JP5451120B2 - Dihydric alcohols, polycarbonate resins, polyester resins, molded articles comprising them, and optical elements - Google Patents

Description

  The present invention relates to a novel dihydric alcohol having a fluorene structure, and a polymer comprising the same, in particular, a polycarbonate resin, a polyester resin, and a molded article comprising the same, and an optical element.

  Since a resin material having a high refractive index has high workability compared with a conventional glass material, a lens such as an eyeglass lens, a camera, an optical disk lens, an fθ lens, and an optical system for an image display medium A wide range of applications are being studied for elements, optical films, films, substrates, various optical filters, prisms, optical elements for communication, and the like.

  In particular, resin materials having a fluorene structure are known to have a relatively high refractive index and relatively low birefringence, and various studies have been made since high heat resistance can be expected. Patent Document 1 discloses a polycarbonate resin having a 9,9′-diphenylfluorene structure and excellent in heat resistance and mechanical strength.

  A structure that is expected to be capable of higher refraction and lower birefringence because of its higher number of conjugated aromatic rings in the molecule and higher molecular structure symmetry than these conventional 9,9'-diphenylfluorene structures. Spirobifluorene exists as a molecule having Patent Document 2 discloses a resin having such a spiro carbon-containing bicyclic structure as a unit skeleton.

Japanese Patent No. 4196326 JP 2006-089585 A

  However, the polycarbonate-based resin described in Patent Document 1 is composed of a resin having a monomer having a 9,9'-diphenylfluorene structure as a copolymer component, or a unit skeleton having a lower refractive index than that. ing. For this reason, in order to further increase the refractive index, it is indispensable to develop a copolymer component exhibiting a higher refractive index.

  Although the bicyclic structure type resin having spiro carbon described in Patent Document 2 can be expected to exhibit higher refractive index properties, the glass transition point is as high as 334 ° C. to 340 ° C. There are problems in processing by thermoforming, such as being easily generated.

  In view of the above problems, the present invention provides a dihydric alcohol capable of producing a high-refractive index resin material having high processability, and a polymer thereof, in particular, a polycarbonate resin, a polyester resin, and a molded article comprising the same, and an optical element Is intended to provide.

  In order to achieve the above object, the present invention provides a dihydric alcohol constituted as described in the following <1> to <7>, a polycarbonate resin comprising the dihydric alcohol, a polyester resin, and a molded article comprising them. And an optical element.

  <1> A dihydric alcohol represented by the following general formula (1).

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]

  <2> A polycarbonate resin containing a repeating unit represented by the following general formula (2) in a polymer.

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]

  <3> In the polycarbonate resin according to <2>, the molar ratio of the repeating unit represented by the general formula (2) [the number of repeating units represented by the general formula (2) is the number of all repeating units in the polymer. A polycarbonate resin characterized by a gradual summation and a value expressed as a percentage] of 10% or more.

  <4> In the polycarbonate resin according to <3>, in the repeating unit in all polymers, the repeating unit other than the repeating unit represented by the general formula (2) described in <2> may be represented by the general formula (3) or A polycarbonate resin comprising at least one type of repeating unit selected from the repeating units represented by (4).

[In General Formulas (3) and (4), T represents an oxyalkylene group having 2 to 12 carbon atoms, a poly (oxyethylene) group having 2 to 12 carbon atoms, or a single bond. R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may be the same or different from each other. Good. U represents an alkylene group having 1 to 13 carbon atoms, an alkylidene group having 2 to 13 carbon atoms, a cycloalkylene group having 5 to 13 carbon atoms, a cycloalkylidene group having 5 to 13 carbon atoms, and 6 to 13 carbon atoms. arylene group, Furuoreniden, -O -, - S -, - SO 2 -, - CO- or a single bond. R1, R2, T and U may be different for each structural unit. ]

  <5> A polyester resin containing a repeating unit represented by the following general formula (2) in a polymer.

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]

  <6> A molded article made of the polycarbonate resin or polyester resin according to <2> to <5>.

  <7> An optical element comprising the polycarbonate resin or polyester resin according to <2> to <5>.

  ADVANTAGE OF THE INVENTION According to this invention, the dihydric alcohol which can manufacture a high refractive index material with high workability, and its polymer, especially a polycarbonate resin, a polyester resin, the molded object consisting of them, and an optical element are provided. be able to.

It is a graph which shows the relationship between the composition ratio of the copolymer of the monomers 1a and 7a, and an optical characteristic. It is a graph which shows the relationship between the carbon and oxygen atom number of L in General formula (2), and a glass transition point.

The present invention can achieve the object of the present invention by the above-described configuration, but specifically, it can be in the following forms.
The dihydric alcohol according to the present invention is characterized by comprising a compound represented by the following general formula (1).

