KR20150095771A - Fluorene polymer, fluorene diol compound, and method for producing said polymer and compound - Google Patents
Fluorene polymer, fluorene diol compound, and method for producing said polymer and compound Download PDFInfo
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- KR20150095771A KR20150095771A KR1020157018212A KR20157018212A KR20150095771A KR 20150095771 A KR20150095771 A KR 20150095771A KR 1020157018212 A KR1020157018212 A KR 1020157018212A KR 20157018212 A KR20157018212 A KR 20157018212A KR 20150095771 A KR20150095771 A KR 20150095771A
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- 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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
(I): < EMI ID =
A fluorene-based polymer containing a constituent unit derived from a fluorene-based diol compound represented by the formula: wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group, and the fluorene-based diol compound [wherein R 1 represents an alkyl group having 2 or more carbon atoms, a cycloalkyl group or an aryl group, and a fluorene-based diol compound wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group.
Description
The present invention relates to a fluorene-based polymer which can be preferably used as a resin (optical resin) constituting an optical member typified by an optical lens or an optical film. The present invention also relates to a fluorene-based diol compound preferable as a monomer for forming the fluorene-based polymer and a method for producing the same.
A polycarbonate resin, a cycloolefin resin, a polymethacrylic resin or the like has been conventionally used as an optical resin because of its relatively high refractive index, low refractive index, transparency and processability. In recent years, fluorene-based polymers having a so-called " cardo (hinge) structure " skeleton in which two phenyl groups are introduced at the 9-position of fluorene are particularly advantageous in achieving both high refractive index and low refractive index. Optical resins have attracted attention, and active research and development have been carried out.
For example, JP-A-06-025398 (Patent Document 1) discloses a polycarbonate resin having 9,9-bis (4-hydroxyphenyl) fluorene as a part of a diol component. Japanese Patent Application Laid-Open No. 06-049186 (Patent Document 2) discloses a polyester polymer for optical materials 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. .
An object of the present invention is to provide a novel fluorene-based polymer exhibiting a high refractive index and being useful as an optical resin. Another object of the present invention is to provide a fluorene-based diol compound useful as a monomer for forming the fluorene-based polymer and a process for producing the same.
The present invention includes the following.
[1] A compound represented by the following general formula (I):
[Chemical Formula 1]
[Wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group]
A fluorene-based polymer containing a constituent unit derived from a fluorene-based diol compound as a main chain.
[2] The fluorene-based polymer according to [1], wherein at least one of a carbonate bond and an ester bond is contained in the main chain.
[3] The fluorene-based polymer according to [1] or [2], wherein the refractive index at 23 ° C is 1.6 or more.
[4] The fluorene-based diol compound represented by the general formula (I) described in [1]
The fluorene-based diol compound in which R 1 in the general formula (I) is an alkyl group, a cycloalkyl group or an aryl group having 2 or more carbon atoms.
[5] A process for producing a fluorene-based diol compound represented by the general formula (I) described in [1]
Under acidic conditions, 9-fluorenone and the following general formula (II):
(2)
[Wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group]
Alkylphenol represented by the following general formula (1).
[6] The process according to [5], wherein 9-fluorenone and the m-alkylphenol are reacted in the presence of paratoluenesulfonic acid and a thiol compound.
The fluorene polymer according to the present invention comprising the constituent unit derived from the fluorene-based diol compound represented by the above general formula (I) has high refractive index and low refractive index, and is excellent in transparency and heat resistance, An optical lens, an optical film, a plastic optical fiber, and an optical disk substrate. In addition, it can be used as a non-optical resin such as a heat resistant resin or an engineering plastic by taking advantage of its high heat resistance, transparency and durability.
Further, according to the present invention, it is possible to provide a fluorene-based diol compound represented by the above general formula (I) which 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 fluorene-based diol compound of high purity can be obtained in good yield.
1 is a two-dimensional NMR (HH COZY) spectrum of a fluorene-based diol compound Ia.
2 is a two-dimensional NMR (CH COZY) spectrum of the fluorene-based diol compound Ia.
3 is a two-dimensional NMR (HH COZY) spectrum of the fluorene-based diol compound Ib.
4 is a two-dimensional NMR (CH COZY) spectrum of the fluorene-based diol compound Ib.
<Fluorene Polymer>
The fluorene-based polymer (hereinafter, simply referred to as "fluorene-based polymer") of the present invention is a polymer containing a constituent unit derived from the fluorene-based diol compound represented by the above 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 linear or branched alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, Or branched alkyl groups. 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 still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms Or branched alkyl group.
Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, an alkyl of 1 to 4 carbon atoms) substituted cyclopentyl group, an alkyl (for example, an alkyl of 1 to 4 carbon atoms) And a cycloalkyl group or an alkyl-substituted cycloalkyl group having 4 to 16 carbon atoms (preferably 5 to 8 carbon atoms) such as an acyl 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, an 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 (e.g., an alkoxyl group, an acyl group, a halogen atom, etc.).
The fluorene-based polymer may be a thermoplastic resin such as a polycarbonate resin, a polyester resin, a polyester carbonate resin, a (meth) acrylic resin or a polyurethane resin, or may be thermoplastic resin such as epoxy resin, (meth) acrylic resin or polyurethane resin A resin or a photo-curable resin may be used, but 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 the above-mentioned modified resins of various resins. Examples of the modified substance include those obtained by introducing a functional group or a molecular chain at the terminal of the polymer and those obtained by introducing a functional group or a molecular chain as a side chain of the polymer.
