WO2013183172A1

WO2013183172A1 - Method for producing thermoplastic resin

Info

Publication number: WO2013183172A1
Application number: PCT/JP2012/073963
Authority: WO
Inventors: 輝幸重松; 学松井; 丹藤　和志; 和徳布目
Original assignee: 帝人株式会社
Priority date: 2012-06-05
Filing date: 2012-09-12
Publication date: 2013-12-12

Abstract

The purpose of the present invention is to provide a method for producing a thermoplastic resin having good hue, excellent molding fluidity, and having few gel byproducts. This method involves producing the thermoplastic resin by reacting (i) a dihydroxy component with (ii) a carbonic acid diester component, a dicarboxylic acid component or a mixture thereof. The method for producing the thermoplastic resin is characterized in that: 9,9-Bis(4-(2-hydroxyethoxy)phenyl)fluorene is used as the dihydroxy component, the purity of which is at least 98%; the content of a polymer (1) represented by formula (1) is less than 0.5% but not less than 0.01%; the content of a polymer (2) represented by formula (2) is less than 0.5% but not less than 0.01%; and the total content of polymer (1) and polymer (2) is less than 1.0% but not less than 0.02%.

Description

Method for producing thermoplastic resin

The present invention relates to a thermoplastic resin using 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter sometimes abbreviated as BPEF) having a low content of impurities affecting physical properties as a raw material. It relates to a manufacturing method.

BPEF is promising as a raw material for resins having heat resistance, transparency, high refractive index and molding fluidity such as epoxy resin, polyester resin, polycarbonate resin, and polyester carbonate resin. These resins are expected as optical materials such as automotive headlamp lenses, CD, CD-ROM pickup lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, and projection lenses for rear projection televisions.
In order to obtain a resin excellent in hue and molding fluidity used in these applications, it is necessary that BPEF as a raw material has high purity. Impurities include substances that induce resin coloring, substances that affect physical properties such as resin molding fluidity, and substances that form gels and become foreign substances. It is necessary to have a small content of impurities that are pure and affect physical properties.
Patent Document 1 discloses a method for producing BPEF in which fluorenone and phenoxyethanol are subjected to dehydration condensation using sulfuric acid and thiols as catalysts. According to Patent Document 1, high-purity BPEF can be obtained. However, Patent Document 1 only describes means relating to removal of sulfuric acid as a catalyst, there is no knowledge about purification of other impurities, and when used as a raw material for resin, molding fluidity and hue deterioration are not known. There is no examination.
Patent Document 2 describes the melting point and crystal structure of BPEF. According to Patent Document 2, it is described that the obtained BPEF is a polymer raw material having excellent volumetric efficiency and the like. However, even in Patent Document 2, no examination has been made on the content of impurities, and there is a problem in the molding fluidity and hue of the resin. In addition, the metal catalyst tends to remain in the monomer and has a drawback of being easily colored when made into a resin.
JP 2010-24248 A Japanese Patent No. 4140975

An object of the present invention is to provide a method for producing a thermoplastic resin having a good hue, excellent molding fluidity and less gel byproduct.
When the present inventors produce a thermoplastic resin using BPEF as a raw material, the purity and the content of the multimer represented by the formulas (1) and (2) are within a predetermined range. The present invention was completed by finding that a thermoplastic resin excellent in molding fluidity and less by-product of gel was obtained.
In the BPEF in the present invention, when BPEF is produced by reacting fluorenone with phenoxyethanol, sulfuric acid is used as a catalyst, toluene is used as a solvent, and the molar ratio of phenoxyethanol to fluorenone is adjusted to 2 or more. Adopted.
As purification conditions, an operation of removing the unreacted phenoxyethanol from the reaction solution by concentrating the reaction solution under reduced pressure, and a decolorization step of adsorbing and purifying the reaction solution with activated carbon were adopted. Further, the operation of crystallization by dissolving the obtained BPEF crude crystals in toluene so as to have a concentration of 10 to 3% by weight was employed.
That is, the present invention is a method for producing a thermoplastic resin by reacting (i) a dihydroxy component and (ii) a carbonic acid diester component, a dicarboxylic acid component or a mixture thereof,
As the dihydroxy component, the purity is 98% or more, the content of the multimer (1) represented by the following formula (1) is less than 0.5% and 0.01% or more, and is represented by the following formula (2). The content of the multimer (2) is less than 0.5% and 0.01% or more, and the total content of the multimer (1) and the multimer (2) is less than 1.0%. It is a method for producing the thermoplastic resin, characterized by using 9,02-bis or more of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.

The present invention includes an optical molded article formed using the thermoplastic resin produced by the production method.