  In the general formula (1), L is an oxyalkylene group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, or poly (oxyethylene having 2 to 12 carbon atoms, preferably 2 to 4 carbon atoms. ) Group. If the number of carbon atoms contained in L in the structure of the dihydric alcohol represented by the general formula (1) is less than 2, the glass transition point of the polycarbonate resin and the polyester resin obtained by polymerizing this is increased, and due to heating Melt molding is difficult. On the other hand, when the number of carbon atoms exceeds 12, a molded article of polycarbonate resin and polyester resin obtained by polymerizing it is difficult to obtain sufficient shape stability against heat.

Next, the manufacturing method of dihydric alcohol which concerns on this invention is demonstrated.
First, the dihydric alcohol represented by the general formula (1) of the present invention is represented by the following formula (5).

In the presence of cesium carbonate or the like, 2,2′-dihydroxy-9,9′-spirobifluorene represented by the following general formula (6)

[Wherein, X represents a fluorine, chlorine, bromine or iodine atom, and L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]
It can manufacture by making halogenated alcohol represented by these. Of these, 2,2'-dihydroxy-9,9'-spirobifluorene is described in Helv. Chim. Acta, 62, 2285 to 2302 (1979).

  The stoichiometric ratio of the halogenated alcohols represented by the general formula (6) that acts on 2,2′-dihydroxy-9,9′-spirobifluorene is expressed by the formula (6). The number of moles of halogenated alcohols / (number of moles of 2,2′-dihydroxy-9,9′-spirobifluorene compounds) is preferably 2 or more and 100 or less. If this value is less than 2, by-products may be generated, and the yield of the dihydric alcohol represented by the general formula (1) may be reduced. If it is greater than 100, it is represented by the general formula (6). The amount of halogenated alcohol used may increase, and production may be costly.

  The reaction conditions are not particularly limited, but polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide are generally used as the reaction solvent, the reaction temperature is from 100 ° C. to 150 ° C., and the reaction time is from 12 hours to 48 hours. The obtained reaction product can be easily purified by a method such as recrystallization or chromatography.

  The polycarbonate resin and polyester resin of the present invention obtained by polymerizing the dihydric alcohol represented by the general formula (1) of the present invention are resins having low birefringence while having a relatively high refractive index. . In general, a polymer having an aromatic ring in a molecule has high molecular orientation, and as a result, it tends to be a resin material having high birefringence. However, since the spirobifluorene skeleton in the dihydric alcohol represented by the general formula (1) is a highly symmetric structure in which two fluorene ring planes are orthogonal, the intrinsic birefringence per unit skeleton is small. It can be considered that the birefringence of the resin is reduced.

  Furthermore, the oxyalkylene group having 2 to 12 carbon atoms and the poly (oxyethylene) group having 2 to 12 carbon atoms represented by L in the general formula (1) are represented by the general formula (1) of the present invention. It functions to lower the glass transition point of a polymer obtained by polymerizing a dihydric alcohol. By lowering the glass transition point, it is possible to improve the workability at the time of melting and simultaneously reduce the melt viscoelasticity and reduce the stress birefringence at the time of molding. It is inferred that these characteristics are combined and the polycarbonate resin and polyester resin of the present invention have low birefringence.

  The polycarbonate resin and the polyester resin of the present invention are synthesized using a dihydric alcohol represented by the general formula (1) as a polymerization component, and the polymer has a repeating unit represented by the following general formula (2). It is characterized by containing.

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]
Here, the molar ratio of the repeating unit represented by the general formula (2) is more preferably 10 percent or more, and further preferably 25 percent or more. Here, the molar ratio of the repeating units refers to a value expressed as a percentage by decreasing the number of repeating units represented by the general formula (2) by the sum of the total number of repeating units in the polymer. As the molar ratio of the repeating unit represented by the general formula (2) is larger, the high refractive index property of the dihydric alcohol analog of the general formula (1) is more strongly reflected by the polymer.

  The other copolymerization component in the polymer is not particularly limited as long as it satisfies the desired characteristics, but the following general formula (7) or (8)

[In General Formulas (7) and (8), T represents an oxyalkylene group having 2 to 12 carbon atoms, a poly (oxyethylene) group having 2 to 12 carbon atoms, or a single bond. R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may be the same or different from each other. Good. U represents an alkylene group having 1 to 13 carbon atoms, an alkylidene group having 2 to 13 carbon atoms, a cycloalkylene group having 5 to 13 carbon atoms, a cycloalkylidene group having 5 to 13 carbon atoms, and 6 to 13 carbon atoms. arylene group, Furuoreniden, -O -, - S -, - SO 2 -, - CO- or a single bond. R1, R2, T and U may be different for each structural unit. ] The copolymerization component shown by can be contained more suitably. Moreover, these copolymerization components may be used independently or may be used in multiple types.

  When the dihydric alcohol represented by the general formula (7) or (8) is used as a copolymerization component, the synthesized polymer is selected from repeating units represented by the following general formulas (3) and (4) At least one kind of repeating unit is contained.

