WO2014091910A1

WO2014091910A1 - Fluorene polymer, fluorene diol compound, and method for producing said polymer and compound

Info

Publication number: WO2014091910A1
Application number: PCT/JP2013/081615
Authority: WO
Inventors: 正晃松原; 俊一平林; 克宏藤井
Original assignee: 田岡化学工業株式会社
Priority date: 2012-12-10
Filing date: 2013-11-25
Publication date: 2014-06-19
Also published as: TW201428021A; KR20150095771A; TWI598374B; CN104812797A; CN104812797B; JP2014114387A; JP6233949B2; KR101997313B1

Abstract

The present invention provides a fluorene polymer containing in the main chain constituent units derived from a fluorene diol compound represented by general formula (I) (in the formula, R ¹ represents an alkyl group, cycloalkyl group, or aryl group), the fluorene diol compound (in the formula, R ¹ represents a C₂ or higher alkyl group, cycloalkyl group, or aryl group), and a method for producing the fluorene diol compound (in the formula, R ¹ represents an alkyl group, cycloalkyl group, or aryl group).

Description

Fluorene polymer, fluorene diol compound and method for producing the same

The present invention relates to a fluorene polymer that can be suitably used as a resin (optical resin) constituting an optical member typified by an optical lens or an optical film. Moreover, this invention relates to the fluorene type diol compound suitable as a monomer which forms the said fluorene type polymer, and its manufacturing method.

Polycarbonate resin, cycloolefin resin, polymethacrylic resin, and the like have been conventionally used as optical resins because they are relatively excellent in high refractive index properties, low birefringence properties, transparency, and processability. In recent years, since it is particularly advantageous for achieving both high refractive index and low birefringence, a skeleton of a so-called “cardo structure” in which two phenyl groups are introduced at the 9-position of fluorene. An optical resin made of a fluorene-based polymer has attracted attention, and active research and development has been conducted.

For example, Japanese Patent Laid-Open No. 06-025398 (Patent Document 1) discloses a polycarbonate resin having 9,9-bis (4-hydroxyphenyl) fluorenes as a part of the diol component. Japanese Patent Application Laid-Open No. 06-049186 (Patent Document 2) discloses a polyester polymer for an optical material having 9,9-bis (4-hydroxyalkoxyphenyl) fluorene as a part of a diol component. Japanese Patent No. 5011450 (Patent Document 3) discloses a polyester carbonate copolymer for optical lenses having 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component. Yes.

Japanese Patent Application Laid-Open No. 06-025398 Japanese Patent Application Laid-Open No. 06-049186 Japanese Patent No. 5011450

An object of the present invention is to provide a novel fluorene polymer that exhibits a high refractive index and is useful as an optical resin. Another object of the present invention is to provide a fluorene diol compound useful as a monomer for forming the fluorene polymer and a method for producing the same.

The present invention includes the following.
[1] The following general formula (I):

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group or an aryl group. ]
A fluorene polymer containing a structural unit derived from a fluorene diol compound represented by the formula:

[2] The fluorene polymer according to [1], wherein the main chain contains at least one of a carbonate bond and an ester bond.

[3] The fluorene polymer according to [1] or [2], wherein the refractive index at 23 ° C. is 1.6 or more.

[4] A fluorene-based diol compound represented by the general formula (I) according to [1],
A fluorene-based diol compound in which R ¹ in the general formula (I) is an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.

[5] A method for producing a fluorene-based diol compound represented by the general formula (I) according to [1],
Under acidic conditions, 9-fluorenone and the following general formula (II):

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group or an aryl group. ]
A process comprising the step of reacting with an m-alkylphenol represented by the formula:

[6] The production method according to [5], wherein 9-fluorenone is reacted with the m-alkylphenol in the presence of paratoluenesulfonic acid and a thiol compound.

The fluorene polymer according to the present invention containing the structural unit derived from the fluorene diol compound represented by the above general formula (I) has both high refractive index and low birefringence, transparency and heat resistance. And is suitable as an optical resin constituting an optical member such as an optical lens, an optical film, a plastic optical fiber, and an optical disk substrate. Further, taking advantage of its high heat resistance, transparency, durability, etc., it can also be used as a non-optical resin such as a heat resistant resin or engineering plastic.

Further, according to the present invention, it is possible to provide a fluorene-based diol compound represented by the above general formula (I) that is useful as a raw material monomer for the fluorene-based polymer. According to the production method of the present invention, the fluorene-based diol compound can be produced with high reaction selectivity, and the high-purity fluorene-based diol compound can be obtained with high yield.

It is a two-dimensional NMR (HH COSY) spectrum of the fluorene diol compound Ia. 2 is a two-dimensional NMR (CH COSY) spectrum of fluorene-based diol compound Ia. It is a two-dimensional NMR (HH COSY) spectrum of the fluorene diol compound Ib. It is a two-dimensional NMR (CH COSY) spectrum of the fluorene diol compound Ib.

<Fluorene polymer>
The fluorene polymer of the present invention (hereinafter also simply referred to as “fluorene polymer”) is a polymer containing a structural unit derived from the fluorene diol compound represented by the general formula (I) in the main chain. In the general formula (I), R ¹ is an alkyl group, a cycloalkyl group or an aryl group.