FIG. 1 is an SEM photograph of BPEF synthesized in Synthesis Example 1.
FIG. 2 is an SEM photograph after image analysis of the BPEF synthesized in Synthesis Example 1.
FIG. 3 is an SEM photograph of BPEF synthesized in Comparative Synthesis Example 2.
FIG. 4 is a SEM photograph after image analysis of BPEF synthesized in Comparative Synthesis Example 2.

The present invention is a method for producing a thermoplastic resin by reacting (i) a dihydroxy component and (ii) a carbonic acid diester component, a dicarboxylic acid component or a mixture thereof, and uses the following BPEF as the dihydroxy component.
[BPEF]
(purity)
In the present invention, the purity of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) can be measured by high performance liquid chromatography (HPLC), and is 98.0% or more. More preferably, it is 99.0% or more. When the purity is out of the above range, the hue of the resin is deteriorated.
(Multimers)
In the present invention, the content of the multimer (1) represented by the following formula (1) in BPEF is less than 0.5% and 0.01% or more, and the multimer represented by the following formula (2) (2 ) Is less than 0.5% and 0.01% or more, and the total content of multimer (1) and multimer (2) is less than 1.0% and 0.02% or more.
When the total content of the multimer (1) and the multimer (2) is 1.0% or more, or if either the multimer (1) or the multimer (2) is 0.5% or more, The molding fluidity of the resin decreases. Further, the multimer (1) and the multimer (2) serve as branch points to form a gel, which becomes a foreign substance when used in a molded product or a film. When the total content of the multimer (1) and the multimer (2) is less than 0.02%, it is necessary to repeatedly carry out purification, which causes a significant decrease in yield, which is not industrially preferable. More preferably, the content of the multimer (1) is less than 0.3% and 0.01% or more, and the content of the multimer (2) is less than 0.3% and 0.01% or more. ) And the multimer (2) are preferably less than 0.6% and 0.02% or more.

(Repose angle)
BPEF preferably has an angle of repose of 55 to 30 degrees. When the angle of repose is greater than 55 degrees, the fluidity is poor, and it is difficult to handle such as forming a rat hole with a hopper or a bunker. In order to eliminate the rathole, a vibrator is required when designing a hopper and a bunker, and equipment improvements are required. Furthermore, since the transportability is also lowered, there is a possibility that the transfer pipe may be clogged, and there are many restrictions on facilities. When used as a raw material for resin, etc., the amount charged into the reaction kettle is reduced, and the production efficiency is lowered. In order to increase the production efficiency, there are methods such as dividing the raw material preparation into two steps, but since the reaction kettle is opened again, it becomes susceptible to oxygen and the hue of the resin deteriorates. Even when a BPEF melting tank is installed, the amount of BPEF to be dissolved is reduced, and the resin is likely to be affected by oxygen and the like, and the resin may be colored. Or it is necessary to enlarge a dissolution tank, and restrictions arise in an installation. If it is less than 30 degrees, the amount charged to the reaction kettle when used as a raw material for the resin can be expected, but it takes a long time to heat and melt, or it is necessary to increase the temperature at which the resin is melted. This causes deterioration of quality such as hue, and reduction of production efficiency. The angle of repose is more preferably 53 to 40 degrees because the fluidity and transportability of the powdery body and the production efficiency and hue of the resin are improved.
(BPEF powder maximum area)
BPEF has a maximum area of 1.0 × 10 ⁴ μm ² It is preferable to contain 1 to 95% or more of the above powdery body. The maximum area in the powder is 1.0 × 10 ⁴ μm ² When not containing 1% or more of the above powdery body, the angle of repose becomes larger than 55 degrees, and the powdery body becomes difficult to handle as described above. It also adversely affects resin production efficiency and hue. Similarly, the angle of repose deteriorates even in the case of 95% or more. Maximum area is 1.0 × 10 ⁴ μm ² The above powdery body and the maximum area are 1.0 × 10 ⁴ μm ² When the following powdery substances coexist, BPEF that improves the production efficiency and hue of the resin can be obtained.
(Water content)
The water content of BPEF is preferably 1% by weight or less. If it exceeds 1% by weight, the angle of repose may be increased, and the fluidity and transportability of the powder will be unfavorable. Moreover, it becomes a member of the cause of coloring at the time of using for resin, and is not preferable. Furthermore, since the catalytic activity of a metal alkoxide type, which is a kind of resin catalyst, is reduced and adverse effects such as poor polymerization are caused, the catalyst to be used is limited and not preferable. Alternatively, an error in the charged weight increases and the copolymer composition is shifted, which adversely affects the reaction and is not preferable. Therefore, the amount of water contained in BPEF is more preferably 0.8% by weight or less, and still more preferably 0.5% by weight or less. As a method for suppressing the amount of moisture, it is effective to perform drying under heat and pressure during the production of BPEF and to use an aluminum moisture-proof bag for storing BPEF.