[In General Formulas (3) and (4), T represents an oxyalkylene group having 2 to 12 carbon atoms, a poly (oxyethylene) group having 2 to 12 carbon atoms, or a single bond. R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may be the same or different from each other. Good. U represents an alkylene group having 1 to 13 carbon atoms, an alkylidene group having 2 to 13 carbon atoms, a cycloalkylene group having 5 to 13 carbon atoms, a cycloalkylidene group having 5 to 13 carbon atoms, and 6 to 13 carbon atoms. arylene group, Furuoreniden, -O -, - S -, - SO 2 -, - CO- or a single bond. R1, R2, T and U may be different for each structural unit. ]

  In this case, the thermal stability and optical properties of the dihydric alcohol analog of the general formula (7) or (8) are reflected in the polymer depending on the copolymerization ratio.

  When the polycarbonate resin and polyester resin of the present invention contain the repeating units of the general formulas (3) and (4), the molar ratio of the repeating units represented by the general formulas (3) and (4) is 90% or less. It is preferable that it is 75 percent or less.

  When the polycarbonate resin and the polyester resin of the present invention include any repeating unit other than the dihydric alcohol residue of the general formulas (2), (3) and (4), the general formulas (2) and (3) It is preferable that the molar ratio of repeating units other than (4) is 10 percent or less. Here, the molar ratio of the repeating units refers to the total number of repeating units other than the general formulas (2), (3) and (4), which is expressed as a percentage by grading the sum of the total number of repeating units in the polymer. . If the molar ratio of the repeating units other than the general formulas (2), (3) and (4) exceeds 10 percent, desired physical properties such as heat resistance stability, high refractive index property and low birefringence may not be obtained. There is.

  The polycarbonate resin and the polyester resin of the present invention can be produced by various methods. However, the polycarbonate resin and the polyester resin can be produced efficiently by performing the following three methods independently or by combining them stepwise. Can do.

  First, the first method involves reacting a dihydric alcohol represented by the general formula (1), (7) or (8) with phosgene or a phosgene derivative in a mixed solution of an organic solvent and a basic aqueous solution. This is a method of condensation polymerization.

  In this reaction, first, phosgene or a mixed solution of a basic aqueous solution in which an alkali metal compound or the like is dissolved, a dihydric alcohol represented by the general formula (1), (7) or (8) and an inert organic solvent is added. A desired polycarbonate is obtained by introducing and reacting with a phosgene derivative. Examples of the inert organic solvent include chlorinated hydrocarbons such as dichloromethane (methylene chloride), dichloroethane, trichloroethane, tetrachloroethane, and chlorobenzene, and acetophenone. The reaction conditions are not particularly limited, but usually it is generally cooled in the range of 0 ° C. to room temperature at the beginning of the reaction, and then allowed to react for 30 minutes to 6 hours in the range of 0 ° C. to 70 ° C.

  The amount of phosgene or phosgene derivative used in the reaction is (number of moles of phosgene or phosgene derivative to act) / (total number of moles of dihydric alcohol used in the reaction) of 0.3 to 1.5. It is preferable to become. If this value is less than 0.3, unreacted dihydric alcohols may remain and the yield may decrease, and if this value is more than 1.5, the amount of phosgene or phosgene derivative used is large. Therefore, separation and purification after the reaction may be difficult.

  For the purpose of promoting the reaction, a phase transfer catalyst may be added to an organic solvent. Here, examples of the phase transfer catalyst include organic bases such as triethylamine, tetramethylethylenediamine, and pyridine.

  Further, for the purpose of adjusting the degree of polymerization, a terminal stopper may be added to the reaction solution. As the terminal terminator, those usually used for polymerization of polycarbonate may be used, and various types can be used. Specific examples thereof include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, bromophenol, and tribromophenol. As phosgene derivatives, bis (trichloromethyl) carbonate, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4-dichlorophenyl) carbonate, bis (cyanophenyl) carbonate, chloroformate And trichloromethyl.

  Next, the second method for synthesizing the resin of the present invention is a method in which a dihydric alcohol represented by the general formula (1), (7) or (8) is transesterified with a carbonic acid diester. There are various types of carbonic acid diesters used in this method, such as diphenyl carbonate, ditolyl carbonate, bis (nitrophenyl) carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bisphenol A bisphenyl carbonate, dimethyl carbonate, diethyl carbonate. Dibutyl carbonate, dicyclohexyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate and the like are preferably used. In this transesterification reaction, any of the dihydric alcohols represented by the general formula (1), (7) or (8) can be used as a carbonic acid diester derivative.

  The amount of carbonic acid diester used is preferably such that (number of moles of carbonic acid diester to act) / (total number of moles of dihydric alcohol used in the reaction) is in the range of 1.0 to 2.5. . If this value is less than 1.0, unreacted dihydric alcohols may remain and the yield may decrease, and if this value is greater than 2.5, the amount of carbonic acid diester used increases. Separation and purification after the reaction may be difficult. Moreover, also in this transesterification reaction, you may add the terminal terminator quoted by the 1st method as needed.