Examples of the alkyl group include straight groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group. A chain or branched alkyl group can be mentioned. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably 1 to 8 carbon atoms. 3 linear or branched alkyl groups.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, alkyl having 1 to 4 carbons) substituted cyclopentyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted cyclohexyl group, and the like. And a cycloalkyl group having 16 to 16 (preferably 5 to 8 carbon atoms) or an alkyl-substituted cycloalkyl group. The cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group.

Examples of the aryl group include a phenyl group, an alkyl (for example, alkyl having 1 to 4 carbon atoms) -substituted phenyl group, and a naphthyl group. The aryl group is preferably a phenyl group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group.

The alkyl group, cycloalkyl group, and aryl group may have a substituent other than the alkyl group (for example, an alkoxyl group, an acyl group, a halogen atom, etc.).

The fluorene polymer may be a thermoplastic resin such as a polycarbonate resin, a polyester resin, a polyester carbonate resin, a (meth) acrylic resin, a polyurethane resin, or a heat such as an epoxy resin, a (meth) acrylic resin, or a polyurethane resin. Although it may be a curable resin or a photocurable resin, it is preferably a thermoplastic resin that can be injection-molded when a molded article such as an optical member is produced. The fluorene-based polymer of the present invention includes modified products of various resins as described above. Examples of the modified product include those having a functional group or molecular chain introduced at the end of the polymer, and those having a functional group or molecular chain introduced as a side chain of the polymer.

The fluorene-based polymer exhibits a very high refractive index while exhibiting a low birefringence due to including a structural unit derived from the fluorene-based diol compound represented by the general formula (I). The refractive index (23 ° C.) is the type of polymer, the chemical structure of the constituent units constituting the polymer, the presence / absence of constituent units derived from other diol components other than the fluorene diol compound, the content rate and / or Although it may vary depending on the chemical structure (type of other diol component) and the like, it is typically 1.6 or more. The fluorene-based polymer can exhibit a refractive index of 1.62 or higher, even 1.64 or higher, and even more 1.65 or higher.

The refractive index (20 ° C.) of a general polycarbonate resin (for example, bisphenol A or the like is used as a diol component), a cycloolefin resin, or a polymethacrylic resin that is widely used as an optical resin is about 1.59. , About 1.53 and about 1.49. Therefore, the fluorene polymer of the present invention is extremely superior in terms of refractive index as compared with these general conventional general-purpose optical resins.

Although it is a fluorene polymer, it is a polyester resin containing 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component and is a conventionally known fluorene heavy polymer as a high refractive index optical resin. For example, there are trade names “OKP4” and “OKP4HT” manufactured by Osaka Gas Chemical Co., Ltd. The refractive index (20 ° C.) of these polyester resins is about 1.60 to about 1.63. Therefore, the fluorene polymer of the present invention containing a structural unit derived from the fluorene-based diol compound represented by the general formula (I) is superior in terms of refractive index as compared with the conventional fluorene-based polymer. It can be said that. Such an improvement in refractive index is presumed to be due to the difference in position of the OH group (or hydroxyalkoxyl group) on the two phenyl groups.

Like the conventional fluorene polymer, the fluorene polymer of the present invention has a “cardo structure” (a fluorene ring, which is a structural unit derived from a fluorene diol compound) and two bonded to the 9-position thereof. Low birefringence is realized by a structure comprising a phenyl group). The birefringence of the conventional fluorene-based heavy compound in which an OH group or a hydroxyalkoxyl group is bonded to the 4-position of two phenyl groups. It tends to be lower than a polymer (for example, a polymer containing 9,9-bis (4-hydroxyphenyl) fluorene or 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component). This is because in the fluorene polymer of the present invention having a bulky OH group at the 2-position of two phenyl groups, the phenyl group is more orthogonal to the fluorene skeleton than the conventional fluorene polymer. This is thought to be due to the conformation.

The fluorene polymer of the present invention is a material suitable as an optical resin even in terms of a low Abbe number. The fluorene-based polymer can exhibit a low Abbe number of 30 or less, further 27 or less, and even 23 or less at 23 ° C., and can also exhibit an Abbe number of 20 or less. The Abbe numbers (20 ° C.) of the trade names “OKP4” and “OKP4HT” manufactured by Osaka Gas Chemical Co., Ltd. are 27 and 23, respectively.

The fluorene polymer of the present invention is advantageous compared to conventional optical resins in terms of heat resistance. That is, the fluorene polymer of the present invention may vary depending on the above-mentioned factors, but typically has a glass transition temperature of about 140 ° C. or higher, 160 ° C. or higher, further 170 ° C. or higher, and still more. Can also have a high glass transition temperature of 180 ° C. or higher. In contrast, the glass transition temperatures of general polycarbonate resins, cycloolefin resins, and polymethacrylic resins that are widely used as optical resins are about 145 ° C., about 140 ° C., and about 110 ° C., respectively. The glass transition temperatures of polyester resins containing bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component (for example, trade names “OKP4” and “OKP4HT” manufactured by Osaka Gas Chemical Co., Ltd.) and polycarbonate resins are respectively About 120 to 140 ° C. and about 150 ° C. (when the diol component consists only of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene).

The fluorene polymer of the present invention also has sufficient transparency, workability (moldability, etc.) and durability required for optical resins.