(Toluene content)
The toluene solvent content of BPEF is preferably 1.0% by weight or less. When toluene remains, it is not preferable because the fluidity and the transportability for increasing the angle of repose are lowered as in the case of the moisture content. Further, the hue of the resin is deteriorated, and an error in the amount charged becomes large during the production of the resin, which may cause a problem in the reaction. Therefore, it is more preferable that the residual amount of toluene is 0.5% by weight or less. In order to reduce the residual amount of toluene solvent, vacuum drying is effective at the time of BPEF production.
(Sulfur content)
The sulfur content of BPEF is preferably 10 ppm or less. When it is 10 ppm or more, the resin is colored when used as a raw material for the resin. The sulfur content is more preferably 5 ppm or less, and even more preferably 3 ppm or less. As a method for reducing sulfur, there is a method in which a sulfur compound such as sulfuric acid is not used as a reaction catalyst. However, a large amount of multimers (1) and multimers (2) are by-produced, and the molding fluidity of the resin is reduced. It is not preferable. In addition, there is a method of neutralizing and washing the sulfur compound in the purification step, but neutralization alone is insufficient, and water washing and rough crystallization after the neutralization step are necessary.
[Manufacturing BPEF]
A method for producing BPEF will be described. BPEF can be produced by reacting fluorenone with 2-phenoxyethanol in the presence of a sulfuric acid catalyst and then purifying the resulting reaction mixture.
When the present inventors react fluorenone and phenoxyethanol to produce BPEF, by adopting specific reaction conditions and purification conditions, the purity of the multimer represented by the formulas (1) and (2) can be reduced. It has been found that BPEF having a content in a predetermined range can be obtained. Moreover, when the BPEF was used, it discovered that the thermoplastic resin with a favorable hue, excellent shaping | molding fluidity | liquidity, and few by-products of a gel was obtained.
That is. As reaction conditions for BPEF production, conditions were used in which sulfuric acid was used as a catalyst, toluene was used as a solvent, and the feed molar ratio of phenoxyethanol to fluorenone was controlled to 2 or more.
As purification conditions, a step of removing the unreacted phenoxyethanol from the reaction solution by concentrating the reaction solution under reduced pressure and a decolorization step of adsorbing and purifying the reaction solution with activated carbon were adopted. Further, the operation of crystallization by dissolving the obtained BPEF crude crystals in toluene so as to have a concentration of 10 to 3% by weight was employed.
<Reaction process>
(Feed ratio)
The charging amount (mol) of 2-phenoxyethanol is 2 to 10 times, preferably 2 to 8 times, more preferably 2 to 4 times the charging amount (mol) of fluorene. If it exceeds 10 times, there is a high possibility that 2-phenoxyethanol will remain in the crude crystal, which inhibits the formation of the crystal structure and makes it impossible to obtain the desired BPEF powder. On the other hand, if the amount of 2-phenoxyethanol charged is less than 2 times, the amount of 2-phenoxyethanol that can react with fluorene decreases, so that side reactions are likely to occur and the number of multimers increases, making it impossible to obtain the desired BPEF. 2-Fexyethanol and multimers are difficult to reduce in water washing and crystallization, and it is necessary to reduce by-products in the reaction. The charged amount (mol) of 2-phenoxyethanol is fluorene. It is preferably 2 to 10 times the charged amount (mol).
(catalyst)
In the reaction, sulfuric acid is used as a catalyst. The type of sulfuric acid is not particularly limited. For example, dilute sulfuric acid (for example, about 30 to 90% by weight sulfuric acid), concentrated sulfuric acid (for example, sulfuric acid having a concentration of 90% by weight or more), fuming sulfuric acid, etc. can be used. If it can be added to sulfuric acid, sulfur trioxide as a precursor may be added to the reaction system as necessary.
Sulfuric acid (H ₂ SO ₄ The conversion amount is 0.001 to 10 times, preferably 0.001 to 5 times, and more preferably about 0.001 to 3 times with respect to fluorenone (1 mole) from the viewpoint of reactivity. In order to increase the coprecipitation efficiency while suppressing the mixing of sulfuric acid, sulfuric acid (H ₂ SO ₄ The conversion amount is 0.3 to 5 times, preferably 0.7 to 2.5 times, more preferably 0.8 to 2.3 times, particularly 1 to 2 times the amount of fluorenone (1 mole). It may be doubled.