  In this transesterification method, it is preferable that the reaction temperature is usually 350 ° C. or less, more preferably 300 ° C. or less, and it is desirable to gradually increase the temperature as the reaction proceeds. If the transesterification exceeds 350 ° C., thermal decomposition of the polymer occurs, which is not preferable. Further, the reaction pressure can be appropriately adjusted so that the reaction can be efficiently performed according to the vapor pressure of the monomer used and the boiling point of the product generated by the reaction. As a result of the transesterification reaction, when by-products other than the polymer generated from the ester compound used can be removed under reduced pressure, the reaction is carried out under reduced pressure conditions to improve the reaction rate and yield. It is preferable to carry out the reaction while removing substances. The reaction time may be carried out until the target molecular weight is reached, and is usually about 10 minutes to 12 hours.

  This transesterification reaction can be carried out batchwise or continuously, and the reactor used is not particularly limited in material and structure, and may have a normal heating function and stirring function. Further, the shape of the reactor may be not only a tank type but also an extruder type reactor.

  And although said transesterification reaction is normally performed on solvent-free conditions, when the melting | fusing point of the dihydric alcohol to be used is high and reaction does not advance easily, it is 1 to 200 weight% with respect to the polymer obtained. You may carry out in presence of an inert organic solvent. Examples of the inert organic solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, diphenyl sulfone, polyphenyl ether, dichlorobenzene, and methylnaphthalene, tricyclo (5.2.10) decane, cyclooctane, and cyclodecane. Chlorinated hydrocarbons such as cycloalkane, dichloromethane (methylene chloride), chloroform, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, and chlorobenzene. Moreover, you may carry out in inert gas atmosphere as needed. Here, examples of the inert gas include helium, argon, carbon dioxide, and nitrogen.

  Moreover, the catalyst normally used in transesterification can be used as needed. Here, examples of the transesterification catalyst that can be used include nitrogen-containing compounds such as alkali metal compounds such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal compounds, amines and quaternary ammonium salts. Examples include basic compounds and boron compounds. Among these, nitrogen-containing basic compounds are preferable in terms of high catalytic ability and ease of removal from the reaction system, such as trihexylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, dimethylaminopyridine and the like. Preferably used.

The amount of the catalyst used is 1 × 10 ⁻² to 1 × 10 ⁻⁸ mol, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁷ mol, relative to 1 mol of all dihydric alcohols. If the amount of the catalyst added is less than 1 × 10 ⁻⁸ mol, a sufficient catalytic effect may not be obtained, and if it exceeds 1 × 10 ⁻² mol, the physical properties of the resulting polymer, particularly heat resistance and water resistance, may be lost. There is a risk of degrading degradation.

  Furthermore, the third method for synthesizing the resin of the present invention is a method in which a dihydric alcohol represented by the general formulas (1), (7) and (8) is reacted with a dicarboxylic acid derivative to perform ester polymerization. . The dicarboxylic acid derivative used in this method is not particularly limited, and aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalene. Aromatic carboxylic acids such as dicarboxylic acids, and acid chlorides of these dicarboxylic acids, methyl esters of these dicarboxylic acids, ethyl esters of these dicarboxylic acids, and dicarboxylic anhydrides such as phthalic anhydride and naphthalenedicarboxylic acid are used. It is done.

  The amount of the dicarboxylic acid derivative used is such that (number of moles of dicarboxylic acid derivative to act) / (total number of moles of dihydric alcohol used in the reaction) is in the range of 0.7 to 1.5. Is preferred. If this value is less than 0.7, a large amount of unreacted dihydric alcohol may remain and the yield may be reduced. If this value is greater than 1.5, a large amount of unreacted dicarboxylic acid derivative remains. The yield may decrease.

  In this ester polymerization, the reaction temperature is preferably preferably 350 ° C. or lower, more preferably 300 ° C. or lower, and it is desirable to gradually raise the temperature as the reaction proceeds. If by-products other than the polymer resulting from the dicarboxylic acid derivative used can be removed under reduced pressure as a result of ester polymerization, the reaction is carried out under reduced pressure conditions to improve the reaction rate and yield. It is preferable to carry out the reaction while removing substances. The reaction time may be carried out until the target molecular weight is reached, and is usually about 10 minutes to 12 hours.

  This ester polymerization reaction can be carried out batchwise or continuously, and the reactor used is not particularly limited in its material and structure, and may have a normal heating function and stirring function. Further, the shape of the reactor may be not only a tank type but also an extruder type reactor.

  And said ester polymerization reaction may be performed in presence of 1 to 200 weight% of an inert organic solvent with respect to the polymer obtained. Examples of the inert organic solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, diphenyl sulfone, polyphenyl ether, dichlorobenzene, and methylnaphthalene, tricyclo (5.2.10) decane, cyclooctane, and cyclodecane. Chlorinated hydrocarbons such as cycloalkane, dichloromethane (methylene chloride), chloroform, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, and chlorobenzene. Moreover, you may carry out in inert gas atmosphere as needed. Here, examples of the inert gas include helium, argon, carbon dioxide, and nitrogen.