Hereinafter, a typical fluorene polymer (resin) will be described more specifically.
(Polycarbonate resin)
The fluorene polymer of the present invention, which is a polycarbonate resin, reacts a diol component containing the fluorene diol compound represented by the general formula (I) with a carbonic acid diester or phosgene in the presence or absence of a polymerization catalyst. It can be obtained according to conventional methods. The polycarbonate resin of the present invention contains a carbonate bond in which the OH group represented by the above general formula (I) (OH group bonded to the 2-position of the phenyl group bonded to the 9-position of the fluorene ring) is involved in the main chain. Resin, specifically, the following general formula (I-1):

[The meaning of R ^{1 in} the formula is as described above. ]
A resin containing a structural unit represented by

The diol component may contain only one kind of fluorene diol compound represented by the general formula (I) (for example, a compound in which R ¹ in the general formula (I) is a methyl group or an ethyl group). Two or more kinds (that is, a plurality of compounds in which R ¹ in general formula (I) are different from each other) may be included. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). Other diol components may be used alone or in combination of two or more.

Specific examples of other diol components include fluorene diol compounds other than the fluorene diol compound represented by the general formula (I) [for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-alkyl-substituted phenyl) fluorene and their alkylene oxides (eg, alkylene oxides having 2 to 6 carbon atoms) adducts, etc.]; alkylene glycols [for example, ethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, linear or branched alkylene glycol having 2 to 12 carbon atoms represented by decanediol, etc.]; (poly) oxyalkylene glycol [for example The Di-, tri- or tetra-alkylene glycols such as tylene glycol, triethylene glycol, dipropylene glycol, etc.]; alicyclic diols [eg, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2 , 2-bis (4-hydroxycyclohexyl) propane and its alkylene oxide adducts, etc.]; aromatic diols [for example, biphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bisphenol AD, bisphenol F And their alkylene oxides (eg, alkylene oxides having 2 to 6 carbon atoms) adducts, xylylene glycol, etc.].

The content ratio (molar ratio) of the fluorene-based diol compound represented by the general formula (I) to the other diol component in the diol component is, for example, [fluorene-based diol compound represented by the general formula (I)] / [others] Diol component] = 100/0 to 40/60, preferably 100/0 to 50/50, more preferably 100/0 to 60/40, still more preferably 100/0 to 70/30 (for example, 100 / 0 to 80/20 or 100/0 to 90/10).

If necessary, in addition to the diol component, a tri- or higher functional polyol component such as glycerin, trimethylolpropane, trimethylolethane, or pentaerythritol may be used in combination.

Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Carbonic acid diester can be used individually or in combination of 2 or more types.

Examples of polymerization catalysts include, for example, alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (zinc, aluminum, germanium, tin, lead, antimony, titanium) , Manganese, cobalt, lancerium, etc.]. Examples of the metal compound include hydroxides, alcoholates, organic acid salts (acetates, propionates, etc.), inorganic acid salts (borate, carbonates, etc.), oxides, and the like. A polymerization catalyst can be used individually or in combination of 2 or more types.

The molecular weight of the polycarbonate resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).

(Polyester resin)
The fluorene polymer of the present invention, which is a polyester resin, is a conventional reaction in which a diol component containing a fluorene diol compound represented by the above general formula (I) and a dicarboxylic acid component are reacted in the presence or absence of a polymerization catalyst. It can be obtained according to a method [for example, direct polymerization method (direct esterification method) or transesterification method]. The polyester resin of the present invention contains in its main chain an ester bond involving the OH group represented by the above general formula (I) (OH group bonded to the 2-position of the phenyl group bonded to the 9-position of the fluorene ring). Resin, specifically, the following general formula (I-2):

[The meaning of R ^{1 in} the formula is as described above. Q is a divalent residue excluding the carboxyl group of the dicarboxylic acid component (or a derivative group capable of forming an ester thereof). ]
A resin containing a structural unit represented by

As in the case of the polycarbonate resin, the diol component may contain only one kind of fluorene diol compound represented by the general formula (I), or may contain two or more kinds. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). Other diol components may be used alone or in combination of two or more. Specific examples of other diol components and the content ratio of the fluorene-based diol compound represented by the general formula (I) to the other diol components in the diol component can be the same as those described for the polycarbonate resin.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and derivatives capable of forming esters thereof (for example, acid anhydrides, acid chlorides, lower alkyl esters, etc.). A dicarboxylic acid component can be used individually or in combination of 2 or more types.

Specific examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, etc. Unsaturated aliphatic dicarboxylic acids [eg, maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.]; and their ester-forming derivatives.

Specific examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids [for example, cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, cycloheptane. Dicarboxylic acid etc.]; unsaturated alicyclic dicarboxylic acid [eg 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid etc.]; polycyclic alkane dicarboxylic acid [eg bornane dicarboxylic acid, norbornane dicarboxylic acid , Adamantane dicarboxylic acid, etc.]; polycyclic alkene dicarboxylic acids [for example, bornene dicarboxylic acid, norbornene dicarboxylic acid, etc.]; and their ester-forming derivatives.

Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), 4,4′-diphenyldicarboxylic acid, diphenylether-4,4′-dicarboxylic acid. 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, and their ester-forming derivatives.

If necessary, a tri- or higher functional carboxylic acid component such as trimellitic acid or pyromellitic acid may be used in combination with the dicarboxylic acid component.

As the polymerization catalyst, the same ones as described for the polycarbonate resin can be used.

The molecular weight of the polyester resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).