(Cocatalyst)
It is preferable to use thiols as a cocatalyst. As thiols, mercaptocarboxylic acid (mercaptoacetic acid (thioglycolic acid), β-mercaptopropionic acid, α-mercaptopropionic acid, thiooxalic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.), thiocarboxylic acid (thioacetic acid, thiopropionic acid) ), Thioglycol (mercaptoethanol, etc.), alkyl mercaptan (methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, 1-octyl mercaptan, t-dodecyl mercaptan, etc., particularly C1 -4 alkyl mercaptan)), aralkyl mercaptan (benzyl mercaptan, etc.) or a salt thereof. Examples of the salt include alkali metal salts (sodium salt and the like). Thiols can be used alone or in combination of two or more.
Among these thiols, mercapto C1-6 carboxylic acid, preferably mercapto C2-6 carboxylic acid, more preferably mercapto C2-4 carboxylic acid (for example, β-mercaptopropionic acid) is preferable.
The amount of thiols used with respect to fluorenone is, for example, 0.001 to 0.1 times, preferably 0.003 to 0.03 times thiols relative to fluorenone (1 mol) from the viewpoint of suppressing mixing into the product. Times, more preferably about 0.005 to 0.02 times. The amount of sulfuric acid used with respect to thiols is, for example, about 1 to 1000 times, preferably 30 to 500 times, more preferably 50 to 400 times (particularly 100 to 300 times) sulfuric acid with respect to thiols.
(Reaction conditions)
In the reaction, fluorenone, 2-phenoxyethanol, a catalyst and a cocatalyst are charged into a reactor, and heated and stirred in the air or in an inert gas atmosphere such as nitrogen or helium and in the presence or absence of an inert solvent such as toluene or xylene. This can be done. At this time, by removing the water in the reaction system, such as catalyst-containing water and reaction product water, by performing the reaction under dehydrating conditions, the reaction proceeds faster than when not dehydrating, and the production of by-products is suppressed, The target product can be obtained with higher yield. The dehydration method is not particularly limited, and examples thereof include dehydration by adding a dehydrating agent, dehydration by reduced pressure, dehydration by azeotropy with a solvent under normal pressure or reduced pressure, and the like.
Although it does not specifically limit as a dehydrating agent used for reaction, A molecular sieve, sodium sulfate, magnesium sulfate, etc. are mentioned. The amount of the dehydrating agent is not particularly limited, but from the viewpoint of dehydration effect and economy, it is usually 0.0001 times or more, preferably 0.001 to 100 times, more preferably fluorenone (1 mole). Preferably it is 0.01 to 50 times.
(solvent)
The reaction solvent is toluene. The amount of toluene used is 0.1 times or more, preferably 0.5 to 100 times, more preferably 1 to 20 times, based on 1 part by weight of fluorenone.
(Reaction temperature)
The reaction temperature is preferably 50 to 300 ° C, more preferably 80 to 250 ° C, and still more preferably 120 to 180 ° C. The reaction can be followed by analytical means such as high performance liquid chromatography.
<Purification process>
In addition to the reaction product BPEF, the reaction mixture obtained by the reaction step contains by-products such as multimers, unreacted fluorenone, unreacted phenoxy alcohol, and catalyst. It is colored. Therefore, it is necessary to remove the by-product multimer, unreacted fluorenone, unreacted phenoxy alcohols, and catalyst by the following purification step.
(Neutralization process)
A neutralization process is a process of removing the sulfuric acid which is a catalyst in a reaction liquid mixture. In the neutralization step, an alkaline aqueous solution is added to the reaction mixture. By neutralizing and washing with an alkaline aqueous solution, sulfuric acid in the reaction mixture can be salted out as a sulfate, and can be efficiently extracted into the alkaline aqueous solution. By this method, it is possible to prevent the sulfuric acid that causes impurities from being mixed in the crude crystals of the target compound, and to obtain a high-purity target compound in a high yield.
When sulfuric acid is mixed in, the production of by-products is promoted in a later purification step, which causes a decrease in purity, hue deterioration and yield, and sufficient polymerization activity cannot be obtained when a resin such as polycarbonate is produced. There is a case.
Examples of the alkali include various bases such as inorganic bases (alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, calcium hydroxide and water. Examples include alkaline earth metal hydroxides such as magnesium oxide, alkaline earth metal carbonates such as calcium carbonate, ammonia, and the like, and organic bases (such as aliphatic, alicyclic, aromatic, and heterocyclic amines). . The alkali is preferably an alkali metal hydroxide (particularly sodium hydroxide). The amount of the base used is usually a neutral pH, for example, about pH 6-8 (particularly pH 7-8), for example, 0.5-1.5 equivalents per 1 equivalent of sulfuric acid. The amount is preferably about 0.7 to 1.3 equivalents.