The fluorene polymer exhibits a very high refractive index while exhibiting a low birefringence due to the constitutional unit derived from the fluorene-based diol compound represented by the general formula (I). The refractive index (23 캜) of the polymer is determined by the chemical structure of the polymer and the constituent unit constituting the polymer, the presence / absence of the constituent unit derived from the diol component other than the fluorene diol compound, and / or the chemical structure Type of diol component), and the like, but is typically 1.6 or more. The fluorene-based polymer may exhibit a refractive index of 1.62 or more, more preferably 1.64 or more, further preferably 1.65 or more.
The refractive index (20 DEG C) of a general polycarbonate resin (diol component, for example, bisphenol A and the like is used as the optical resin), a cycloolefin resin and a polymethacrylic resin are about 1.59, about 1.53, 1.49. Therefore, the fluorene-based polymer of the present invention is very excellent in refractive index as compared with these general conventional general-purpose optical resins.
Is a fluorene-based polymer, but is a polyester resin containing 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component, and a conventionally known fluorene- Examples of the polymer include trade name "OKP4" and "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. The refractive index (20 DEG C) of these polyester resins is about 1.60 to about 1.63. Therefore, the fluorene-based polymer of the present invention comprising the constituent unit derived from the fluorene-based diol compound represented by the above general formula (I) can be said to be excellent in the refractive index in comparison with the above- have. Such improvement of the refractive index is presumably due to the difference in the positions of the OH groups (or hydroxyalkoxyl groups) on the two phenyl groups.
The fluorene-based polymer of the present invention has a "cardo (hinge) structure" having a constituent unit derived from a fluorene-based diol compound, such as a fluorene ring and 2 (For example, a structure comprising a phenyl group and a phenyl group). However, the birefringence is lower than that of a conventional fluorene polymer in which OH groups or hydroxyalkoxyl groups are bonded at four positions of two phenyl groups (for example, 9, A polymer containing 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 two positions of two phenyl groups, the phenyl group takes a more orthogonal three-dimensional symmetric structure than the fluorene skeleton as compared with the above-mentioned conventional fluorene polymer .
The fluorene-based polymer of the present invention is also a preferable material as an optical resin in that the Abbe number is low. The fluorene polymer may exhibit a low Abbe number of not more than 30, more preferably not more than 27, and even not more than 23 at 23 占 폚, and Abbe number of not more than 20 may be exhibited. The Abbe number (20 占 폚) of the trade name "OKP4" and "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. are 27 and 23, respectively.
The fluorene-based polymer of the present invention is also advantageous in terms of heat resistance compared with conventional optical resins. That is, the fluorene-based polymer of the present invention may be varied according to the above-described factors, and typically has a glass transition temperature of about 140 캜 or higher, a glass having a melting point higher than 160 캜, more than 170 캜, It can also have a transition temperature. On the contrary, the general polycarbonate resins, cycloolefin resins and polymethacrylic resins generally used as optical resins have glass transition temperatures of about 145 ° C, about 140 ° C and about 110 ° C, respectively, and 9,9-bis [4- OKP4 " and " OKP4HT " manufactured by Osaka Gas Chemical Co., Ltd.) and a polycarbonate resin having a glass transition temperature of (The case where the diol component consists of only 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene) is about 120 to 140 ° C and about 150 ° C, respectively.
The fluorene-based polymer of the present invention also has sufficient transparency, processability (moldability, etc.) and durability required for optical resins.
Hereinafter, a representative fluorene polymer (resin) will be described in more detail.
(Polycarbonate resin)
The fluorene polymer of the present invention which is a polycarbonate resin is obtained by reacting a diol component containing a fluorene diol compound represented by the above general formula (I) with a carbonic acid diester or phosgene in the presence or in the absence of a polymerization catalyst It can be obtained according to the method of tolerance. The polycarbonate resin of the present invention is a polycarbonate resin comprising a main chain containing a carbonate bond which is involved in the OH group (OH group bonded at two positions of the phenyl group bonded to the 9 position of the fluorene ring) represented by the above general formula (I) As the resin, specifically, a resin represented by the following general formula (I-1):
(3)
[Wherein the meaning of R < 1 > is as described above]
Is contained in the main chain.
The diol component may contain only one fluorene-based 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) (I.e., a plurality of compounds in which R < 1 > in the general formula (I) are different from each other). In addition, the diol component may contain a diol component other than the fluorene-based diol compound represented by the 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-based diol compounds other than the fluorene-based diol compounds represented by the general formula (I) [e.g., 9,9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-alkyl substituted phenyl) fluorenes, and alkylene oxides thereof (e.g., alkylene oxides having 2 to 6 carbon atoms) adducts; Alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol, hexanediol, neopentyl glycol, octanediol, decanediol, Branched or branched alkylene glycol, etc.]; (Poly) oxyalkylene glycols [for example, di-, tri- or tetra-alkylene glycols represented by diethylene glycol, triethylene glycol, dipropylene glycol, etc.]; Cycloaliphatic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, and alkylene oxide adducts thereof; Bisphenol A, bisphenol F, and alkylene oxides thereof (e.g., alkylene oxides having 2 to 6 carbon atoms), and aromatic diols such as biphenol, 2,2-bis (4-hydroxyphenyl) Adduct, 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 may be, for example, [the fluorene-based diol compound represented by the general formula (I)] / Diol component] = 100/0 to 40/60, preferably 100/0 to 50/50, more preferably 100/0 to 60/40, and further preferably 100/0 to 70/30 For example, 100/0 to 80/20 or 100/0 to 90/10).