  The polymer obtained by the above three methods can be purified by a known method, and can be purified by a reprecipitation method using a poor solvent such as methanol or water. The polycarbonate resin and polyester resin of the present invention can be produced by heating and drying the polymer obtained by reprecipitation under reduced pressure to remove the residual solvent. The drying temperature is usually preferably in the range of 100 ° C to 350 ° C. If it is less than 100 ° C., the residual solvent cannot be removed sufficiently, and if it exceeds 350 ° C., the polymer may be thermally decomposed and desired physical properties may not be obtained.

  In the polycarbonate resin and the polyester resin of the present invention, an additive may be contained within a range in which the original purpose is not impaired. Additives include glass materials such as glass fibers, glass beads, and glass powder, inorganic fillers of metal oxide fine particles such as silicon oxide, titanium oxide, zirconium oxide, and aluminum oxide, phosphorus-based processing heat stabilizers, hydroxylamines Processing heat stabilizers, antioxidants such as hindered phenols, light stabilizers such as hindered amines, ultraviolet absorbers such as benzotriazoles, triazines, benzophenones and benzoates, phosphate esters and phthalates Plasticizers such as acid esters, citrate esters and polyesters, mold release agents such as silicones, flame retardants such as phosphate esters and melamines, antistatic agents for fatty acid ester surfactants, organic dyes Substances such as colorants and impact modifiers can be mentioned. These additives may be used alone or in combination.

  The polycarbonate resin and polyester resin of the present invention can be mixed with the above additives by a known method. Examples thereof include a method using a screw extruder, a roller type mill, a kneader mill, a mixer, a high-pressure homogenizer, a wet media pulverizer (bead mill, ball mill, disk mill), an ultrasonic disperser, and the like. The polycarbonate resin and polyester resin thus obtained can be used for producing various molded articles and optical elements by known molding methods such as injection molding, hollow molding, extrusion molding, press molding, calendar molding, and the like. .

  When the polycarbonate resin and polyester resin of the present invention are molded by injection molding to produce an optical element, the polycarbonate resin and polyester resin of the present invention are preferably pelletized with a pelletizer in advance. The pellets can be injected into an injection molding apparatus equipped with a kneading part composed of a melting cylinder and a screw, and can be injected into a molding die having an arbitrary shape through heat melting and kneading in the kneading part. An optical element having an arbitrary shape can be manufactured by using a molding die whose mold surface is a plane, concave, or convex surface having an arbitrary shape subjected to a mirror finish.

  When the polycarbonate resin and the polyester resin of the present invention are molded by press molding to produce an optical element, the polycarbonate resin and the polyester resin of the present invention are pulverized in advance by a pulverizer such as a mortar, a stamp mill, or a ball mill. Is preferred. The powder is sealed in a molding die whose surface is mirror-treated in any shape, concave or convex, and the mold is heated to a temperature above the glass transition point of the resin to melt it. An optical element having an arbitrary shape can be manufactured by applying a press pressure after the process.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
[Example 1-1]
Synthesis of monomer (1a)

  First, 2,2′-dihydroxy-9,9′-spirobifluorene (5), which is a synthetic precursor of monomer 1a

Was synthesized.
A 1 L four-necked flask was charged with aluminum chloride (127 g, 0.948 mol) and nitromethane (250 mL). To this solution was added acetyl chloride (67.3 mL, 0.948 mol) and the solution was kept at 0 ° C. To this solution, 9,9′-spirobifluorene (9)

A solution prepared by dissolving (100 g, 0.316 mol) in dry dichloromethane (300 mL) was added dropwise over 1 hour. After stirring at 0 ° C. for 1 hour, the mixture was warmed to room temperature and stirred for 2 hours. The solution after the reaction was poured into an aqueous hydrochloric acid solution (concentration: 1M) containing ice to decompose unreacted aluminum chloride, and then the organic layer was washed with a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a solid. This solid was dissolved in dichloromethane, poured into n-hexane and reprecipitated, and 2,2'-diacetyl-9,9'-spirobifluorene (10)

(95.4 g, yield 76%) was obtained.
Subsequently, 2,2′-diacetyl-9,9′-spirobifluorene (10) (10.0 g, 25 mmol) and metachloroperbenzoic acid (40% water content) (21.6 g, 75 mmol) were added to a 500 mL eggplant flask. After the addition, the mixture was heated to reflux for 12 hours.

  After cooling to room temperature, a saturated aqueous solution of sodium sulfite was added and stirred, and the organic layer was washed with a saturated aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Ethyl acetate, n-hexane and dichloromethane were mixed (mixing ratio, ethyl acetate: n-hexane: dichloromethane = 1: 4: 2). Separation and purification by silica gel column chromatography using a solvent as a developing solvent was performed. . The solvent was removed by drying under reduced pressure, and 2,2′-diacetoxy-9,9′-spirobifluorene (11)

(9.45 g, yield 87%) was obtained.
A 2,2′-diacetoxy-9,9′-spirobifluorene (11) (6.35 g, 14.7 mmol) and methanol (20 mL) were placed in a 100 mL eggplant flask. To this solution was added an aqueous solution (10 mL) in which sodium hydroxide (1.25 g, 31.3 mmol) was dissolved, and the mixture was stirred for 30 minutes at room temperature.

  After dilute hydrochloric acid (concentration 3M) was added to acidify the solution, the organic layer was extracted with diethyl ether. The organic layer was washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. Separation and purification were performed by silica gel column chromatography using ethyl acetate and n-hexane mixed (mixing ratio, ethyl acetate: n-hexane = 1: 4) as a developing solvent. The solvent was removed by drying under reduced pressure to obtain 2,2′-dihydroxy-9,9′-spirobifluorene (5) (5.05 g, yield 99%).

  To a 100 mL two-necked eggplant flask, 2,2′-dihydroxy-9,9′-spirobifluorene (5) (1.50 g, 4.31 mmol), N, N-dimethylformamide (10 mL) synthesized by the above method was added. ), 2-chloroethanol (0.604 mL, 9.00 mmol) and cesium carbonate (2.93 g, 9.00 mmol) were added, and the mixture was stirred at 110 ° C. for 12 hours under an argon atmosphere.

  After completion of the reaction, the mixture was poured into water to dissolve N, N-dimethylformamide and cesium carbonate in water, and the remaining solid was filtered. This solid was dissolved in dichloromethane, the solution was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Ethyl acetate and n-hexane were mixed (mixing ratio, ethyl acetate: n-hexane = 1: 2 to 3: 2). Separation and purification by silica gel column chromatography using a solvent as a developing solvent was performed. The solvent was removed by drying under reduced pressure to obtain monomer 1a (933 mg, yield 50%).

[Example 1-2]
Synthesis of monomer (1b)

  As a result of carrying out the reaction using 2-bromohexanol (1.22 mL, 9.00 mmol) instead of 2-chloroethanol under the same conditions as in Example 1-1, monomer 1b (1.30 g, yield) 55%).

[Example 1-3]
Synthesis of monomer (1c)

  As a result of reaction using 12-bromododecanol (1.83 g, 6.90 mmol) instead of 2-chloroethanol under the same conditions as in Example 1-1, monomer 1c (1.02 g, yield) was obtained. 33%).

[Example 1-4]
Synthesis of monomer (1d)

  The reaction was carried out using 2- (2-chloroethoxy) ethanol (0.949 mL, 9.00 mmol) instead of 2-chloroethanol under the same conditions as in Example 1-1. After the reaction, ethanol was used as a developing solvent. Separation and purification by silica gel column chromatography was performed. As a result of removing the solvent by drying under reduced pressure, monomer 1d (2.04 g, yield 86%) was obtained.

[Example 1-5]
Synthesis of monomer (1e)

  To a 100 mL two-necked eggplant flask, 2,2′-dihydroxy-9,9′-spirobifluorene 5 (4.00 g, 11.5 mmol), N, N-dimethylformamide (40 mL), 2- {2- ( 2-Chloroethoxy) ethoxy} ethanol (3.64 mL, 25.0 mmol) and cesium carbonate (8.14 g, 25.0 mmol) were added, and the mixture was stirred at 110 ° C. for 12 hours under an argon atmosphere.

  After completion of the reaction, the mixture was poured into water to dissolve N, N-dimethylformamide and cesium carbonate in water, and the remaining solid was filtered. This solid was dissolved in dichloromethane, the solution was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Separation and purification by silica gel column chromatography using a mixed solvent of ethyl acetate and n-hexane (ethyl acetate: methanol = 1: 9: 1 in a mixing ratio) as a developing solvent was performed. The solvent was removed by drying under reduced pressure to obtain monomer 1e (6.23 g, yield 86%).

[Example 2-1]
Synthesis of polycarbonate polymer (1) of 1a Monomer 1a (800 mg, 1.83 mmol), diphenyl carbonate (393 mg, 1.83 mmol) and 4-dimethylaminopyridine (2.24 mg, 18.3 μmol) was added and stirred with heating at 180 ° C. for 30 minutes. Furthermore, the reaction temperature was gradually raised as the pressure in the reaction vessel was reduced stepwise (400 hPa, 200 ° C. for 20 minutes, 20 minutes at 160 hPa, 220 ° C., 20 minutes at 40 hPa, 230 ° C.) Stir for 30 minutes at 1 hPa, 250 ° C. for 30 minutes).

  After cooling to room temperature, the obtained solid was dissolved in dichloromethane (20 mL), and this solution was added to methanol (100 mL) with stirring to reprecipitate. The resulting precipitate was dried under reduced pressure to obtain polymer (1) (745 mg, yield 88%).

[Example 2-2]
Synthesis of polycarbonate copolymer (2) of 1a (90%) and 7a (10%)

  Monomer 1a (1.80 g, 4.12 mmol), monomer 7a (manufactured by Osaka Gas Chemicals: BPEF [product name], 201 mg, 0.458 mmol), diphenyl carbonate (981 mg, 4.12 mmol) in a 20 mL Schlenk type reaction tube under an argon atmosphere. 58 mmol) and 4-dimethylaminopyridine (5.6 mg, 45.8 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (2) (1.59g, 75% of yield) was obtained.

[Example 2-3]
Synthesis of Polycarbonate Copolymer (3) of 1a (75%) and 7a (25%) Monomer 1a (1.50 g, 3.44 mmol), monomer 7a (502 mg, 1.4 mmol) in a 20 mL Schlenk type reaction tube under an argon atmosphere. 15 mmol), diphenyl carbonate (981 mg, 4.58 mmol) and 4-dimethylaminopyridine (5.6 mg, 45.8 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (3) (1.63 g, yield 77%) was obtained.

[Example 2-4]
Synthesis of Polycarbonate Copolymer (4) of 1a (50%) and 7a (50%) In a 20 mL Schlenk-type reaction tube, monomer 1a (1.00 g, 2.29 mmol), monomer 7a (1.01 mg, 2.29 mmol), diphenyl carbonate (981 mg, 4.58 mmol) and 4-dimethylaminopyridine (5.6 mg, 45.8 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (4) (1.68g, yield 79%) was obtained.

[Example 2-5]
Synthesis of Polycarbonate Copolymer (5) of 1a (25%) and 7a (75%) Monomer 1a (500 mg, 1.15 mmol), monomer 7a (1.51 g, 3. 44 mmol), diphenyl carbonate (981 mg, 4.58 mmol) and 4-dimethylaminopyridine (5.6 mg, 45.8 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (5) (1.83g, 86% of yield) was obtained.

[Example 2-6]
Synthesis of polycarbonate copolymer (6) of 1a (10%) and 7a (90%) Monomer 1a (200 mg, 0.458 mmol) and monomer 7a (1.81 g, 4. 12 mmol), diphenyl carbonate (981 mg, 4.58 mmol) and 4-dimethylaminopyridine (5.6 mg, 45.8 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (6) (1.81g, 85% of yield) was obtained.

[Example 2-7]
Synthesis of polycarbonate polymer (1b) of 1b Monomer 1b (427 mg, 0.779 mmol), diphenyl carbonate (162 mg, 0.779 mmol) and 4-dimethylaminopyridine (0.951 mg, 0.95 mg) in a 20 mL Schlenk-type reaction tube under an argon atmosphere. 7.8 μmol). Subsequently, the reaction and post-treatment were performed under the same conditions as in Example 2-1, to obtain a polymer 7 (412 mg, yield 92%).

[Example 2-8]
Synthesis of polycarbonate polymer (1) of 1c Monomer 1c (668 mg, 0.931 mmol), diphenyl carbonate (199 mg, 0.931 mmol) and 4-dimethylaminopyridine (1.13 mg, 1.1 g) in a 20 mL Schlenk type reaction tube under an argon atmosphere. 9.3 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (8) (567 mg, yield 82%) was obtained.

[Example 2-9]
Synthesis of 1d polycarbonate polymer (9) Monomer 1d (1.77 mg, 3.38 mmol), diphenyl carbonate (724 mg, 3.38 mmol), 4-dimethylaminopyridine (4. 13 mg, 33.8 μmol) and triphenyl phosphite (3.38 μL, 12.9 μmol) as an antioxidant. Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (9) (1.46g, yield 78%) was obtained.

[Example 2-10]
Synthesis of polycarbonate polymer (1) of 1e Monomer 1e (1.14 g, 1.82 mmol), diphenyl carbonate (390 mg, 1.82 mmol) and 4-dimethylaminopyridine (2. 22 mg, 18.2 μmol). Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (10) (1.10g, yield 95%) was obtained.

[Comparative Example 2-1]
Synthesis of polycarbonate polymer (7) of 7a Monomer 7a (1.00 g, 2.28 mmol), diphenyl carbonate (489 mg, 2.28 mmol), 4-dimethylaminopyridine (2. 8 mg, 22.8 μmol) and triphenyl phosphite (2.28 μL, 8.7 μmol) as an antioxidant were added. Then, reaction and a post-process were performed on the conditions equivalent to Example 2-1, and the polymer (11) (932 mg, 88% of yield) was obtained.

[Example 3-1]
Example of preparation of optical element disc molding Polymer 1 (0.30 g) was pulverized in an agate mortar and then placed in a cylindrical mold having an inner diameter of 15 mm. Both surfaces of the open part of the mold were sealed with a cylindrical mold having a diameter of 15 mm and having a mirror-finished plane. After heating at 200 ° C. for 10 minutes to melt the sealed resin, a pressure of 50 MPa was applied from both sides of the mold. After cooling to 100 ° C., the pressure was released to obtain a disk-shaped transparent molded body.

[Analysis and evaluation of each polymer]
An analysis / evaluation method of the prepared polymer will be described. Analysis / evaluation items include molecular weight distribution measurement, glass transition point, and refractive index measurement, and the details of the measurement method of each item will be described below.

(1) Molecular weight distribution About the polymer, the gel permeation chromatograph (GPC: Gel Permeation Chromatography) measurement which performed chloroform as liquid feeding (0.085 mL / min) was performed. The analyzer uses two types of polystyrene gel columns (manufactured by Tosoh Corporation, TSKgel G5000HXL [product name], G4000HXL [product name]) loaded with a high performance liquid chromatograph (JASCO Corporation: Gulliver [product name]). It was. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were approximately calculated by comparing the retention time of the polymer in the apparatus flow path with the retention time of standard polystyrene having a known molecular weight.

(2) Glass transition point (Tg)
Using a differential scanning calorimeter (DSC: Differential Scanning Calorimetry, manufactured by Shimadzu Corporation: DSC-60 [product name]), the polymer is measured in the range from room temperature to 300 ° C., and the glass transition point (Tg) is determined. Asked.

(3) Refractive index (nd) and Appe number (νd)
The polymer was dissolved in N-methyl-2-pyrrolidone, and the solution was dropped onto the glass substrate. Then, the glass substrate was heated to 250 ° C. and held for 30 minutes, and the solvent was distilled off to obtain a thickness average of 0.00. A 7 mm film was formed. At 27 ° C., the refractive index (nd) with respect to the d spectral line (wavelength 587.56 nm) was measured using a Karnew refractometer (manufactured by Shimadzu Device Manufacturing Co., Ltd .: KPR-30 [product name]). (Νd) was calculated.

  The results obtained for each polymer are shown in Table 1 below.

  Table 2 and FIG. 1 below show the relationship between the composition ratio of the copolymer of monomers 1a and 7a and the optical characteristics, which was obtained from the results of Table 1.

  Moreover, the following Table 3 and FIG. 2 show the relationship between the number of carbon / oxygen atoms of L in the general formula (2) and the glass transition point obtained from the results of Table 1.

  As is clear from the results shown in Table 1 and FIG. 1, the polymers of Examples 2-1 to 2-9 exhibit a higher refractive index than the homopolymers of known monomers of Comparative Example 2-1. Moreover, all of the polymers of Examples 2-1 to 2-10 exhibit a lower Abpe number than the homopolymers of known monomers of Comparative Example 2-1.

  In addition, any of the polymers in Examples has a glass transition point of 156 ° C. or less, and can be easily molded by heating. As shown in FIG. 2, in the structure of the repeating unit represented by the general formula (2), various glass transition temperature depending on the length of the molecular chain of the oxyalkylene group or poly (oxyethylene) group represented by L. Can be produced. Among them, the polymers of Examples 2-1 and 2-5 to 2-10 have a glass transition point lower than that of the known monomer homopolymer of Comparative Example 2-1, and thus can be molded at a lower temperature. .

  From the above, it can be seen that the resin of the present invention has at least one or more of the properties of high refractive index, low appetite, and low glass transition point as compared with homopolymers of known monomers. Therefore, the dihydric alcohol of the present invention can adjust the resin of the present invention to a desired refractive index, Abbe number, and glass transition temperature according to various optical systems, and is a high refractive thermoplastic resin for optics. It can be said that it is particularly useful as a raw material.

  Since the dihydric alcohol of the present invention can produce a high refractive index resin material with high processability, a molded article made of a polycarbonate resin of the polymer, a polyester resin, a camera lens, an optical disk lens, It can be used for an optical element such as an fθ lens, an optical element of an image display medium, an optical film, or a prism.

Claims (7)

A dihydric alcohol represented by the following general formula (1).

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ] A polycarbonate resin comprising a repeating unit represented by the following general formula (2) in a polymer.

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]   The polycarbonate resin according to claim 2, wherein the molar ratio of the repeating unit represented by the general formula (2) contained in the polymer is 10% or more. The polycarbonate resin according to claim 2 or 3, further comprising at least one repeating unit selected from repeating units represented by the following general formulas (3) and (4) in the polymer. .

[In General Formulas (3) and (4), T represents an oxyalkylene group having 2 to 12 carbon atoms, a poly (oxyethylene) group having 2 to 12 carbon atoms, or a single bond. R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may be the same or different from each other. Good. U represents an alkylene group having 1 to 13 carbon atoms, an alkylidene group having 2 to 13 carbon atoms, a cycloalkylene group having 5 to 13 carbon atoms, a cycloalkylidene group having 5 to 13 carbon atoms, and 6 to 13 carbon atoms. arylene group, Furuoreniden, -O -, - S -, - SO 2 -, - CO- or a single bond. R1, R2, T and U may be different for each structural unit. ] A polyester resin comprising a repeating unit represented by the following general formula (2) in a polymer.

[In the formula, L represents an oxyalkylene group having 2 to 12 carbon atoms or a poly (oxyethylene) group having 2 to 12 carbon atoms. ]   A molded body comprising the polycarbonate resin or polyester resin according to any one of claims 2 to 5.   An optical element comprising the polycarbonate resin or polyester resin according to any one of claims 2 to 5.

Images