Since the reaction solution is solidified when the alkali is charged in a solid state, the alkali is preferably charged as an aqueous solution. The concentration of the alkaline aqueous solution is preferably 10 to 60% by weight, more preferably 30 to 60% by weight, further preferably 30 to 55% by weight, more preferably 40 to 55% by weight, and particularly preferably 40 to 50% by weight. is there.
The alkaline aqueous solution may be added dropwise to the acidic reaction mixture continuously or intermittently. In dropping the alkaline aqueous solution, the temperature of the acidic reaction mixture may be preferably maintained at about 50 to 90 ° C., more preferably 60 to 90 ° C., and even more preferably about 70 to 90 ° C. By heating the reaction solution, the sulfate is easily distributed to the alkaline aqueous solution, which is more efficient.
A solvent such as toluene may be added at the time of washing with an alkaline aqueous solution. The additional amount is not particularly limited, but from the viewpoint of economy, it is usually 0.1 times or more, preferably 0.5 to 100 times, more preferably 1 to 20 times with respect to 1 part by weight of fluorenone. is there. Further, an organic solvent may be added. By adding an organic solvent, the distribution efficiency of the sulfate to the alkaline aqueous solution is improved, and washing can be performed more efficiently. Furthermore, water may be added after the addition of the alkaline aqueous solution. The additional amount of water is not particularly limited. Addition of water not only improves the distribution efficiency of sulfate, but also improves the separation performance of the organic solvent and water, thereby improving the washing efficiency, which is more preferable.
(Washing process)
The water washing step is a step of washing and removing sulfuric acid and unreacted 2-phenoxyethanol that could not be removed in the neutralization step in the reaction solution.
Even when the neutralization step is performed, sulfate and thiol-based sulfur compounds remain in the reaction solution, and the reaction solution contains an inorganic base derived from an alkaline aqueous solution. These not only cause a decrease in the purity of BPEF, but also may inhibit the reaction when used as a raw material for the resin. When unreacted 2-phenoxyethanol is used to produce a resin such as polycarbonate, the reaction terminal is blocked, and sufficient polymerization activity may not be obtained. Therefore, it is necessary to remove by washing with water.
Since sulfuric acid, sulfur compounds, unreacted 2-phenoxyethanol, and inorganic salts are highly distributable to water, washing with water is effective. The water used in the water washing step can be industrial water, tap water, deionized water, distilled water, or the like. It is preferable to use deionized water or distilled water because the metal content in BPEF decreases. The number of water washings is preferably performed until the water conductivity is 50 S / m or less. It is preferable to perform washing 3 to 5 times. When the electrical conductivity is high, there are a lot of inorganic salts and metals, which not only leads to a decrease in purity, but there is a possibility that an influence such as a reaction failure may occur when used as a resin raw material.
(Concentration process)
The concentration step is a step of heating the reaction solution, distilling unreacted 2-phenoxyethanol together with toluene as a reaction solvent, and concentrating the reaction solution.
2-phenoxyethanol is added in excess to the fluorenone to improve reaction efficiency and suppress by-products, and remains in the reaction solution in large quantities. If a large amount of this 2-phenoxyethanol remains in the BPEF crude crystal, formation of the crystal structure may be hindered during crystallization, and the target BPEF powder may not be obtained. Moreover, when manufacturing resin, such as a polycarbonate, the reaction terminal is blocked and sufficient polymerization activity may not be obtained. Therefore, the reaction solution is heated, and unreacted 2-phenoxyethanol is distilled together with toluene as a reaction solvent.
The heating conditions are normal pressure or reduced pressure, preferably at a pressure of 0.1 kPa to 4.7 kPa, preferably 80 to 250 ° C., more preferably 100 to 170 ° C., and even more preferably 100 to 150 ° C. To do. When the heating temperature is high, the yield and purity decrease due to the decomposition reaction. Moreover, it is preferable to distill off the whole amount of unreacted 2-phenoxyethanol.
(Decolorization process)
The decoloring step is a step of decolorizing the colored reaction solution with activated carbon. The reaction solution contains impurities such as by-products such as multimers and colored unreacted fluorenone. Therefore, it is necessary to remove impurities and decolorize, and an effective method is a method of decolorizing with activated carbon.