(Polyester carbonate resin)
The fluorene polymer of the present invention which is a polyester carbonate resin comprises a diol component containing a fluorene diol compound represented by the above general formula (I), a carbonic acid diester or phosgene, and a dicarboxylic acid component in the presence of a polymerization catalyst or It can be obtained according to a conventional method of reacting in the absence. The polyester carbonate resin of the present invention comprises a carbonate bond involving the OH group (OH group bonded to the 2-position of the phenyl group bonded to the 9-position of the fluorene ring) represented by the general formula (I), and the OH A resin containing an ester bond involving a group in the main chain, specifically, a resin containing the structural units represented by the general formula (I-1) and the general formula (I-2) in the main chain. .

As in the case of the polycarbonate resin, the diol component may contain only one kind of fluorene diol compound represented by the general formula (I), or may contain two or more kinds. Moreover, the diol component can contain other diol components other than the fluorene-type diol compound represented by general formula (I). The other diol component, carbonic acid diester and dicarboxylic acid component can be used alone or in combination of two or more. Specific examples of other diol components, carbonic acid diesters and dicarboxylic acid components, and the content ratio of the fluorene-based diol compound represented by the general formula (I) in the diol component to other diol components are described for polycarbonate resins and polyester resins. Can be similar to

The molecular weight of the polyester carbonate resin is not particularly limited, and is, for example, about 5,000 to 500,000, preferably about 10,000 to 100,000 in terms of weight average molecular weight (polystyrene conversion).

(Polyurethane resin)
The fluorene polymer of the present invention, which is a polyurethane resin, is a conventional method in which a diol component containing a fluorene diol compound represented by the above general formula (I) and a diisocyanate component are urethanated in the presence or absence of a polymerization catalyst. Can be obtained according to the method.

Specific examples of the diisocyanate component include aromatic diisocyanates [for example, paraphenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis (isocyanato Phenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis (isocyanatophenyl) propane, 1,4-bis (isocyanatophenyl) butane, polymeric MDI, etc.]; Alicyclic diisocyanates [eg, cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI, etc.]; Aliphatic diisocyanates Preparative [for example, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), etc.] containing. A diisocyanate component can be used individually or in combination of 2 or more types. If necessary, a tri- or higher functional polyisocyanate component may be used in combination with the diisocyanate component.

The amount of the diisocyanate component used in the urethanization reaction is usually about 0.7 to 2.5 mol, preferably about 0.8 to 2.2 mol, relative to 1 mol of the diol component. As a polymerization catalyst, well-known urethanation catalysts, such as an amine type, a tin type, and a lead type, can be used, for example.

The fluorene polymer (resin) of the present invention may be used alone as a material for a resin member such as an optical member [for example, an optical lens, an optical film], or combined with other components to form a resin composition. This may be used as a material for the resin member. The resin composition can contain a resin other than the fluorene polymer of the present invention, and can contain an appropriate additive as required. Specific examples of additives include plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, fillers, flame retardants, colorants, dispersants, flow agents Contains modifiers, leveling agents, antifoaming agents, etc. An additive can be used individually or in combination of 2 or more types.

The fluorene polymer (resin) of the present invention or a resin composition containing the same is, for example, an injection molding method, an injection compression molding method, an extrusion molding method, a transfer molding method, a blow molding method, a pressure molding method, a casting molding method, etc. It can shape | mold to resin members, such as an optical member, by the well-known shaping | molding method.

<Fluorene-based diol compound and method for producing the same>
The fluorene-based diol compound according to the present invention represented by the above general formula (I) (hereinafter also simply referred to as “fluorene-based diol compound”) is a compound suitably used as a raw material monomer for forming the above-mentioned fluorene polymer. It is. In the general formula (I), R ¹ is an alkyl group, a cycloalkyl group or an aryl group. Specific examples of the alkyl group, cycloalkyl group and aryl group are as described above.

Specific examples of the fluorene-based diol compound suitably used as a raw material monomer for forming a fluorene-based polymer include, for example, R ¹ is a methyl group, ethyl group, n-propyl group, isopropyl group, cyclopentyl group, cyclohexyl group, phenyl More preferred examples include compounds in which R ¹ is a methyl group, an ethyl group, an n-propyl group, or a phenyl group.

Since the fluorene-based diol compound itself has a high refractive index, a fluorene-based polymer formed using the fluorene-based diol compound exhibits a high refractive index as described above. The refractive index (23 ° C.) of the fluorene diol compound is about 1.65 when R ¹ is, for example, a methyl group or an ethyl group. This refractive index value is approximately 1 for 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, which is a raw material monomer of a fluorene polymer that is conventionally known to exhibit a high refractive index. Still higher than .62.

Further, the fluorene-based diol compound itself has a low Abbe number, about 18 when R ¹ is a methyl group, and about 20 when R ¹ is an ethyl group (23 ° C.). These Abbe numbers are based on the Abbe number of about 22, which is 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, which is a raw material monomer of a fluorene polymer that is conventionally known to exhibit a low Abbe number. Is still low.

The method for producing the fluorene-based diol compound is not particularly limited, but preferably, a method in which 9-fluorenone and a m-alkylphenol represented by the above general formula (II) are subjected to a condensation reaction under acidic conditions is used. The meaning of R ¹ in general formula (II) is the same as in general formula (I). Among them, the method of performing the above condensation reaction in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound can form a desired fluorene-based diol compound with high reaction selectivity, and the high-purity Since a fluorene diol compound can be obtained in a high yield, it can be preferably employed.

In the above condensation reaction, m-alkylphenol is usually used in an excess amount relative to 9-fluorenone. The ratio of the amount of m-alkylphenol used relative to the amount of 9-fluorenone used is usually 2.0 to 40 times (eg, 2.1 to 40 times), preferably 3 to 30 times, more preferably, molar ratio. 4 to 20 times. The condensation reaction can be carried out in the presence or absence of a solvent, and an excess amount of m-alkylphenol is also preferably used as the solvent.

As the organic acid, paratoluenesulfonic acid, methanesulfonic acid, or the like can be used. As the inorganic acid, hydrohalic acid such as hydrochloric acid (hydrogen chloride aqueous solution), phosphoric acid, or the like can be used. The hydrogen chloride concentration of hydrochloric acid is preferably 10 to 37% by weight, more preferably 20 to 37% by weight, and still more preferably 25 to 37% by weight. Among them, it is preferable to use paratoluenesulfonic acid, hydrochloric acid (especially high-concentration hydrochloric acid) or the like because high reaction selectivity and thus high yield can be obtained. The acidic compound (organic acid and / or inorganic acid) can be used alone or in combination of two or more.

If sulfuric acid (concentrated sulfuric acid) is used as the inorganic acid, the following general formula (III):

It has been clarified by the present inventors that a xanthene compound represented by the formula (1) is produced as a main reaction product, and the use of sulfuric acid (concentrated sulfuric acid) is relatively disadvantageous in this respect. By using paratoluenesulfonic acid, hydrochloric acid (especially high-concentration hydrochloric acid), etc., it is possible to effectively suppress the formation of the xanthene compound and obtain the desired fluorene diol compound with high reaction selectivity. is there.

The ratio of the amount of acidic compound (organic acid or inorganic acid) used relative to the amount of 9-fluorenone used (in the case of a solution such as hydrochloric acid, the amount of acidic compound contained in the solution) is usually 0.05. -3 times, preferably 0.1-2 times, more preferably 0.2-1.5 times.

Examples of the thiol compound include alkyl mercaptans [eg, alkyl mercaptans having 1 to 20 carbon atoms such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, n-lauryl mercaptan]; aralkyl mercaptans [eg, benzyl mercaptan Etc.]; mercaptocarboxylic acids (eg, thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.); and salts thereof (eg, Na Salt, K salt, etc.] can be used. A thiol compound can be used individually or in combination of 2 or more types.

The ratio of the amount of the thiol compound used relative to the amount of 9-fluorenone used is usually 0.01 to 0.5 times, preferably 0.02 to 0.3 times, more preferably 0.03 to 0.3 in terms of molar ratio. 0.2 times.

If the condensation reaction is carried out in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound, for example, the starting materials 9-fluorenone and m-alkylphenol, acidic compound, thiol compound, Moreover, it can carry out by charging the solvent used as needed to reaction container, and stirring in air or inert gas atmosphere, such as nitrogen and helium. Liquid containing an acidic compound (for example, liquid acid itself (hydrochloric acid hydrochloric acid itself), solid acid dissolved in a solvent), or liquid containing an acidic compound and a thiol compound It is also effective to add the solution to a reaction vessel charged with another reagent while stirring.

The reaction temperature is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher from the viewpoint of the reaction rate. On the other hand, when the reaction temperature is excessively high, the by-product of the xanthene compound becomes prominent. Therefore, the reaction temperature is preferably 60 ° C or lower, more preferably 50 ° C or lower, and 40 ° C or lower. More preferably, it is particularly preferably 35 ° C. or lower. The progress of the reaction can be monitored by high performance liquid chromatography (HPLC) or the like.

After completion of the reaction, an appropriate post-treatment operation can be performed to isolate the fluorene diol compound as crystals. Examples of the post-treatment operations include extraction of a fluorene-based diol compound into an organic layer (organic solvent), neutralization of an acidic compound with an alkali, washing of the organic layer, concentration of the organic layer, crystallization, filtration, and drying. One or more of these operations may be omitted, or other operations may be added. Moreover, you may refine | purify the isolated crystal | crystallization as needed. Examples of the purification method include recrystallization (recrystallization) and impurity removal treatment using an adsorbent such as activated carbon. You may use for the manufacturing process of the above-mentioned fluorene type polymer, without isolating the fluorene type diol compound produced | generated by the condensation reaction as a crystal | crystallization.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Measured values measured for the fluorene diol compound and the fluorene polymer were in accordance with the following methods and measurement conditions.

[1] HPLC purity The area percentage value when HPLC measurement was performed under the following measurement conditions was defined as HPLC purity.

・ Equipment: “LC-2010AHT” manufactured by Shimadzu Corporation
・ Column: “L-column ODS” manufactured by the Chemical Substance Evaluation Research Organization
(5 μm, 4.6 mmφ × 250 mm),
Column temperature: 40 ° C
・ Detection wavelength: UV 254 nm,
-Mobile phase: A liquid = water, B liquid = acetonitrile,
-Mobile phase flow rate: 1.0 ml / min,
Mobile phase gradient: Liquid B concentration: 30% (0 minutes) → 100% (after 25 minutes) → 100% (after 35 minutes).

[2] Melting point and glass transition temperature Using a differential scanning calorimeter (“EXSTAR DSC 7020” manufactured by SII Nano Technology Co., Ltd.), the temperature was increased at a rate of 10 ° C./min.

[3] Refractive Index and Abbe Number Using an Abbe refractometer (“Multi-wavelength Abbe Refractometer DR-2M” manufactured by Atago Co., Ltd.), the refractive index at 23 ° C. (wavelength: 589 nm) and the Abbe number at 23 ° C. (wavelength : 486, 589, 656 nm). In addition, about the fluorene type diol compound, the refractive index and the Abbe number were measured as follows. First, fluorene diol compounds were dissolved in dimethyl sulfoxide to prepare 10 wt%, 20 wt% and 30 wt% solutions, and the refractive index and Abbe number of each solution were measured. Next, an approximate curve was derived from the obtained three measured values, and values obtained by extrapolating the approximate curve to 100% by weight were taken as the refractive index and Abbe number of the fluorene-based diol compound. Moreover, about the fluorene type polymer, it measured using the test piece cut out into the strip shape from what shape | molded this in the film form.

[4] Weight average molecular weight of fluorene polymer The weight average molecular weight was measured (polystyrene conversion) using a high-speed GPC apparatus ("HLC-8200 GPC" manufactured by Tosoh Corporation).

[5] Haze of fluorene polymer Haze was measured using a haze meter (“HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.).

(1) Production of fluorene-based diol compound <Example 1>
In a 300 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, 9-fluorenone 40.00 g (0.222 mol), m-ethylphenol 161.76 g (1.324 mol), n-lauryl mercaptan (1 -Dodecanethiol) 2.25 g (0.011 mol) and paratoluenesulfonic acid 21.11 g (0.111 mol) were charged, and the temperature was raised to 30 ° C. When the reaction mixture was analyzed by HPLC when the mixture was stirred at the same temperature for 12 hours, the residual amount of 9-fluorenone was 1.0% or less.

Toluene and water were added to the resulting reaction mixture, the temperature was raised to 85 ° C., 24 wt% sodium hydroxide was added for neutralization, and then the aqueous layer was separated and removed. Next, the organic layer was washed three times with water, and then the organic layer was concentrated under reduced pressure to partially distill off toluene and m-ethylphenol. Toluene was added to the resulting slurry, the temperature was raised to 110 ° C., and then allowed to cool to room temperature. The precipitated crystals are filtered and dried, and white crystals of the fluorene diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] in which R ¹ in the general formula (I) is an ethyl group are obtained. 67.59 g was obtained (yield based on 9-fluorenone: 74.9%). The HPLC purity of the white crystals was 98.7%.

Next, the whole amount of the white crystals and toluene were charged into a glass reaction vessel, heated to 110 ° C., and then gradually cooled to room temperature. The precipitated crystals were filtered and dried to obtain 47.5 g of a purified product (9-fluorenone standard yield: 52.5%). The HPLC purity of this purified product was 99.2%.

<Example 2>
In a 300 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, 40.00 g (0.222 mol) of 9-fluorenone, 161.76 g (1.324 mol) of m-ethylphenol and n-lauryl mercaptan ( 1.25 g (0.011 mol) of 1-dodecanethiol) was charged, and the temperature was raised to 30 ° C. Thereafter, 22.70 g (0.218 mol) of 35 wt% hydrochloric acid was added dropwise at 30 ° C. When the reaction mixture was analyzed by HPLC after stirring at the same temperature for 20 hours, the residual amount of 9-fluorenone was 1.0% or less.

Toluene and water were added to the obtained reaction mixture, the temperature was raised to 85 ° C., and 24 wt% sodium hydroxide was added for neutralization, and then the aqueous layer was separated and removed. Next, the organic layer was washed three times with water, and then the organic layer was concentrated under reduced pressure to partially distill off toluene and m-ethylphenol. Toluene was added to the resulting slurry, the temperature was raised to 110 ° C., and then allowed to cool to room temperature. The precipitated crystals were filtered and dried to obtain 61.8 g of white crystals of fluorene diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] (yield based on 9-fluorenone) : 68.5%). The HPLC purity of the white crystals was 97.1%.

<Example 3>
In a 300 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, 40.00 g (0.222 mol) of 9-fluorenone, 279.89 g (2.588 mol) of m-cresol, and n-lauryl mercaptan (1 -Dodecanethiol) 2.25 g (0.011 mol) was charged, and the temperature was raised to 30 ° C. Thereafter, 22.70 g (0.218 mol) of 35 wt% hydrochloric acid was added dropwise at 30 ° C. When the reaction mixture was analyzed by HPLC at the time of stirring for 8 hours at the same temperature, the residual amount of 9-fluorenone was 1.0% or less.

Toluene and water were added to the resulting reaction mixture, the temperature was raised to 85 ° C., 24 wt% sodium hydroxide was added for neutralization, and then the aqueous layer was separated and removed. Next, the organic layer was washed three times with water, and then the organic layer was concentrated under reduced pressure, whereby toluene and m-cresol were partially distilled off. Toluene was added to the resulting slurry, the temperature was raised to 110 ° C., and then allowed to cool to room temperature. The precipitated crystals are filtered and dried, and white crystals of the fluorene diol compound Ib [9,9-bis (2-hydroxy-4-methylphenyl) fluorene] in which R ¹ in the above general formula (I) is a methyl group 48.1 g was obtained (9-fluorenone based yield: 57.3%). The HPLC purity of the white crystals was 90.3%.

Next, the whole amount of the white crystals and toluene were charged into a glass reaction vessel, heated to 110 ° C., and then gradually cooled to room temperature. The precipitated crystals were filtered and dried to obtain 35.1 g of a purified product (9-fluorenone based yield: 41.8%). The HPLC purity of this purified product was 97.0%.

<Reference Example 1>
In a 300 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer, 9-fluorenone 40.00 g (0.222 mol), m-ethylphenol 161.76 g (1.324 mol), β-mercaptopropionic acid 1 .17 g (0.011 mol) and 98 wt% concentrated sulfuric acid 11.11 g (0.111 mol) were charged, and the temperature was raised to 55 ° C. When the reaction mixture was analyzed by HPLC at the time of stirring at the same temperature for 6 hours, as the most abundant product, xanthene compounds (R ¹ = ethyl group) represented by the above general formula (III) were produced. Confirmed (HPLC: 35%).

<Reference Example 2>
The reaction was performed in the same manner as in Reference Example 1 except that 143.18 g (1.324 mol) of m-cresol was used instead of m-ethylphenol. When the reaction mixture was analyzed by HPLC when the mixture was stirred at 55 ° C. for 6 hours, as the most abundant product, xanthene compounds (R ¹ = methyl group) represented by the above general formula (III) were produced. It was confirmed (HPLC: 67%).

A purified product of the fluorene diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] obtained in Example 1, and the fluorene diol compound Ib [9] obtained in Example 3 , 9-Bis (2-hydroxy-4-methylphenyl) fluorene] ¹ H-NMR data are as follows.

[A] Fluorene-based diol compound Ia
¹ H-NMR (CDCl ₃ , 400 MHz, TMS) δ (ppm): 1.17 (t, J = 7.56, 6H), 2.55 (q, J = 7.56, 4H), 5.26 (S, 2H), 6.60 (d, J = 7.79, 2H), 6.75 (s, 2H), 6.81 (d, J = 8.24, 2H), 7.28 (t , J = 7.56, 2H), 7.39 (t, J = 7.76, 2H) 7.76 (d, J = 8.24, 2H).

[B] Fluorene diol compound Ib
¹ H-NMR (CDCl ₃ , 400 MHz, TMS) δ (ppm): 2.24 (s, 6H), 5.24 (s, 2H), 6.57 (d, J = 7.79, 2H), 6.71 (s, 2H), 6.79 (d, J = 8.24, 2H), 7.27 (t, J = 7.56, 2H), 7.38 (t, J = 7.56) , 2H), 7.76 (d, J = 7.79, 4H).

Further, FIGS. 1 and 2 show HH COSY and CH COSY spectra of the fluorene diol compound Ia, respectively. FIGS. 3 and 4 show HH COSY and CH COSY spectra of the fluorene diol compound Ib, respectively. Shown in From these two-dimensional NMR spectra, the fluorene-based diol compounds Ia and Ib have a structure as shown in the general formula (I), in particular, the OH group is bonded to the 2-position of the phenyl group. , R ¹ was confirmed to be bonded to the 4-position.

The melting point, refractive index, and Abbe number of the purified product of fluorene diol compound Ia obtained in Example 1 and the purified product of fluorene diol compound Ib obtained in Example 3 were measured. The results are shown in Table 1. In Table 1, for comparison, the following general formula (IV), which is a conventionally known fluorene diol compound:

The measurement results of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene represented by the formula are also shown.

(2) Production of fluorene polymer <Example 4: Production of polycarbonate resin>
17.27 parts by weight of fluorene-based diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene], 9.42 parts by weight of diphenyl carbonate and 2.1 × 10 ⁻ sodium bicarbonate as a polymerization catalyst ⁵ parts by weight was charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 200 ° C. in a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Then, the pressure reduction degree in reaction container was adjusted to 27 kPa, and it stirred for 40 minutes on 200 degreeC and 27 kPa conditions. Next, the temperature was raised to 210 ° C. at a rate of 60 ° C./hr, and the mixture was stirred at the same temperature for 30 minutes. Then, it heated up to 220 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 40 minutes at the same temperature. Subsequently, after adjusting the pressure reduction degree in reaction container to 24 kPa, it heated up to 230 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 20 minutes at the same temperature. Next, after adjusting the pressure reduction degree in reaction container to 20 kPa, it heated up to 240 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 40 minutes at the same temperature. Finally, the pressure reduction degree in reaction container was made into 133 Pa or less over 1 hour, and it stirred on 240 degreeC and 133 Pa or less conditions for 1 hour, and was complete | finished. Thereafter, the polycarbonate resin A1 produced while nitrogen was blown into the reaction vessel was taken out.

<Example 5: Production of polycarbonate resin>
Fluorene diol compound Ib [9,9-bis (2-hydroxy-4-methylphenyl) fluorene] 20.49 parts by weight of diphenyl carbonate 12.01 parts by weight of sodium hydrogen carbonate as a polymerization catalyst 2.7 × 10 ^{- 5} parts by weight was charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 200 ° C. in a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Then, the pressure reduction degree in reaction container was adjusted to 27 kPa, and it stirred for 40 minutes on 200 degreeC and 27 kPa conditions. Next, the temperature was raised to 210 ° C. at a rate of 60 ° C./hr, and the mixture was stirred at the same temperature for 30 minutes. Then, it heated up to 220 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 40 minutes at the same temperature. Subsequently, after adjusting the pressure reduction degree in reaction container to 24 kPa, it heated up to 230 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 10 minutes at the same temperature. Next, after adjusting the pressure reduction degree in reaction container to 20 kPa, it heated up to 240 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 30 minutes at the same temperature. Finally, the pressure reduction degree in reaction container was made into 133 Pa or less over 1 hour, and it stirred on 240 degreeC and 133 Pa or less conditions for 1 hour, and was complete | finished. Thereafter, the polycarbonate resin A2 produced while nitrogen was blown into the reaction vessel was taken out.

<Example 6: Production of polyester resin>
20.00 parts by weight of fluorene diol compound Ib [9,9-bis (2-hydroxy-4-methylphenyl) fluorene], 15.07 parts by weight of dimethyl terephthalate, 1.54 parts by weight of ethylene glycol and a polymerization catalyst 2.65 × 10 ⁻⁵ parts by weight of titanium tetraisopropoxide was charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 220 ° C. in a nitrogen atmosphere, and stirred to melt. Thereafter, stirring was continued at 220 ° C. while distilling the produced methanol out of the reaction system. When methanol was almost not distilled off, 6.6 × 10 ⁻⁵ parts by weight of germanium oxide was added, and then the temperature was raised to 280 ° C. at a rate of 60 ° C./hr, followed by stirring at the same temperature for 10 minutes. Further, the degree of vacuum in the reaction vessel was gradually reduced to 133 Pa or less, and the reaction was completed by stirring for 3 hours while removing the distilled ethylene glycol from the reaction system. Thereafter, the polyester resin A3 produced while nitrogen was blown into the reaction vessel was taken out.

<Comparative Example 1: Production of polycarbonate resin>
A stirrer was charged with 20.00 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 10.10 parts by weight of diphenyl carbonate and 2.2 × 10 ⁻⁵ parts by weight of sodium bicarbonate as a polymerization catalyst. The mixture was charged into a reaction vessel equipped with a distillation apparatus, heated to 200 ° C. under a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Then, the pressure reduction degree in reaction container was adjusted to 27 kPa, and it stirred for 40 minutes on 200 degreeC and 27 kPa conditions. Next, the temperature was raised to 210 ° C. at a rate of 60 ° C./hr, and the mixture was stirred at the same temperature for 30 minutes. Then, it heated up to 220 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 40 minutes at the same temperature. Subsequently, after adjusting the pressure reduction degree in reaction container to 24 kPa, it heated up to 230 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 20 minutes at the same temperature. Next, after adjusting the pressure reduction degree in reaction container to 20 kPa, it heated up to 240 degreeC at the speed | rate of 60 degreeC / hr, and stirred for 40 minutes at the same temperature. Finally, the pressure reduction degree in reaction container was made into 133 Pa or less over 1 hour, and it stirred on 240 degreeC and 133 Pa or less conditions for 1 hour, and was complete | finished. Thereafter, the polycarbonate resin B1 produced while blowing nitrogen into the reaction vessel was taken out.

<Comparative Example 2: Production of polyester resin>
9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 20.00 parts by weight, dimethyl terephthalate 13.02 parts by weight, ethylene glycol 2.66 parts by weight, and titanium tetraisopropoxide 2 as a polymerization catalyst .29 × 10 ⁻⁵ parts by weight were charged into a reaction vessel equipped with a stirrer and a distillation apparatus, heated to 220 ° C. in a nitrogen atmosphere, and stirred to melt. Thereafter, stirring was continued at 220 ° C. while distilling the produced methanol out of the reaction system. When methanol was almost not distilled, 5.7 × 10 ⁻⁵ parts by weight of germanium oxide was added, and then the temperature was raised to 280 ° C. at a rate of 60 ° C./hr, followed by stirring at the same temperature for 10 minutes. Further, the degree of vacuum in the reaction vessel was gradually reduced to 133 Pa or less, and the reaction was completed by stirring for 3 hours while removing the distilled ethylene glycol from the reaction system. Thereafter, the produced polyester resin B2 was taken out while blowing nitrogen into the reaction vessel.

The glass transition temperature, refractive index, Abbe number, weight average molecular weight and haze of the polycarbonate resins and polyester resins obtained in Examples 4 to 6 and Comparative Examples 1 and 2 were measured. The results are shown in Table 2.

Claims

The following general formula (I):
[Wherein, R 1 represents an alkyl group, a cycloalkyl group or an aryl group. ]
A fluorene polymer containing a structural unit derived from a fluorene diol compound represented by the formula:
The fluorene-based polymer according to claim 1, comprising at least one of a carbonate bond and an ester bond in the main chain.
The fluorene polymer according to claim 1 or 2, wherein the refractive index at 23 ° C is 1.6 or more.
A fluorene-based diol compound represented by the general formula (I) according to claim 1,
A fluorene-based diol compound in which R 1 in the general formula (I) is an alkyl group, cycloalkyl group or aryl group having 2 or more carbon atoms.
A method for producing a fluorene-based diol compound represented by the general formula (I) according to claim 1,
Under acidic conditions, 9-fluorenone and the following general formula (II):

[Wherein, R 1 represents an alkyl group, a cycloalkyl group or an aryl group. ]
A process comprising the step of reacting with an m-alkylphenol represented by the formula:
The production method according to claim 5, wherein 9-fluorenone and the m-alkylphenol are reacted in the presence of paratoluenesulfonic acid and a thiol compound.