If necessary, polyol components having three or more functional groups such as glycerin, trimethylolpropane, trimethylol ethane, and pentaerythritol may be used in combination in addition to the diol component.
As the carbonic acid diester, for example, diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be used. The carbonic acid diester can be used singly or in combination of two or more kinds.
Examples of the polymerization catalyst include alkali metals [lithium, sodium, potassium, etc.], alkaline earth metals [magnesium, calcium, barium and the like], transition metals [zinc, aluminum, germanium, tin, lead, antimony, , Cobalt, lanthanum, cerium and the like]. Examples of the metal compound include hydroxides, alcoholates, organic acid salts (such as acetic acid salts and propionic acid salts), inorganic acid salts (such as borates and carbonates), and oxides. The polymerization catalysts may be used alone or in combination of two or more.
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 weight average molecular weight (in terms of polystyrene).
(Polyester resin)
The fluorene-based polymer of the present invention which is a polyester resin is obtained by reacting a diol component containing a fluorene-based diol compound represented by the above general formula (I) with a dicarboxylic acid component in the presence or absence of a polymerization catalyst (For example, a direct polymerization method (direct esterification method) or an ester exchange method]. The polyester resin of the present invention is a polyester resin comprising an ester linkage in which an OH group (OH group bonded at two positions of a phenyl group bonded to the 9-position of the fluorene ring) shown in the general formula (I) As the resin, specifically, a resin represented by the following general formula (I-2):
[Chemical Formula 4]
[Wherein R 1 has the same meaning as described above]. And Q is a divalent residue other than the carboxyl group of the dicarboxylic acid component (or ester-forming inducible group thereof).
As in the case of the polycarbonate resin, the diol component may contain only one kind of the fluorene-based diol compound represented by the general formula (I), or may contain two or more kinds. In addition, the diol component may contain a diol component other than the fluorene-based diol compound represented by the general formula (I). Other diol components may be used alone or in combination of two or more. Specific examples of the other diol component and the content ratio of the diene component and the fluorene diol compound represented by the general formula (I) in the diol component may be the same as those described for the polycarbonate resin.
If necessary, polyol components having three or more functional groups such as glycerin, trimethylolpropane, trimethylol ethane, and pentaerythritol may be used in combination in addition to the diol component.
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids and derivatives capable of forming an ester thereof (for example, acid anhydrides, acid chlorides, lower alkyl esters, etc.) have. The dicarboxylic acid component may be used alone or in combination of two or more.
Specific examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acids [e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandicarboxylic acid , Dodecanedicarboxylic acid, hexadecanedicarboxylic acid, etc.]; Unsaturated aliphatic dicarboxylic acids [e.g., maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.]; And their esterifiable derivatives.
Specific examples of the alicyclic dicarboxylic acid include saturated alicyclic dicarboxylic acids [e.g., cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Acid, 1,2-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, etc.]; Unsaturated alicyclic dicarboxylic acids [for example, 1,2-cyclohexene dicarboxylic acid, 1,3-cyclohexene dicarboxylic acid and the like]; Polycyclic alkanedicarboxylic acids [for example, boranadicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid and the like]; Polycyclic alkydicarboxylic acids [for example, bornendecarboxylic acid, norbornenedicarboxylic acid and the like]; And their esterifiable derivatives.
Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid (such as 2,6-naphthalenedicarboxylic acid), 4,4'-diphenyldicarboxylic acid, 4,4'-dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, and ester-forming derivatives thereof.
If necessary, in addition to the dicarboxylic acid component, a carboxylic acid component having three or more functional groups such as trimellitic acid and pyromellitic acid may be used in combination.
As the polymerization catalyst, those same as those 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 weight average molecular weight (in terms of polystyrene).
(Polyester carbonate resin)
The fluorene-based polymer of the present invention, which is a polyester carbonate resin, is obtained by reacting a diol component containing a fluorene-based diol compound represented by the above general formula (I), a carbonate diester or phosgene with a dicarboxylic acid component, In the presence or in the absence of a solvent. The polyester carbonate resin of the present invention is characterized in that the carbonate group in which the OH group (OH group bonded at two positions of the phenyl group bonded to the 9-position of the fluorene ring) involved in the above-mentioned general formula (I) Specifically, the resin contains a structural unit represented by the above 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 the fluorene-based diol compound represented by the general formula (I), or may contain two or more kinds. The diol component may contain a diol component other than the fluorene-based diol compound represented by the general formula (I). The other diol component, the carbonic acid diester and the dicarboxylic acid component may be used either individually or in combination of two or more. Specific examples of the other diol component, the carbonic acid diester and the dicarboxylic acid component, and the content ratio of the fluorene-based diol compound represented by the general formula (I) and the other diol component in the diol component may be polycarbonate resin or polyester May be the same as described with respect to the resin.