Solvents used for decolorization treatment include aromatic hydrocarbon solvents such as toluene and xylene, halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane, dichloromethane, 1, Halogenated aliphatic hydrocarbon solvents such as 2-dichloroethane, aliphatic and cyclic ether solvents such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, etc. Ester solvents, nitrile solvents such as acetonitrile, propionitrile, butyronitrile, benzonitrile, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone, Examples of solvents used for the reaction, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol and pentanol, and ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone, diisobutyl ketone and cyclohexanone Etc. Preferred are alcohol solvents and ketone solvents, and more preferred are methanol and acetone.
The activated carbon used is preferably powdered charcoal. It is preferable that the particle size is 1 to 150 μm and the activated carbon pores are about 50 nm to 2 nm. Also. Decoloring conditions are usually performed at room temperature or below the boiling point of the solvent, and the decoloring time is about 10 minutes to 2 hours. You may repeat a decoloring process several times as needed.
(Preliminary crystallization process)
The preliminary crystallization step is a step in which a solution obtained by adding a solvent to the neutralized, washed, concentrated, and decolored reaction mixture is cooled to less than 50 ° C. to precipitate BPEF crude crystals.
Toluene is used as the solvent. The temperature at the end of cooling is not particularly limited as long as it is lower than 50 ° C., and is usually −20 to 49 ° C., preferably 0 to 40 ° C., more preferably 10 to 30 ° C. The cooling rate is not particularly limited, and is usually 0.01 to 2 ° C. per minute, preferably 0.1 to 0.5 ° C. per minute.
The precipitated BPEF crude crystals are recovered by filtration or the like. The obtained BPEF crude crystals may be washed with toluene used in the reaction or may be dried.
Since 2-phenoxyethanol adversely affects the BPEF crystal growth, it is preferable to reduce the residual amount. Before performing the crystallization step, the BPEF crude crystal calculated by absorption at a wavelength of 254 nm in high performance liquid chromatography (HPLC) measurement. It is preferable that the purity of is not less than 95% and the residual amount of 2-phenoxyethanol is not more than 0.5%.
The residual amount of 2-phenoxyethanol in the BPEF crude crystal is controlled by controlling the feed ratio of 2-phenoxyethanol and fluorene as raw materials, and heating the reaction solution in the concentration step, and using unreacted 2-phenoxyethanol as the reaction solvent toluene. It can be reduced by distilling together.
(Crystallization process)
The crystallization step is a step of cooling a solution in which BPEF crude crystals are dissolved in toluene to precipitate a BPEF powder.
In order to obtain the BPEF powder of the present invention, it is preferable to selectively use a solvent for crystallization. Depending on the solvent used for crystallization, the crystal growth rate and the generation of crystal nuclei differ and the crystal structure changes. Along with this, the properties of the powdery body change. Therefore, toluene is used as a solvent to obtain the BPEF powder of the present invention.
The amount of the toluene solvent used is 10 to 50 times, preferably 10 to 30 times, and more preferably 10 to 25 times with respect to 1 part by weight of BPEF crude crystals. When the amount of the toluene solvent is large, not only the economy and productivity are deteriorated, but also a substantial single crystal form may not be obtained. In addition, when the amount of toluene solvent is small, a sufficient purification effect cannot be obtained, the impurities increase, and a single BPEF may not be obtained.
In the present invention, the amount of the toluene solvent relative to the BPEF crude crystals is increased more than usual, and the concentration of BPEF as a solute in the solution is preferably 3 to 10% by weight, more preferably 4 to 10% by weight. And By suppressing the precipitation of crystals by relatively reducing the concentration of BPEF, which is a solute, large crystals can be precipitated, and a BPEF powder excellent in fluidity and transportability can be obtained.
The temperature at which the BPEF crude crystals are dissolved in toluene is preferably 55 ° C. or higher, more preferably 60 to 150 ° C., and still more preferably 70 to 110 ° C. If this temperature is low, a substantially single crystal form may not be obtained.
By cooling the solution, a BPEF powder is precipitated. The deposition start temperature is preferably less than 50 ° C, more preferably 20 to 49 ° C, and even more preferably 30 to 49 ° C. The deposition start temperature is controlled by the concentration of BPEF, which is a solute in the solution, and the deposition temperature can be adjusted to a preferred temperature by adjusting to the above concentration.
The temperature at the end of cooling is usually −20 to 49 ° C., preferably 0 to 40 ° C., more preferably 10 to 30 ° C. When the crystal precipitation temperature is low, the purity tends to decrease, and when the crystal precipitation temperature is high, the loss to the solvent increases, resulting in poor economic efficiency and productivity.
The cooling rate is preferably 0.01 to 3 ° C. per minute, more preferably 0.1 to 2 ° C. per minute. During cooling, BPEF crystals may be added as seed crystals in the solution. When adding a crystal seed, it is preferable to add the crystal seed of BPEF at a metastable region width, for example, 1 to 10 ° C., preferably 1 to 3 ° C. lower than the temperature of the saturation melting point of BPEF.
