-Indol-2-one 3,3-bis (5-ethyl-4- (2-hydroxyethoxy) -3-phenylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis ( 4- (2-hydroxyethoxy) -3,5-diphenylphenyl
  • the production method of the dihydroxy compound represented by the general formula (1) of the present invention is not particularly limited.
  • a bisphenol compound having an indoline skeleton represented by the following general formula (7) is obtained by using a phenylphenol compound represented by the formula (6) as a raw material and reacting them in the presence of an acid catalyst, and the obtained bisphenol It can be obtained by reacting a compound with any of alkylene carbonates, alkylene oxides and halogenated alcohols.
  • R 3 and n are the same as those in the general formula (1).
  • Preferred examples and specific examples of R 3 and n are also the same as those in the general formula (1).
  • N-phenylisatin compound represented by the general formula (5) include 1-phenyl-1H-indole-2,3-dione 1- (4-methylphenyl)- Examples thereof include 1H-indole-2,3-dione 1- (2-methylphenyl) -1H-indole-2,3-dione 1- (4-methoxyphenyl) -1H-indole-2,3-dione. Also, (In the formula, R 1 , R 2 and m are the same as those in the general formula (1).) Preferred examples and specific examples of R 1 , R 2 and m are also the same as those in the general formula (1).
  • phenylphenol compound represented by the general formula (6) examples include 2-phenylphenol 6-methyl-2-phenylphenol 6-ethyl-2-phenylphenol 2,6-diphenyl. Examples include phenol 5,6-dimethyl-2-phenylphenol 3,6-dimethyl-2-phenylphenol 2- (4-methylphenyl) phenol 2- (3-methylphenyl) phenol, and the like. Also, (In the formula, R 1 , R 2 , R 3 , m and n are the same as those in the general formula (1).) Preferred examples and specific examples relating to R 1 , R 2 , R 3 , m, and n are the same as those in formula (1).
  • the bisphenol compound represented by the general formula (7) is preferably a bisphenol compound represented by the following general formula (8).
  • R 1 , R 2 , R 3 , m and n are the same as those in the general formula (1).
  • Preferred examples and specific examples relating to R 1 , R 2 , R 3 , m, and n are the same as those in formula (1).
  • bisphenol compound represented by the general formula (8) examples include 3,3-bis (4-hydroxy-3-phenylphenyl) -1-phenyl-1H-indole-2- on 3,3-bis (4-hydroxy-5-methyl-3-phenylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (5-ethyl-4-hydroxy-3-phenylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis (4-hydroxy-3,5-diphenylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis (4-hydroxy -5,6-Dimethyl-3-phenylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4-hydroxy-2,5-dimethyl-3-phenylphenyl) -1-phenyl- 1H-Indol-2-one 3,3-bis (4-hydroxy-3- (4-methylphenyl) phenyl
  • the alkylene carbonates are preferably represented by the following general formula (10).
  • R 4 is the same as that of the general formula (3).
  • Preferred examples and specific examples relating to R 4 are also the same as those in the general formula (3).
  • Specific examples of the alkylene carbonates represented by the general formula (10) include ethylene carbonate propylene carbonate 1,2-butylene carbonate and the like.
  • the alkylene oxides are preferably represented by the following general formula (11).
  • R 4 is the same as that of the general formula (3).
  • Preferred examples and specific examples relating to R 4 are also the same as those in the general formula (3).
  • Specific examples of the alkylene oxides represented by the general formula (11) include ethylene oxide propylene oxide 1,2-butylene oxide and the like.
  • the halogenated alcohols are represented by the following general formula (12).
  • R is the same as that in formula (1), X represents a halogen atom, and X is not substituted with a carbon atom substituted with a hydroxy group.
  • Preferred examples and specific examples relating to R are also the same as those in the general formula (1).
  • Specific examples of the halogenated alcohol represented by the general formula (12) include 2-chloroethanol 2-bromoethanol 2-chloro-1-methylethanol 2-bromo-1-methylethanol. Examples include 2-chloro-2-methylethanol.
  • the manufacturing method of the dihydroxy compound of this invention is not specifically limited, As an example, the bisphenol compound represented by General formula (7) mentioned above is synthesize
  • the method for producing the dihydroxy compound of the general formula (1) will be described in detail.
  • the condensation reaction is carried out by reacting the N-phenylisatin compound represented by the general formula (5) with the phenylphenol compound represented by the general formula (6) in the presence of an acid catalyst.
  • the charged molar ratio of the phenylphenol compound to the N-phenylisatin compound is not particularly limited as long as it is the theoretical value (2.0) or more, but usually 2.5 times the molar amount or more, Preferably, it is used in the range of 2.5 to 20 times the molar amount, particularly preferably in the range of 3 to 10 times the molar amount.
  • the acid catalyst examples include hydrochloric acid, hydrogen chloride gas, 60-98% sulfuric acid, 85% phosphoric acid and other inorganic acids, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, etc. And solid acids such as organic acids and heteropolyacids. Hydrogen chloride gas is preferred. The amount of such an acid catalyst used varies depending on the reaction conditions.
  • the hydrogen chloride gas concentration in the gas phase in the reaction vessel is preferably 75 to 100% by volume, and the hydrogen chloride concentration in the reaction solution is preferably saturated.
  • hydrochloric acid it is used in the range of 5 to 70 parts by weight, preferably in the range of 10 to 40 parts by weight, more preferably in the range of 20 to 30 parts by weight with respect to 100 parts by weight of the phenylphenol compound.
  • a co-catalyst may be used together with the acid catalyst as necessary.
  • the reaction rate can be accelerated by using thiols as a co-catalyst.
  • thiols include alkyl mercaptans and mercaptocarboxylic acids, preferably alkyl mercaptans having 1 to 12 carbon atoms and mercaptocarboxylic acids having 1 to 12 carbon atoms, such as methyl mercaptan.
  • alkali metal salts such as ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, and sodium salts thereof, thioacetic acid, ⁇ -mercaptopropionic acid, and the like.
  • the amount of thiols used as a co-catalyst is usually in the range of 1 to 30 mol%, preferably in the range of 2 to 10 mol%, relative to the starting N-phenylisatin compound.
  • the reaction solvent is not required to be used if the N-phenylisatin compound and the phenylphenol compound as raw materials have low melting points and there is no problem in operability. It may be used for reasons such as improving the reaction rate.
  • the reaction solvent is not particularly limited as long as it does not distill from the reactor at the reaction temperature and is inert to the reaction.
  • aromatic hydrocarbons such as toluene and xylene, methanol, n-propyl alcohol, isobutyl alcohol, etc.
  • aliphatic alcohols such as hexane, heptane and cyclohexane, carboxylic acid esters such as ethyl acetate and butyl acetate, and mixtures thereof.
  • aliphatic alcohols are preferably used.
  • a small amount of water may be added as necessary.
  • the acid catalyst is hydrogen chloride gas
  • water is preferable for promoting the absorption of hydrogen chloride gas by the catalyst.
  • the addition amount is preferably in the range of 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the phenylphenol compound.
  • the reaction temperature varies depending on the conditions of the catalyst etc. used, it is generally in the range of 10-60 ° C, preferably 25-50 ° C.
  • the reaction pressure is usually carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under pressure or reduced pressure so that the reaction temperature falls within the above range. If the reaction is carried out under such conditions, the reaction is usually completed in about 1 to 30 hours.
  • the end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis.
  • the end point of the reaction is preferably the point at which the unreacted N-phenylisatin compound disappears and no increase in the desired product is observed.
  • the reaction yield based on the phenylphenol compound is usually about 75 to 95 mol%.
  • the resulting reaction mixture is added with an alkaline solution such as aqueous ammonia or aqueous sodium hydroxide solution to neutralize the acid catalyst, and contains the bisphenol compound represented by the general formula (7) according to the present invention.
  • a reaction mixture is obtained.
  • a known method can be used.
  • the neutralized reaction-terminated mixture is directly or once heated to be a uniform solution, and then cooled, or a crystallization solvent such as methanol is added, and then cooled to precipitate crystals. By filtering off, a crude or high-purity target product can be obtained.
  • the bisphenol compound thus obtained may be further purified as necessary to obtain a high purity product.
  • the obtained target crystal is again dissolved in an appropriate solvent, for example, an aromatic solvent such as toluene, an aliphatic ketone solvent such as methyl ethyl ketone, and cooled or crystallized such as methanol or water. Add the precipitation solvent, cool again, crystallize, filter and dry.
  • the reaction solvent and the like are concentrated from the reaction completion mixture under reduced pressure, and the residue can be purified by column chromatography or the like to obtain a high-purity product of the target product. .
  • Examples of the production method other than the above preferred production method of the dihydroxy compound represented by the general formula (1) of the present invention include an N-phenylisatin compound represented by the following general formula (5) and phenylphenoxy alcohol. And a method obtained by reacting a compound in the presence of an acid catalyst.
  • hydroxyalkylation which manufactures the dihydroxy compound of General formula (1) using alkylene carbonate is demonstrated.
  • Hydroxyalkylation is usually performed in the presence of a base catalyst.
  • the base catalyst include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, quaternary ammonium halides such as tetra-n-butylammonium bromide, tetraethylammonium chloride and tetramethylammonium chloride. These base catalysts can be used alone or in combination of two or more.
  • the amount of such a base catalyst used varies depending on the reaction conditions, but is usually in the range of 0.005 to 0.5 mol, preferably 0.01 to 0.4 mol, relative to 1 mol of the bisphenol compound. Used in a range.
  • the amount of alkylene carbonate used relative to the bisphenol compound is usually in the range of 2 to 10 moles, preferably in the range of 2.5 to 5 moles per mole of the bisphenol compound.
  • the reaction temperature is usually in the range of 100 to 150 ° C, preferably 120 to 130 ° C.
  • the reaction is usually carried out using a reaction solvent.
  • reaction solvent examples include aromatic hydrocarbons such as toluene and xylene, aliphatic alcohols such as 1-butanol, 2-butanol and ethylene glycol, ketones such as acetone and methyl isobutyl ketone, tetrahydrofuran, dioxane, 1, 2 and the like. -Ethers such as diethoxyethane, aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide or mixtures thereof.
  • the amount of these reaction solvents used is preferably in the range of 50 to 300 parts by weight and more preferably in the range of 100 to 200 parts by weight with respect to 100 parts by weight of the bisphenol compound.
  • the hydroxyalkylation method is not particularly limited, and a known method can be used.
  • the reaction raw material, catalyst, reaction solvent, etc. may be charged into the reaction vessel at once, and the temperature may be raised to the reaction temperature.
  • the mixed solution of the bisphenol compound, the reaction solvent, and the catalyst may be heated to a predetermined temperature, and alkylene carbonates may be added dropwise thereto.
  • the target product can be taken out from the reaction mixture as a crude crystal or high-purity product by a known purification method.
  • water is added to the reaction completion mixture to decompose excess alkylene carbonate with water.
  • an alkali catalyst it may be neutralized by adding an acid.
  • the target substance with higher purity can be obtained.
  • each R independently represents an alkylene group having 2 to 6 carbon atoms
  • each R 1 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, phenyl
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom
  • R 3 represents 1 to 8 carbon atoms.
  • the polycarbonate containing a preferable repeating unit in the polycarbonate containing the repeating unit represented by the general formula (2) is represented by the following general formula (13).
  • R 1 , R 2 , R 3 , m and n are the same as those in the general formula (2), and R 4 is the same as that in the general formula (3).
  • Preferred examples and specific examples relating to R 1 , R 2 , R 3 , m and n are the same as those in the general formula (1), and preferred examples and specific examples relating to R 4 are the same as those in the general formula (3). .
  • any conventionally well-known arbitrary methods can be used. Specific examples include an interfacial polymerization method, a melt transesterification method, a solid phase polymerization method, a ring-opening polymerization method of a cyclic carbonate compound, a pyridine method, etc. Among them, interfacial weight using a dihydroxy compound and a carbonate precursor as raw materials.
  • a combined method and a melt transesterification method are preferable, and it is particularly preferable to produce a dihydroxy compound represented by the general formula (1) and a carbonate such as diphenyl carbonate by a melt transesterification reaction in the presence of a transesterification catalyst.
  • the dihydroxy compound used as a raw material for the aromatic polycarbonate containing the repeating unit represented by the general formula (2) is a compound other than the dihydroxy compound represented by the general formula (1) as long as the effects of the present invention are not hindered.
  • other dihydroxy compounds such as bisphenol A can also be used as a copolymerization raw material.
  • the ratio of the dihydroxy compound copolymer raw material other than the dihydroxy compound represented by the general formula (1) mainly used in all dihydroxy compounds is not particularly limited as long as the effect of the present invention is not hindered.
  • melt transesterification method for producing a polycarbonate containing the repeating unit represented by the general formula (2) by melt polycondensation will be described in more detail.
  • a conventionally known method can be used as the melt transesterification method.
  • the starting dihydroxy compound is 3,3-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) -1-phenyl-1H-indol-2-one and the starting carbonic acid diester is diphenyl carbonate
  • the reaction for obtaining the above aromatic polycarbonate is shown by the following reaction formula.
  • the melt transesterification reaction is carried out by distilling the produced phenol by stirring the dihydroxy compound and the carbonic acid diester in the presence of a catalyst while heating the carbonic acid diester in an atmospheric pressure or reduced pressure inert gas atmosphere.
  • the carbonic acid diester to be reacted with the dihydroxy compound include, for example, diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and bis (m-cresyl) carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dicyclohexyl carbonate, and methyl.
  • diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and bis (m-cresyl) carbonate
  • dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dicyclohexyl carbonate, and methyl.
  • alkylaryl carbonates such as phenyl carbonate, ethylphenyl carbonate and cyclohexyl phenyl carbonate
  • dialkenyl carbonates such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate.
  • Diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.
  • the aromatic polycarbonate which adjusted the desired molecular weight and the amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of a dihydroxy compound and carbonic acid diester, and the pressure reduction degree at the time of transesterification.
  • the carbonic acid diester is usually used in an amount of 0.5 to 1.5 moles, preferably 0.6 to 1.2 moles per mole of the dihydroxy compound.
  • a transesterification catalyst is used as necessary to increase the reaction rate.
  • the transesterification catalyst is not particularly limited, and examples thereof include inorganic alkali metal compounds such as lithium, sodium and cesium hydroxides, carbonates and hydrogen carbonate compounds, and alkali alkali compounds such as alcoholates and organic carboxylates.
  • Metal compounds hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron and tetraethyl Basic boron compounds such as sodium salts such as boron and butyltriphenylboron, calcium salts and magnesium salts; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine; or 4 derived from these compounds Basic phosphorus compounds such as quaternary phosphonium salts; Use a known transesterification catalyst such as basic ammonium compounds such as lamethylammonium hydroxide, tetra
  • the amount of the catalyst used is within a range where the catalyst residue does not cause a problem in the quality of the produced polycarbonate, and since the preferred addition amount varies depending on the type of catalyst, it cannot be said unconditionally, for example, the general formula ( The amount is usually 0.05 to 100 ⁇ mol, preferably 0.08 to 50 ⁇ mol, more preferably 0.1 to 20 ⁇ mol, still more preferably 0.1 to 5 ⁇ mol with respect to 1 mol of the dihydroxy compound represented by 1). is there.
  • the catalyst may be added as it is, or may be added after being dissolved in a solvent.
  • the temperature is usually in the range of 120 to 360 ° C, preferably in the range of 150 to 280 ° C, more preferably in the range of 180 to 270 ° C. If the reaction temperature is too low, the transesterification reaction does not proceed, and if the reaction temperature is high, side reactions such as a decomposition reaction proceed.
  • the reaction is preferably carried out under reduced pressure, and the reaction pressure is preferably a pressure at which the diester carbonate as a raw material does not distill out of the system at the reaction temperature and phenol by-produced distills. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.
  • the reaction product containing polycarbonate obtained in this way is then subjected to a separation reduction treatment of low molecular weight components as necessary, and then subjected to a drying step, thereby being represented by the general formula (2).
  • a polycarbonate containing repeating units is obtained.
  • the reaction-finished product containing polycarbonate obtained by the reaction step is usually a transparent viscous material in a molten state near the reaction temperature, and is a solid body near normal temperature.
  • the low molecular weight component separation and reduction treatment that may be performed as needed is, for example, as disclosed in JP-A-7-192310, in which polycarbonate is dissolved in an appropriate good solvent, and then the polycarbonate is dissolved in a poor solvent such as methanol.
  • the above-mentioned aromatic polycarbonate having a reduced low molecular weight component such as particles, powders, and flakes
  • a more preferable method for obtaining a high molecular weight polycarbonate as described in JP-A-3-223330 and WO00 / 18822, preliminary polymerization is performed in the reaction (first step) to obtain a polycarbonate oligomer, and the polycarbonate oligomer Is subjected to solid phase polymerization or swelling solid phase polymerization in the presence of a catalyst (second step) to obtain a high molecular weight polycarbonate.
  • the prepolymerization in the first step is carried out by a melt transesterification reaction, and a dihydroxy compound and diphenyl carbonate are distilled at a temperature of 120 to 360 ° C., preferably 150 to 280 ° C., particularly preferably while distilling phenol in the presence of a catalyst.
  • a polycarbonate oligomer is obtained by reacting at 180 to 270 ° C. for 0.5 to 10 hours.
  • the polycarbonate oligomer obtained in the first step is preferably made into a solid body such as flakes, powders or particles according to a known method from the viewpoint of operability in the second step.
  • the above-described transesterification catalyst such as a quaternary phosphonium salt
  • the above-described transesterification catalyst is optionally added to the polycarbonate oligomer obtained in the first step as necessary under reduced pressure, and an inert gas is introduced.
  • an inert gas is introduced.
  • a molecular weight polycarbonate is obtained.
  • the reaction in the first step and the reaction in the second step may be performed separately or continuously.
  • the polycarbonate oligomer usually has a weight average molecular weight of, for example, about 500 to 15,000.
  • the high molecular weight polycarbonate usually has a weight average molecular weight of, for example, about 15000 to 100,000.
  • the polycarbonate using the dihydroxy compound of the present invention as a raw material is not limited to such a molecular weight.
  • the polycarbonate obtained as described above is a high molecular weight polycarbonate, which is excellent in transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc., and optical lenses and flat panel displays used in optical disks, smartphones, etc. It can be expected to be used in various fields such as optical applications such as optical films, and automotive plastics, electrical / electronics, and various containers as engineering plastics.
  • Polycarbonate oligomers can be used not only as raw materials for producing high molecular weight polycarbonate by various polymerization methods, but also as surface modifiers, flame retardants, ultraviolet absorbers, fluidity modifiers, plasticizers. Also, it can be widely used as additives such as polymer modifiers such as resin alloy solubilizers. Furthermore, as other uses, the dihydroxy compound of the present invention uses an epoxy resin, an oxetane resin, an acrylic resin, a polyester, a polyarylate, a polyether ether ketone, a polysulfone, in addition to a polycarbonate, using a terminal hydroxy group.
  • a resin raw material such as novolak and resol
  • other photosensitive composition raw materials such as resist additives, developers, and antioxidants
  • it can be expected to be used as an acrylic monomer or acrylic resin raw material such as diacrylate obtained by reacting the dihydroxy compound of the present invention with acrylic acid or the like, and as an optical hard coating material using them.
  • Refractive index measuring device Refractometer RA-500N manufactured by Kyoto Electronics Industry Co., Ltd. Measuring method: A THF solution (THF refractive index of 1.40) having a concentration of 10, 15, or 30% was adjusted, and the refractive index of the measurement compound was calculated from the refractive index of the solution by extrapolation. 3.
  • Purity measurement device CLASS-LC10 manufactured by Shimadzu Corporation Pump: LC-10ATvp Column oven: CTO-10Avp Detector: SPD-10Avp Column: Shim-pack CLC-ODS inner diameter 6mm, length 150mm Oven temperature: 50 °C Flow rate: 1.0ml / min
  • Mobile phase (A) Acetonitrile, (B) 0.2 vol% acetic acid water Gradient condition: (A) Volume% (Time from the start of analysis) 60% (0min) ⁇ 60% (20min) ⁇ 100% (40min) ⁇ 100% (50min) Sample injection volume: 20 ⁇ l Detection wavelength: 280nm
  • Step 1 Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine (Step 1)
  • a four-necked flask equipped with a thermometer, a stirrer, and a condenser tube was charged with 902.5 g (9.70 mol) of aniline, and after the reaction vessel was purged with nitrogen, 192.7 g of methanesulfonic acid was maintained at 85 to 95 ° C. Was dropped into the system.
  • 385.4 g (1.21 mol) of phenolphthalein was added at 90 to 100 ° C., and after completion of the addition, the mixture was stirred for 21.5 hours while maintaining 147 to 153 ° C.
  • Table 1 shows the melting point, softening point, and refractive index of the compound obtained in Example 1 and the compound obtained in Comparative Example 1. Since the compound of Example 1 according to the present invention has higher heat resistance (softening point temperature) and higher refractive index than the known compound of Comparative Example 1, it is useful as a polycarbonate raw material for optical materials. It was confirmed that.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Indole Compounds (AREA)

Abstract

La présente invention traite le problème de la fourniture d'un nouveau composé dihydroxy ayant un squelette indoline, le nouveau composé dihydroxy étant approprié comme matière première pour un oligomère ou une résine de polycarbonate aromatique, etc.. Le problème peut être résolu par un composé dihydroxy représenté par la formule générale (1).　
PCT/JP2017/011625 2016-03-28 2017-03-23 Nouveau composé dihydroxy Ceased WO2017170094A1 (fr)

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JP2018509158A JP7267008B2 (ja) 2016-03-28 2017-03-23 新規なジヒドロキシ化合物
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CN201780022066.2A CN108884040A (zh) 2016-03-28 2017-03-23 新颖的二羟基化合物

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JP2010505011A (ja) * 2006-09-28 2010-02-18 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 金属への接着が改良されたポリカーボネートおよびコポリカーボネート
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JP7267008B2 (ja) 2023-05-01
KR20180128931A (ko) 2018-12-04
JPWO2017170094A1 (ja) 2019-02-07
CN108884040A (zh) 2018-11-23
KR102263143B1 (ko) 2021-06-08
TW201802069A (zh) 2018-01-16

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