If necessary, polyol components having three or more functional groups such as glycerin, trimethylolpropane, trimethylol ethane, and pentaerythritol may be used in combination in addition to the diol component.
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 weight average molecular weight (in terms of polystyrene).
(Polyurethane resin)
The fluorene-based polymer of the present invention which is a polyurethane resin is obtained by reacting a diol component containing a fluorene-based diol compound represented by the above general formula (I) with a diisocyanate component in the presence or absence of a polymerization catalyst ≪ / RTI >
As in the case of the polycarbonate resin, the diol component may contain only one kind of the fluorene-based diol compound represented by the general formula (I), or may contain two or more kinds. The diol component may contain a diol component other than the fluorene-based diol compound represented by the general formula (I). Other diol components may be used alone or in combination of two or more. Specific examples of the other diol component and the content ratio of the diene component and the fluorene diol compound represented by the general formula (I) in the diol component may be the same as those described for the polycarbonate resin.
If necessary, polyol components having three or more functional groups such as glycerin, trimethylolpropane, trimethylol ethane, and pentaerythritol may be used in combination in addition to the diol component.
Specific examples of the diisocyanate component include aromatic diisocyanates such as p-phenylenediisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), naphthalene diisocyanate (Isocyanatophenyl) methane (MDI), toluidine diisocyanate (TODI), 1,2-bis (isocyanatophenyl) ethane, 1,3-bis 4-bis (isocyanatophenyl) butane, polymeric MDI, etc.]; Alicyclic diisocyanates [for example, cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated MDI and the like]; Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI) and the like]. The diisocyanate components may be used alone or in combination of two or more. If necessary, a trifunctional or higher polyisocyanate component may be used together with a diisocyanate component.
The amount of the diisocyanate component used in the urethanization reaction is usually about 0.7 to 2.5 moles, preferably about 0.8 to 2.2 moles, per 1 mole of the diol component. As the polymerization catalyst, for example, a known urethanation catalyst such as an amine-based, tin-based or lead-based catalyst may be used.
The fluorene-based 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 or an optical film), or may be used as a resin composition in combination with other components. It may be used as a material for a resin member. The resin composition may contain a resin other than the fluorene-based polymer of the present invention, and may contain appropriate additives as required. Specific examples of the additives include plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, fillers, flame retardants, colorants, dispersants, flow regulators, leveling agents, defoamers and the like. The additives may be used alone or in combination of two or more.
The fluorene-based polymer (resin) of the present invention or the resin composition containing the same can be produced by a known molding method such as 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, It can be molded with a resin member such as an optical member.
≪ Fluorene-based diol compound and its production method >
The fluorene-based diol compound (hereinafter simply referred to as "fluorene-based diol compound") according to the present invention represented by the above-mentioned general formula (I) is a compound that is preferably used as the raw material monomer for fluorene- to be. 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 preferably used as the raw material monomer for fluorene-based polymer formation include, for example, a compound in which R 1 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopentyl group, , A phenyl group, and the like. More preferred examples thereof include compounds wherein R 1 is a methyl group, an ethyl group, an n-propyl group, or a phenyl group.
Since the fluorene-based diol compound has a high refractive index in itself, the fluorene-based polymer formed using the fluorene-based polymer exhibits a high refractive index as described above. The refractive index (23 캜) 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 shows a high refractive index, which is higher than the refractive index value 1.62 of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene which is a conventionally known raw material monomer of a fluorene polymer.
Further, the fluorene-based diol compound has a low Abbe number of itself and is about 18 when R 1 is a methyl group and about 20 when it is an ethyl group (23 ° C.). These Abbe numbers represent low Abbe numbers and are lower than the Abbe number of about 22 of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene which is a raw material monomer of a conventionally known fluorene-based polymer.
The method of producing the fluorene-based diol compound is not particularly limited, but a method of condensation reaction of 9-fluorenone and m-alkylphenol represented by the above formula (II) is preferably used under acidic conditions. The meaning of R 1 in the general formula (II) is the same as in the general formula (I). Among them, the method of carrying out the 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, Diol compounds can be preferably employed because they can be obtained at a high yield.
In the condensation reaction, m-alkylphenol is usually used in an excess amount relative to 9-fluorenone. The ratio of the amount of m-alkylphenol to the amount of 9-fluorenone to be used is usually 2.0 to 40 times (for example, 2.1 to 40 times), preferably 3 to 30 times, more preferably 4 to 30 times, 20 times. The condensation reaction can be carried out in the presence or absence of a solvent, and it is also preferable to use an excessive amount of m-alkylphenol as a solvent.
As the organic acid, para-toluenesulfonic acid, methanesulfonic acid and the like can be used. As the inorganic acid, a hydrohalic acid such as hydrochloric acid (aqueous solution of hydrogen chloride), phosphoric acid and the like can be used. The concentration of hydrogen chloride in 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, para-toluenesulfonic acid and hydrochloric acid (particularly, hydrochloric acid at a high concentration) are preferably used because high reaction selectivity and further high yield can be obtained. The acidic compound (organic acid and / or inorganic acid) may be used alone or in combination of two or more.