The precipitated crystals are collected by filtration or the like. The obtained crystal may be washed with toluene or dried. If necessary, this crystallization may be repeatedly purified, and after crystallization, purification such as washing with water may be performed.
(Drying process)
The separated BPEF powder is dried and removed, for example, by heating under normal pressure or reduced pressure in order to dry and remove residual solvent and residual moisture, if any.
Since the obtained BPEF powder has a high purity of 99.0% or more, it can be used for applications other than those where mixing of solvents is not preferable. However, the BPEF powder is applied under normal pressure or reduced pressure. It is preferable to heat and dry.
In order to improve the hue of the BPEF powder, the interior of the dryer system is preferably replaced with an inert gas such as nitrogen during drying.
The drying temperature (final temperature) and pressure are preferably in the range of 40 to 120 ° C., more preferably in the range of 50 to 100 ° C., and the pressure (absolute pressure) is preferably in the range of 0.1 to 101.3 kPa. More preferably, it is in the range of 0.1 to 80.0 kPa. The drying time is preferably 0.5 to 12 hours. If the temperature is 120 ° C. or higher, or if the drying time is too long, the BPEF powder is colored, and if the drying temperature is 40 ° C. or lower or too short, moisture and solvent remain, which is not preferable.
The dryers used are paddle dryers, single dryers, continuous fluidized bed dryers, tornesh dryers, tower dryers, filter dryers, multi-fin processors, steam tube dryers, popper dryers, batch fluid dryers, and fluid fluid dryers. It is preferable to use a dryer, an instantaneous air dryer, a Nauta mixer type dryer, a container rotating and shaking type dryer, or the like.
(Preservation method)
A preferred method for preserving the dried BPEF powder will be described. Since BPEF powder absorbs moisture, when it is stored in a paper bag or flexible container bag, it is possible to prevent moisture absorption by using a bag of polyethylene or the like having a double structure or more and an aluminum moisture-proof bag. It is preferred to go and store. Further, when storing in a popper or silo, it is preferable to suppress moisture absorption by replacing the popper or silo with a dry inert gas such as nitrogen.
[Method for producing thermoplastic resin]
The present invention is a method for producing a thermoplastic resin by reacting BPEF described above as a dihydroxy component with a carbonic acid diester component, a dicarboxylic acid component or a mixture thereof.
Examples of the thermoplastic resin include polycarbonate resin, polyester resin, and polyester carbonate resin. These manufacturing methods will be described.
(Polycarbonate resin)
The polycarbonate resin is a resin obtained by reacting a dihydroxy component and a carbonic acid diester component. In the present invention, the aforementioned BPEF is used as the dihydroxy component. The dihydroxy component and the carbonic acid diester component may be a single component, or two or more kinds of compounds may be used for each. That is, a copolymer component may be included.
Examples of dihydroxy components that can be used with BPEF include 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis ( 4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- ( o-hydroxyphenyl) propyl] polydimethylsiloxane, aromatic diols such as 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol. In addition, aliphatic diols such as ethylene glycol and tricyclo [5.2.1.0 ^2,6 Decane dimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: An alicyclic diol such as 3,6-dianhydro-D-sorbitol, 1,4: 3,6-dianhydro-D-mannitol, 1,4: 3,6-dianhydro-L-iditol may also be included. These may be used alone or in combination of two or more.
Examples of the carbonic acid diester include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and dinaphthyl carbonate. Among them, diphenyl carbonate is preferable. These aromatic carbonic acid diesters may be used alone or in combination of two or more.
As a method for producing a polycarbonate resin, an ester exchange reaction between a dihydroxy component and a carbonic acid diester is preferably employed.
In the transesterification reaction, a diol and bisaryl carbonate are mixed in the presence of an inert gas, and usually 120 to 350 ° C. under reduced pressure in the presence of a mixed catalyst comprising an alkali metal compound catalyst or an alkaline earth metal compound or both. The reaction is preferably carried out at 150 to 300 ° C. The degree of vacuum is changed stepwise, and finally the alcohol produced at 133 Pa or less is distilled out of the system. The reaction time is usually about 1 to 4 hours.
As a polymerization catalyst, an alkali metal compound or an alkaline earth metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.
The alkali metal compound used as the catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate. Sodium stearate, potassium stearate, lithium stearate, sodium salt, potassium salt, lithium salt of bisphenol A, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.
Nitrogen-containing basic compounds used as promoters include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine Etc.
These catalysts may be used alone or in combination of two or more, and the amount of these polymerization catalysts used is 10 with respect to a total of 1 mol of the dihydroxy component. ^-9 ~ 10 ^-3 Used in molar ratios. Moreover, you may add antioxidant, a heat stabilizer, etc. for a hue improvement.
In the polycarbonate resin, the catalyst may be removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known acidic substance is preferably carried out. Specific examples of the acidic substance for deactivation include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, butyl p-toluenesulfonate, and hexyl p-toluenesulfonate. Aromatic sulfonic acid esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-phosphite Phosphites such as propyl, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, Phosphate esters such as dibutyl phosphate, dioctyl phosphate, monooctyl phosphate, diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphone Phosphonates such as diethyl phosphonate, phosphonates such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, tetrabutylphosphonium dodecylbenzenesulfonate Aromatic sulfonic acid salts such as stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride and the like, alkyl sulfuric acid such as dimethyl sulfate, and organic halides such as benzyl chloride are preferably used. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times with respect to 1 mol of the catalyst. When the amount is less than 0.01 times the catalyst amount, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.
After deactivation of the catalyst, a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. may be provided.
(Polyester resin)
The polyester resin is a resin obtained by reacting a dihydroxy component with a dicarboxylic acid component containing dicarboxylic acid and / or a reactive derivative thereof. The aforementioned BPEF is used as the dihydroxy component of the present invention. Each of the dihydroxy component and the dicarboxylic acid component may be a single component, or the dihydroxy component and / or the dicarboxylic acid component may include two or more compounds, that is, may include a copolymer component.
Other dihydroxy components that can be used with BPEF include alkylene glycols (eg, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, tetramethylene glycol (1,4-butanediol), hexanediol, neo Linear or branched C such as pentyl glycol, octanediol, decanediol _2-12 (Poly) oxyalkylene glycol (for example, diethylene glycol, triethylene glycol, dipropylene glycol); and the like. These diols can be used alone or in combination of two or more.
Preferred examples of diols used in combination with BPEF are linear or branched C _2-10 And more preferably linear or branched C _2-6 An alkylene glycol, more preferably linear or branched C _2-4 An alkylene glycol (for example, ethylene glycol, propylene glycol, tetramethylene glycol (1,4-butanediol)).
Typical dicarboxylic acids include, for example, alkane dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, etc.), alkene dicarboxylic acids (maleic acid, fumaric acid, etc.) aliphatic dicarboxylic acids; cycloalkane dicarboxylic acids Alicyclic dicarboxylic acids such as acids (cyclohexanedicarboxylic acid etc.), di- or tricycloalkanedicarboxylic acids (decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid etc.); arene dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid and the like), and biphenyl dicarboxylic acid (such as 2,2′-biphenyldicarboxylic acid) and the like. In addition, these reactive derivatives (acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride, lower grades such as dimethyl ester and diethyl ester (C _1-4 ) Derivable esters such as alkyl esters and acid halides corresponding to dicarboxylic acids) can be used.
These dicarboxylic acids may be used alone or in combination of two or more. Of these, cyclohexanedicarboxylic acid and terephthalic acid are preferable because they are inexpensive and easily available industrially.
In the present embodiment, a dicarboxylic acid component (dicarboxylic acid and / or ester-forming dicarboxylic acid derivative) and a dihydroxy component containing BPEF are subjected to a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, an interface The polyester resin can be obtained by reacting according to various methods such as a polymerization method. Among these, a melt polymerization method using no reaction solvent is preferable.
The transesterification method, which is one of the melt polymerization methods, is a method in which a polyester is obtained by reacting a dicarboxylic acid ester with a diol compound in the presence of a catalyst and transesterifying while distilling off the generated alcohol. Used for the synthesis of polyester resins.
As a catalyst for the transesterification reaction, it is desirable to use at least one metal compound. Examples of the metal element contained in the preferred metal compound include sodium, potassium, calcium, titanium, lithium, magnesium, manganese, zinc, tin, and cobalt. Among these, calcium and manganese compounds are preferable because of high reactivity and good color tone of the resulting resin. The amount of transesterification catalyst used is 10 with respect to the polyester resin produced. ^-9 ~ 10 ^-3 Used in molar ratios.
In the direct polymerization method, a polyester resin is obtained by performing a dehydration reaction between a dicarboxylic acid and a diol compound to form an ester compound, and then performing an ester exchange reaction while distilling off excess diol compound under reduced pressure. Is the method. The direct polymerization method has the advantage that no distillate of alcohol is used unlike the transesterification method, and an inexpensive dicarboxylic acid can be used as a raw material.
As a catalyst for the polymerization reaction in carrying out these melt polymerization methods, it is preferable to use at least one metal compound. