WO2017170095A1 - Nouveau composé dihydroxy - Google Patents

Nouveau composé dihydroxy Download PDF

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Publication number
WO2017170095A1
WO2017170095A1 PCT/JP2017/011626 JP2017011626W WO2017170095A1 WO 2017170095 A1 WO2017170095 A1 WO 2017170095A1 JP 2017011626 W JP2017011626 W JP 2017011626W WO 2017170095 A1 WO2017170095 A1 WO 2017170095A1
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general formula
group
reaction
phenyl
dihydroxy compound
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PCT/JP2017/011626
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English (en)
Japanese (ja)
Inventor
隼 溝口
緒旺 路
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本州化学工業株式会社
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Application filed by 本州化学工業株式会社 filed Critical 本州化学工業株式会社
Priority to KR1020187029623A priority Critical patent/KR102350817B1/ko
Priority to JP2018509159A priority patent/JPWO2017170095A1/ja
Priority to CN201780020433.5A priority patent/CN108884038A/zh
Publication of WO2017170095A1 publication Critical patent/WO2017170095A1/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
    • C08G64/02—Aliphatic polycarbonates

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.
  • a method for producing bisphenoxy alcohols there is known a method in which a bisphenol compound is reacted with an alkylene carbonate or an alkylene oxide. In this method, as a impurity, a monohydroxyalkoxy compound or a target product is produced. Bisphenoxy alcohols further react with alkylene carbonates and alkylene oxides to produce a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group, resulting in a low reaction selectivity.
  • the resulting compound since there are raw materials and intermediates having an aromatic hydroxyl group, the resulting compound is colored and has poor thermal stability, so it must be repeatedly purified for use as an optical application, which is industrially disadvantageous. is there.
  • 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.
  • the present inventors have found that the dihydroxy compound of the present invention having an indoline skeleton is excellent in optical properties such as high heat resistance and high refractive index, and completed the present invention. did.
  • a dihydroxy compound represented by the following general formula (1) (Wherein R represents an alkylene group having 2 to 6 carbon atoms, R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different. When n is 2, R 2 is the same But it may be different.)
  • the dihydroxy compound according to the present invention has high heat resistance and a high refractive index, an excellent effect as a polycarbonate raw material for optical materials can be expected.
  • the dihydroxy compound according to the present invention is a monohydroxyalkoxy compound (sometimes referred to as 1EO form) or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (sometimes referred to as multi-EO form). High purity without containing, and excellent optical properties such as thermal stability and product hue.
  • the polycarbonate using the dihydroxy compound of the present invention as a raw material monomer is a monohydroxyalkoxy compound (1EO form) in which the raw material monomer is an impurity, or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (multi-EO form). ), It is expected to have high purity, high heat resistance, and high refractive index, and in particular, an excellent effect is expected in polycarbonate for optical materials.
  • the dihydroxy compound of the present invention is represented by the following general formula (1).
  • R represents an alkylene group having 2 to 6 carbon atoms
  • R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
  • m represents an integer of 0 to 3
  • n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different.
  • R 2 is the same But it may be different.
  • 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 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when R 1 is an alkyl group having 1 to 8 carbon atoms, Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • R 1 and R 2 are alkoxy groups 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.
  • Preferred R 1 and R 2 are methyl groups.
  • m is 0, 1, 2, or 3, Preferably it is 0, 1 or 2, Especially preferably, it is 0 or 1.
  • n is 0, 1 or 2, Preferably it is 0 or 1, Especially preferably, it is 0.
  • the “—O—R—OH” group substituted for the phenyl group directly bonded to the 3-position carbon atom of the indoline skeleton and the substitution position of R 1 are first described as “
  • 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 at the 4-position.
  • R 1 is preferably substituted at the o-position or the p-position with respect to the “—O—R—OH” group, and is a phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton.
  • the “—O—R—OH” group when the “—O—R—OH” group is substituted at the 4-position, it is preferably substituted at the 3-position or the 5-position, and the “—O—R—OH” group is substituted at the 2-position. When it is, it is preferable to substitute at the 3-position or 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, or R 1 is substituted on 3-position and 5-position "-O-R-OH” group is 4-position, it is preferred that R 1 is substituted on the 2- and 5-positions.
  • 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, R 1 is preferably substituted at the 2-position, 3-position and 5-position.
  • the dihydroxy compound represented by the general formula (1) is preferably represented by the following general formula (3).
  • R 2 and n are the same as those in formula (1), and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • each R 4 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 for each hydroxyethoxy group is 4 or less.
  • preferred examples and specific examples relating to R 2 and n are the same as those in the general formula (1).
  • R 3 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
  • preferred examples and specific examples thereof are represented by the general formula (1 ) Is the same as when R 1 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • R 3 is more preferably a hydrogen atom or a methyl group.
  • At least one of R 3 at the 3-position and the 5-position is preferably a hydrogen atom with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton
  • R 3 in the 2nd and 5th positions is preferably a hydrogen atom with respect to a phenyl carbon atom directly bonded to the 3rd carbon atom of the indoline skeleton
  • all R 3 are preferably hydrogen atoms.
  • R 4 is an alkyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, and the like.
  • R 4 is particularly preferably a hydrogen atom or a methyl group.
  • dihydroxy compound represented by the general formula (1) of the present invention examples include 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indole-2- on 3,3-bis (4- (2-hydroxy-2-methylethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxy-1-methylethoxy) Phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -1-phenyl-1H-indole-2-one 3,3- Bis (3-ethyl-4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis (4- (2-hydroxyethoxy)
  • the production method of the dihydroxy compound represented by the general formula (1) of the present invention is not particularly limited.
  • the N-phenylisatin compound represented by the following general formula (5) and the following general formula It can be obtained by using a phenoxy alcohol compound represented by the formula (6) as a raw material and reacting them in the presence of an acid catalyst.
  • the raw material N-phenylisatin compound of the above production method is represented by the following general formula (5).
  • R 2 and n are the same as those in the general formula (1).
  • Preferred examples and specific examples of R 2 and n are the same as those in the general formula (1).
  • N-phenylisatin compound represented by the general formula (5) examples 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.
  • the raw material phenoxy alcohol compound of the above-mentioned manufacturing method is represented by the following general formula (6).
  • R, R 1 and m are the same as those in the general formula (1).
  • Preferred examples and specific examples relating to R, R 1 and m are also the same as those in the general formula (1).
  • a phenoxy alcohol compound represented by the general formula (6) a compound represented by the general formula (7) is preferable.
  • R 3 and R 4 are the same as those in the general formula (3).
  • Preferred examples and specific examples relating to R 3 and R 4 are also the same as those in the general formula (3).
  • Specific examples of the compound represented by the general formula (7) include 2-phenoxyethanol 2-phenoxypropanol 1-phenoxy-2-propanol 2- (2-methylphenoxy) ethanol 2- (2 -Ethylphenoxy) ethanol 2- (2,6-dimethylphenoxy) ethanol 2- (2,5-dimethylphenoxy) ethanol 2- (2,3,6-trimethylphenoxy) ethanol and the like.
  • the manufacturing method of the dihydroxy compound of this invention is not specifically limited, As an example of the preferable manufacturing method for obtaining the more preferable dihydroxy compound (1EO body and 3EO body are not included) of this invention, it represents with General formula (5).
  • the dihydroxy compound represented by the general formula (1) having an indoline skeleton is produced by reacting the N-phenylisatin compound produced with the phenoxy alcohol compound represented by the general formula (6) or (7).
  • the method of performing will be described in detail.
  • the condensation reaction is carried out by reacting the above N-phenylisatin compound with a phenoxy alcohol compound, usually in the presence of an acid catalyst.
  • the charged molar ratio of the phenoxy alcohol compound to the N-phenylisatin compound is not particularly limited as long as it is the theoretical value (2.0) or more, but preferably 3.0 times the molar amount or more, More preferably, it is used in the range of 3.5 to 20 times the molar amount, particularly preferably in the range of 4.0 to 15 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.
  • 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.
  • 35% 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 phenoxy alcohol compound.
  • thiols examples 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, thioglycolic acid, ⁇ -mercaptopropionic acid, and the like.
  • these can be used individually or in combination of 2 or more types.
  • the amount of thiols used as a co-catalyst is usually in the range of 0.5 to 20 mol%, preferably in the range of 2 to 10 mol%, relative to the starting N-phenylisatin compound.
  • the reaction solvent As the reaction solvent, the starting N-phenylisatin compound and the phenoxyalcohol compound have a low melting point, and if there is no problem in operability, it is not necessary to use a solvent. 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. Of these, 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 15.0 parts by weight with respect to 100 parts by weight of the phenoxy alcohol compound.
  • reaction temperature varies depending on the conditions of the catalyst used, for example, when hydrogen chloride gas is used as the catalyst, the range of 20 to 70 ° C. is preferable, and the range of 30 to 60 ° C. is more preferable.
  • 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 phenoxy alcohol 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 dihydroxy compound represented by the general formula (1) according to the present invention.
  • a reaction mixture is obtained.
  • water washing treatment is performed to add water and an insoluble organic solvent to the water and sufficiently stir to separate the oil layer. Do.
  • the organic solvent used at this time it is necessary to dissolve the dihydroxy compound of the general formula (1) and to have a low solubility in water.
  • an aromatic hydrocarbon such as toluene or xylene, an aliphatic hydrocarbon such as cyclohexane or n-heptane, an aliphatic ketone such as methyl isobutyl ketone, or an alcohol solvent such as butanol is employed.
  • the organic solvent layer obtained after the neutralization and washing with water is partially removed by distillation, if necessary, and then the organic solvent layer is heated as it is or once to a uniform solution, cooled, or appropriately When crystals are precipitated by adding a crystallization solvent or a poor solvent and cooling, a crude or high-purity target product can be obtained by filtering the crystals.
  • the target product obtained above can be further purified by recrystallization using a solvent.
  • Organic solvents used at this time include aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and alcohols such as butanol.
  • a solvent is mentioned, These can be used individually or in mixture of 2 or more types. Instead of the above crystallization operation, after completion of the reaction, the reaction solvent and the like are concentrated under reduced pressure, and the residue is purified by column chromatography or the like to obtain a high purity product.
  • the dihydroxy compound represented by the general formula (1) may contain, a 1EO body (monohydroxyalkoxy body) represented by the following general formula (8), and the following general formula (9) And a multi-EO body represented by the formula (a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group).
  • a method of reacting the N-phenylisatin compound represented by the general formula (5) with the phenoxy alcohol compound represented by the general formula (6) or the general formula (7) which is the above-described production method.
  • the 1EO body represented by the following general formula (8), the multi-EO body represented by the following general formula (9) and the 3EO body represented by the following general formula (10) do not contain impurities. It is possible to produce a dihydroxy compound represented by the formula (1).
  • the above 1EO body is represented by the following general formula (8). (In the formula, R, R 1 , R 2 , m and n are the same as those in the general formula (1).) Preferred examples and specific examples relating to R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the above multi-EO body is represented by the following general formula (9).
  • R, R 1 , R 2 , m, and n are the same as those in the general formula (1), and k each independently represents an integer of 1 to 5, provided that k is 1 at the same time. except for.)
  • Preferred examples and specific examples relating to R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the 3EO body which is a compound more likely to be contained in the multi-EO body represented by the general formula (9) is represented by the following general formula (10).
  • R, R 1 , R 2 , m and n are the same as those in the general formula (1).
  • Preferred examples and specific examples relating to R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the purity of the dihydroxy compound represented by the general formula (1) of the present invention and the amount of impurities contained are not particularly limited, but the following range calculated from area% by high performance liquid chromatography is preferred.
  • the purity of the dihydroxy compound represented by the general formula (1) of the present invention is preferably 97.5% or more, more preferably 98.0% or more, still more preferably 98.5% or more, and particularly preferably 99.0. % Or more.
  • the content of 1EO is preferably 0.5% or less, more preferably 0.3% or less, still more preferably 0.1% or less, and particularly preferably substantially free (below the detection limit).
  • the content of the multi-EO body is preferably 1.5% or less, more preferably 1.0% or less, further preferably 0.5% or less, particularly preferably 0.1% or less, and most preferably substantially contained. No (below detection limit).
  • the content of 3EO bodies is preferably 1.5% or less, more preferably 1.0% or less, still more preferably 0.5% or less, particularly preferably 0.1% or less, and most preferably It is not substantially contained (below the detection limit).
  • the polycarbonate is represented by the following general formula (2).
  • R represents an alkylene group having 2 to 6 carbon atoms
  • R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
  • m represents an integer of 0 to 3
  • n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different.
  • R 2 is the same But it may be different.
  • R 2 and n are the same as those in the general formula (1), and R 3 and R 4 are the same as those in the general formula (3).
  • Preferred examples and specific examples relating to R 2 and n are the same as those in the general formula (1), and preferred examples and specific examples relating to R 3 and R 4 are the same as those in the general formula (3).
  • the polycarbonate containing the repeating unit represented by the general formula (2) is not particularly limited as to its production method, and any conventionally known method 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 of the polycarbonate containing the repeating unit represented by the general formula (2) is, for example, 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 copolymer 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) phenyl) -1-phenyl-1H-indol-2-one and the starting carbonic acid diester is diphenyl carbonate
  • the reaction for obtaining the group polycarbonate is shown by the following reaction formula.
  • the melt transesterification reaction is performed by stirring the dihydroxy compound and the carbonic acid diester in the presence of a catalyst while heating the carbonic acid diester and an atmospheric pressure or a reduced pressure inert gas atmosphere to distill the produced phenol.
  • 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 molecular weight component such as particles, powders, and flakes
  • prepolymerization is performed in the reaction as described in JP-A-3-223330 and WO00 / 18822 (first step) to obtain a polycarbonate oligomer.
  • a high molecular weight polycarbonate can be obtained by solid phase polymerization or swelling solid phase polymerization in the presence of a catalyst (second step).
  • 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) Methanol, (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
  • Example 1 Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one
  • 2-phenoxyethanol 331 .2 g (2.40 mol) and 14.6-phenyl-1H-indole-2,3-dione (44.6 g, 0.20 mol) were charged, the reaction vessel was purged with nitrogen, and hydrogen chloride gas was blown at 40 ° C.
  • the hydrogen chloride gas concentration in the gas phase was set to 95% or more.
  • the obtained oil layer was heated to 160 ° C., the solvent was removed by distillation under a reduced pressure of 1.0 kPa, then cooled, 582.2 g of toluene was added at 110 ° C., and 72.3 g of methanol at 70 ° C. Was added. Thereafter, the mixture was cooled to 30 ° C., and the precipitated crystals were separated by filtration to obtain 61.4 g of crude crystals as white crystals. After adding 226.5 g of 1-butanol to 55.5 g of the obtained crude crystals and dissolving at 110 ° C., 112.7 g of 1-butanol was removed by distillation under normal pressure, then cooled to 30 ° C. and precipitated.
  • 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.
  • Step 2 Purity 99.6% (high performance liquid chromatography) Yield 75% (vs. phenolphthalein) Melting point 291.5 ° C (differential scanning calorimetry) (Process 2) 30.0 g (0.076 mol) of 3,3-bis (4-hydroxyphenyl) -2-phenylphthalimidine obtained in Step 1 was added to a four-necked flask equipped with a thermometer, a stirrer and a condenser. 19.5 g (0.22 mol) of ethylene carbonate, 0.44 g of 48% potassium hydroxide aqueous solution (0.0038 mol as potassium hydroxide) and 45.0 g of 1-butanol were charged, and the reaction vessel was purged with nitrogen.
  • 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine obtained in Step 2 of Comparative Example 1 is an 1EO compound represented by the following general formula (12), which is an impurity And a 3EO body represented by the following general formula (13).
  • the 1EO body in Comparative Example 1 is represented by the general formula (12).
  • the 3EO body in Comparative Example 1 is represented by the general formula (13).
  • the production method of Step 2 of Comparative Example 1 cannot avoid the production of 1EO body represented by the general formula (12) and 3EO body represented by the general formula (13), and these impurities are industrially used in the purification process.
  • Table 1 shows the melting point, softening point, and refractive index of the compound obtained in Example 1 and the compound obtained in Step 2 of Comparative Example 1.
  • Example 1 of the present invention Since the compound of Example 1 of the present invention has higher heat resistance (softening point temperature) and higher refractive index than the known compound of Step 2 of Comparative Example 1, it is used for optical materials. It is useful as a raw material for polycarbonate.
  • Example 1 The experimental results of Example 1 and Comparative Example 2 of the present invention show that 1-phenyl-1H-indole-2,3-dione reacts with 2-phenoxyethanol to produce 3,3-bis (4- (2-hydroxyethoxy) (Phenyl) -1-phenyl-1H-indol-2-one is produced (Example 1), whereas N-phenylphthalimide does not undergo a condensation reaction with 2-phenoxyethanol under the same reaction conditions. This shows that -bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine is not produced (Comparative Example 2).
  • Comparative Example 3 shows that in the condensation reaction of N-phenylphthalimide and 2-phenoxyethanol, even when phosphotungstic acid was used as a catalyst, the reaction did not proceed and 3,3-bis (4- (2 This shows that -hydroxyethoxy) phenyl) -2-phenylphthalimidine is not produced (Comparative Example 3). That is, it is clear that the N-phenylisatin compound represented by the general formula (5) has extremely high reactivity with the phenoxy alcohol represented by the general formula (6) as compared with the N-phenylphthalimide compound. became.
  • the N-phenylisatin compound represented by the general formula (5) contains a conventionally known compound because the reaction with the phenoxy alcohol represented by the general formula (6) easily proceeds due to its unique chemical structure. It is represented by high-purity general formula (1) that does not contain impurities such as a hydroxyalkoxy compound (1EO form) or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (multi-EO form). It becomes possible to obtain a dihydroxy compound. Since the dihydroxy compound represented by the general formula (1) of the present invention is highly pure, it is excellent in optical properties such as thermal stability and product hue.
  • the polycarbonate using the dihydroxy compound of the present invention as a raw material uses the dihydroxy compound represented by the general formula (1) having a high purity as a raw material monomer, it may have a high purity, a high heat resistance, and a high refractive index. Expected to be particularly effective in polycarbonate for optical materials.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Epoxy Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

La présente invention aborde le problème consistant à fournir un nouveau composé dihydroxy ayant un squelette indoline qui présente une résistance élevée à la chaleur et un indice de réfraction élevé. La présente invention est une solution d'un composé dihydroxy représenté par la formule générale (1) (dans la formule, R représente un groupe alcylène en C2 à C6, R1 et R2 représentent chacun indépendamment un groupe alkyle en C1 à C8 ou un groupe alcoxy en C1 à C8, m représente un nombre entier d'une valeur de 0 à 3, et n représente un nombre entier d'une valeur de 0 à 2; cependant, lorsque m a la valeur de 2 ou plus, R1 peut être identique ou différent, et lorsque n a la valeur de 2, R2 peut être identique ou différent).
PCT/JP2017/011626 2016-03-28 2017-03-23 Nouveau composé dihydroxy WO2017170095A1 (fr)

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WO2022112943A1 (fr) * 2020-11-26 2022-06-02 Shpp Global Technologies B.V. Polycarbonate et compositions et articles comprenant le polycarbonate

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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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TW201738207A (zh) 2017-11-01
KR102350817B1 (ko) 2022-01-13

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