When sulfuric acid (concentrated sulfuric acid) is used as the inorganic acid, the following general formula (III):
[Chemical Formula 5]
Is produced as a main reaction product by the present inventors, and the use of sulfuric acid (concentrated sulfuric acid) is relatively disadvantageous in this respect. The use of para-toluenesulfonic acid, hydrochloric acid (particularly, hydrochloric acid at a high concentration) or the like makes it possible to effectively suppress the production of the zettenic compound and to obtain a desired fluorene-based diol compound with high reaction selectivity.
The ratio of the amount of the acidic compound (organic acid or inorganic acid) to the amount of 9-fluorenone used (the amount of the acidic compound contained in the solution in the case of a solution such as hydrochloric acid) is usually 0.05 to 3 times, Is 0.1 to 2 times, and more preferably 0.2 to 1.5 times.
Examples of the thiol compound include alkylmercaptans such as methylmercaptan, ethylmercaptan, propylmercaptan, isopropylmercaptan, n-butylmercaptan, n-laurylmercaptan and the like having 1 to 20 carbon atoms Mercaptane]; Aralkyl mercaptans [e.g., benzyl mercaptan, etc.]; Mercaptocarboxylic acids [for example, thioacetic acid,? -Mercaptopropionic acid,? -Mercaptopropionic acid, thioglycolic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.]; And their salts [for example, Na salt, K salt, etc.] can be used. The thiol compounds may be used alone or in combination of two or more.
The ratio of the amount of the thiol compound to the amount of 9-fluorenone to be used is usually 0.01 to 0.5 times, preferably 0.02 to 0.3 times, more preferably 0.03 to 0.2 times as much as the molar ratio.
The above-mentioned condensation reaction can be carried out, for example, in the case where the reaction is carried out in the presence of an acidic compound (organic acid and / or inorganic acid) and a thiol compound, 9-fluorenone and m-alkylphenol as raw materials, A solvent to be used may be injected into a reaction vessel as required and stirred in air or in an atmosphere of an inert gas such as nitrogen or helium. A solution containing an acidic compound [for example, a liquid acid itself (a hydrochloric acid hydrochloric acid itself) or a solution of a solid acid dissolved in a solvent], or a solution containing an acidic compound and a thiol compound, A method of dropping into a reaction vessel under stirring is also effective.
The reaction temperature is preferably 5 占 폚 or higher, more preferably 10 占 폚 or higher, and even more preferably 15 占 폚 or higher from the viewpoint of the reaction rate. On the other hand, when the reaction temperature is excessively high, the reaction temperature is preferably 60 ° C or lower, more preferably 50 ° C or lower, still more preferably 40 ° C or lower, Or less. The progress of the reaction can be traced by high performance liquid chromatography (HPLC) or the like.
After completion of the reaction, the fluorene-based diol compound can be isolated as crystals by an appropriate post-treatment. Examples of the post-treatment operation include extraction of a fluorene-based diol compound in an organic layer (organic solvent), neutralization of an acidic compound with an alkali, washing of an organic layer, concentration of an organic layer, crystallization, filtration and drying One or more of these operations may be omitted or other operations may be added. If necessary, the isolated crystals may be purified. Examples of the purification method include an impurity removal treatment using an adsorbent such as a refractory (recrystallization) or activated carbon. The fluorene-based diol compound produced by the condensation reaction may be provided in the process for producing the fluorene-based polymer described above without being isolated as crystals.
Example
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
The measured values of the fluorene-based diol compound and the fluorene-based polymer were measured according to the following method and measurement conditions.
[1] HPLC purity
The percentage of area when the HPLC measurement was carried out under the following measurement conditions was determined as HPLC purity.
· Device: "LC-2010AHT" manufactured by Shimadzu Corporation,
Column: "L-columnODS" (5 μm, 4.6 mmφ × 250 mm) manufactured by Chemical Evaluation Research Institute,
Column temperature: 40 DEG C,
Detection wavelength: UV 254 nm,
· Mobile phase: liquid A = water, liquid B = acetonitrile,
Flow rate of mobile phase: 1.0 ml / min,
· Mobile phase gradient: B liquid concentration: 30% (0 minutes) → 100% (after 25 minutes) → 100% (after 35 minutes).
[2] Melting point and glass transition temperature
And the temperature was measured at a heating rate of 10 ° C / min using a differential scanning calorimeter ("EXSTARDSC 7020" manufactured by SII Nanotechnology Co., Ltd.).
[3] Refractive index and Abbe number
(Wavelength: 589 nm) at 23 占 폚 and Abbe number at 23 占 폚 (wavelength: 486, 589, and 656 nm) at 23 占 폚 using an Abbe refractometer ("Multi-wavelength Abbe refractometer DR- Nm) was measured. The refractive index and the Abbe number of the fluorene-based diol compound were measured as follows. First, 10% by weight, 20% by weight and 30% by weight of a fluorene-based diol compound was dissolved in dimethyl sulfoxide, and the refractive index and the Abbe number were measured for each solution. Subsequently, an approximate curve was derived from the measured values of the obtained three points, and the value obtained by extrapolating it to 100% by weight was defined as the refractive index and the Abbe number of the fluorene-based diol compound. The fluorene-based polymer was subjected to measurement using a test piece cut into a short fence from a film-like molded product.
[4] The fluorene-based polymer has a weight average molecular weight
Weight average molecular weight was measured (in terms of polystyrene) using a high-speed GPC apparatus ("HLC-8200 GPC" manufactured by Tosoh Corporation).
[5] The haze of the fluorene-based polymer
The haze was measured using a haze meter ("HGM-2DP" manufactured by Suga Test Instruments Co., Ltd.).
(1) Preparation of Fluorene Diol Compound
≪ Example 1 >
To a 300 ml glass reaction vessel equipped with a stirrer, a condenser and a thermometer was added 40.00 g (0.222 mol) of 9-fluorenone, 161.76 g (1.324 mol) of m-ethylphenol, ) And 21.11 g (0.111 mol) of p-toluenesulfonic acid were charged, and the temperature was raised to 30 占 폚. When the reaction mixture was stirred at the same temperature for 12 hours, analysis of the reaction mixture was carried out by HPLC. As a result, the remaining amount of 9-fluorenone was 1.0% or less.
Toluene and water were added to the reaction mixture obtained, and the mixture was heated to 85 DEG C and neutralized by adding 24 wt% sodium hydroxide, and then the aqueous layer was separated and removed. Subsequently, the organic layer was washed three times with water, and then the organic layer was concentrated under reduced pressure to partially remove toluene and m-ethylphenol. Toluene was added to the obtained slurry, the temperature was raised to 110 캜, and the mixture was cooled to room temperature. Precipitated crystals are filtered and dried to obtain a fluorene-based diol compound Ia wherein R 1 in the general formula (I) is an ethyl group, such as [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] 67.59 g of white crystals were obtained (yield based on 9-fluorenone: 74.9%). The HPLC purity of this white crystal was 98.7%.
Next, the total amount of the white crystals and toluene were poured into a glass reaction vessel, and the temperature was elevated to 110 DEG C, and then slowly cooled to room temperature. The precipitated crystals were filtered and dried to obtain 47.5 g of a purified product (yield based on 9-fluorenone: 52.5%). The HPLC purity of this purified product was 99.2%.
≪ Example 2 >
To 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 1 mol of n-lauryl mercaptan 2.25 g (0.011 mol) of thionyl chloride was added thereto, and the temperature was raised to 30 占 폚. Thereafter, 22.70 g (0.218 mol) of 35 wt% hydrochloric acid was added dropwise at 30 占 폚. When the reaction mixture was stirred at the same temperature for 20 hours, the reaction mixture solution was analyzed by HPLC. As a result, the remaining amount of 9-fluorenone was 1.0% or less.
Toluene and water were added to the reaction mixture obtained, and the mixture was heated to 85 DEG C and neutralized by adding 24 wt% sodium hydroxide, and then the aqueous layer was separated and removed. Subsequently, the organic layer was washed three times with water, and then the organic layer was concentrated under reduced pressure to partially remove toluene and m-ethylphenol. Toluene was added to the obtained slurry, the temperature was raised to 110 캜, and the mixture was cooled to room temperature. The precipitated crystals were filtered and dried to obtain 61.8 g of a white crystal of a fluorene-based diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] (yield of 9- : 68.5%). The HPLC purity of this white crystal 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 the temperature was raised to 30 占 폚. Thereafter, 22.70 g (0.218 mol) of 35 wt% hydrochloric acid was added dropwise at 30 占 폚. When the reaction mixture was stirred at the same temperature for 8 hours, analysis of the reaction mixture was carried out by HPLC. As a result, the remaining amount of 9-fluorenone was 1.0% or less.
Toluene and water were added to the reaction mixture obtained, and the mixture was heated to 85 DEG C and neutralized by adding 24 wt% sodium hydroxide, and then the aqueous layer was separated and removed. Subsequently, the organic layer was washed three times with water, and then the toluene and m-cresol were partially distilled off by concentrating the organic layer under reduced pressure. Toluene was added to the obtained slurry, the temperature was raised to 110 캜, and the mixture was cooled to room temperature. The precipitated crystals were collected by filtration and dried to obtain a fluorene diol compound Ib [9,9-bis (2-hydroxy-4-methylphenyl) fluorene] in which R 1 in the general formula (I) 48.1 g of crystals were obtained (yield based on 9-fluorenone: 57.3%). The HPLC purity of this white crystal was 90.3%.
Next, the total amount of the white crystals and toluene were poured into a glass reaction vessel, and the temperature was elevated to 110 DEG C, and then slowly cooled to room temperature. The precipitated crystals were filtered and dried to obtain 35.1 g of a purified product (yield based on 9-fluorenone: 41.8%). The HPLC purity of this purified product was 97.0%.
≪ Reference Example 1 &
(0.222 mol) of 9-fluorenone, 161.76 g (1.324 mol) of m-ethylphenol, 1.17 g (0.011 mol) of? -Mercaptopropionic acid and , And 11.11 g (0.111 mol) of 98 wt% concentrated sulfuric acid were injected, and the temperature was raised to 55 캜. When the reaction mixture was stirred at the same temperature for 6 hours, analysis of the reaction mixture was carried out by HPLC. As a result, the production of the zettenic compound (R 1 = ethyl group) represented by the general formula (III) 35%).
<Reference Example 2>
The reaction was carried out 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 stirred at 55 占 폚 for 6 hours, analysis of the reaction mixture was performed by HPLC. As a result, it was confirmed that the most significant product was the generation of the zettene compound represented by the formula (III) (R 1 = methyl group) (HPLC: 67%).
The purified product of the fluorene-based diol compound Ia [9,9-bis (2-hydroxy-4-ethylphenyl) fluorene] obtained in Example 1 and the fluorene-based diol compound Ib [9,9 -Bis (2-hydroxy-4-methylphenyl) fluorene] are shown in the following respective 1 H-NMR data.
[a] Fluorene Diol Compound Ia
The [b] fluorene-based diol compound Ib
The HH COZY and CH COYY spectra of the fluorene diol compound Ia are shown in FIGS. 1 and 2, respectively, and the HH COZY and CH COYY spectra of the fluorene diol compound Ib are shown in FIGS. 3 and 4, respectively. Those from the two-dimensional NMR spectra, fluoren-diol compounds Ia and Ib, the one that has the structure as represented by formula (I), in particular, and OH groups are bonded to the 2-position of the phenyl group, R 1 is the 4-position Lt; / RTI >
The refractory diol compound Ia obtained in Example 1 and the purified product of the fluorene diol compound Ib obtained in Example 3 were measured for melting point, refractive index and Abbe's number. The results are shown in Table 1. Table 1 shows, for comparison, the following general formula (IV), which is a conventionally known fluorene diol compound:
[Chemical Formula 6]
Bis [4- (2-hydroxyethoxy) phenyl] fluorene represented by the following formula.
(2) Preparation of Fluorene Polymer
≪ Example 4: Production of polycarbonate resin >
Fluorene diol compound Ia [9,9- bis (2-hydroxy-4-ethylphenyl) fluorene] 17.27 parts by weight of di-sodium hydrogen carbonate as a phenyl carbonate 9.42 parts by weight of the polymerization catalyst 2.1 × 10 -5 parts by weight The mixture was poured into a reaction vessel equipped with a stirrer and a distillation apparatus, heated at 200 DEG C under a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Thereafter, the degree of vacuum in the reaction vessel was adjusted to 27 ㎪, and the mixture was stirred at 200 캜 and 27 40 for 40 minutes. Next, the temperature was raised to 210 DEG C at a rate of 60 DEG C / hr, and the mixture was stirred at the same temperature for 30 minutes. Subsequently, the temperature was raised to 220 ° C at a rate of 60 ° C / hr, and the mixture was stirred at the same temperature for 40 minutes. Subsequently, the vacuum degree in the reaction vessel was adjusted to 24 ㎪, the temperature was raised to 230 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 20 minutes. Next, after the pressure reduction degree in the reaction vessel was adjusted to 20 ㎪, the temperature was raised to 240 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 40 minutes. Finally, the pressure reduction in the reaction vessel was adjusted to 133 Pa or less over one hour, and the reaction was carried out for one hour under the conditions of 240 캜 and 133 Pa or less, and the reaction was terminated. Thereafter, the polycarbonate resin A1 produced was blown into the reaction vessel by blowing nitrogen therein.
≪ Example 5: Production of polycarbonate resin >
, 20.49 parts by weight of a fluorene-based diol compound Ib [9,9-bis (2-hydroxy-4-methylphenyl) fluorene], 12.01 parts by weight of diphenyl carbonate and 2.7 10 -5 parts by weight of sodium hydrogencarbonate as a polymerization catalyst And an outlet device, heated at 200 占 폚 under a nitrogen atmosphere, and stirred for 20 minutes to be completely melted. Thereafter, the degree of vacuum in the reaction vessel was adjusted to 27 ㎪, and the mixture was stirred at 200 캜 and 27 40 for 40 minutes. Next, the temperature was raised to 210 DEG C at a rate of 60 DEG C / hr, and the mixture was stirred at the same temperature for 30 minutes. Subsequently, the temperature was raised to 220 ° C at a rate of 60 ° C / hr, and the mixture was stirred at the same temperature for 40 minutes. Subsequently, after the pressure reduction degree in the reaction vessel was adjusted to 24 ㎪, the temperature was raised to 230 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 10 minutes. Next, after the pressure reduction degree in the reaction vessel was adjusted to 20 ㎪, the temperature was raised to 240 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 30 minutes. Finally, the pressure reduction in the reaction vessel was adjusted to 133 Pa or less over one hour, and the reaction was carried out for one hour under the conditions of 240 캜 and 133 Pa or less, and the reaction was terminated. Thereafter, the polycarbonate resin A2 produced was blown out by blowing nitrogen into the reaction vessel.
≪ Example 6: Production of polyester resin >
20.00 parts by weight of the fluorene-based 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 titanium tetraisopropoxide 2.65 x 10 -5 parts by weight were charged into a reaction vessel equipped with a stirrer and an outlet device, heated to 220 ° C under a nitrogen atmosphere, and stirred to melt. Thereafter, stirring was continued at 220 占 폚 while allowing the produced methanol to flow out of the reaction system. 6.6 × 10 -5 parts by weight of germanium oxide was added at the point of time when almost no methanol flowed out, the temperature was raised to 280 ° C. at a rate of 60 ° C./hr and the mixture was stirred at the same temperature for 10 minutes. The pressure in the reaction vessel was gradually reduced to 133 Pa or less, and the reaction was terminated by stirring for 3 hours while removing the outflowed ethylene glycol from the reaction system. Thereafter, the resulting polyester resin A3 was taken out while blowing nitrogen into the reaction vessel.
≪ Comparative Example 1: Production of polycarbonate resin >
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 hydrogencarbonate as a polymerization catalyst were added with stirring , And the mixture was heated to 200 占 폚 in a nitrogen atmosphere and stirred for 20 minutes to be completely melted. Thereafter, the degree of vacuum in the reaction vessel was adjusted to 27 ㎪, and the mixture was stirred at 200 캜 and 27 40 for 40 minutes. Next, the temperature was raised to 210 DEG C at a rate of 60 DEG C / hr, and the mixture was stirred at the same temperature for 30 minutes. Subsequently, the temperature was raised to 220 ° C at a rate of 60 ° C / hr, and the mixture was stirred at the same temperature for 40 minutes. Subsequently, the vacuum degree in the reaction vessel was adjusted to 24 ㎪, the temperature was raised to 230 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 20 minutes. Next, after the pressure reduction degree in the reaction vessel was adjusted to 20 ㎪, the temperature was raised to 240 캜 at a rate of 60 캜 / hr, and the mixture was stirred at the same temperature for 40 minutes. Finally, the pressure reduction in the reaction vessel was adjusted to 133 Pa or less over one hour, and the reaction was carried out for one hour under the conditions of 240 캜 and 133 Pa or less, and the reaction was terminated. Thereafter, the polycarbonate resin B1 produced was blown out while nitrogen was blown into the reaction vessel.
≪ Comparative Example 2: Production of polyester resin >
20.00 parts by weight of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 13.02 parts by weight of dimethyl terephthalate, 2.66 parts by weight of ethylene glycol, and titanium tetraisopropoxide 2.29 × 10 -5 Were charged into a reaction vessel equipped with a stirrer and an outlet device, heated to 220 DEG C under a nitrogen atmosphere, and stirred to effect melting. Thereafter, stirring was continued at 220 占 폚 while allowing the produced methanol to flow out of the reaction system. 5.7 × 10 -5 parts by weight of germanium oxide was added at the time when almost no methanol flowed out, the temperature was raised to 280 ° C. at a rate of 60 ° C./hr and the mixture was stirred at the same temperature for 10 minutes. The pressure in the reaction vessel was gradually reduced to 133 Pa or less, and the reaction was terminated by stirring for 3 hours while removing the outflowed 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 resin and polyester resin obtained in Examples 4 to 6 and Comparative Examples 1 and 2 were measured. The results are shown in Table 2.
Claims (6)
[Chemical Formula 1]
[Wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group]
A fluorene-based polymer containing a constituent unit derived from a fluorene-based diol compound as a main chain.
Wherein at least one of a carbonate bond and an ester bond is contained in the main chain.
And a refractive index at 23 占 폚 of 1.6 or more.
The fluorene-based diol compound in which R 1 in the general formula (I) is an alkyl group, a cycloalkyl group or an aryl group having 2 or more carbon atoms.
Under acidic conditions, 9-fluorenone and the following general formula (II):
(2)
[Wherein R 1 represents an alkyl group, a cycloalkyl group or an aryl group]
Alkylphenol represented by the following general formula (1).
Wherein the 9-fluorenone and the m-alkylphenol are reacted in the presence of para-toluenesulfonic acid and a thiol compound.
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| JP2012269633A JP6233949B2 (en) | 2012-12-10 | 2012-12-10 | Fluorene polymer, fluorene diol compound and method for producing the same |
| JPJP-P-2012-269633 | 2012-12-10 | ||
| PCT/JP2013/081615 WO2014091910A1 (en) | 2012-12-10 | 2013-11-25 | Fluorene polymer, fluorene diol compound, and method for producing said polymer and compound |
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| EP3674280A4 (en) * | 2017-08-22 | 2020-08-12 | Mitsubishi Chemical Corporation | Bisphenol composition containing aromatic alcohol sulfonate and method for producing same, polycarbonate resin and method for producing same, and bisphenol production method |
| KR20200036941A (en) | 2017-08-22 | 2020-04-07 | 미쯔비시 케미컬 주식회사 | Bisphenol composition and manufacturing method thereof, and polycarbonate resin and manufacturing method thereof |
| CN108034344B (en) * | 2017-11-30 | 2020-05-26 | 中国船舶重工集团公司第七二五研究所 | Wide-temperature-range polyurethane damping coating for medium temperature and preparation method thereof |
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| JP6139508B2 (en) * | 2012-03-09 | 2017-05-31 | 本州化学工業株式会社 | Method for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, crystal thereof, and method for producing the crystal |
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- 2013-11-25 WO PCT/JP2013/081615 patent/WO2014091910A1/en active Application Filing
- 2013-11-25 CN CN201380062254.XA patent/CN104812797B/en not_active Expired - Fee Related
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| JP2014114387A (en) | 2014-06-26 |
| TW201428021A (en) | 2014-07-16 |
| JP6233949B2 (en) | 2017-11-22 |
| CN104812797B (en) | 2017-04-26 |
| CN104812797A (en) | 2015-07-29 |
| WO2014091910A1 (en) | 2014-06-19 |
| TWI598374B (en) | 2017-09-11 |
| KR101997313B1 (en) | 2019-07-05 |
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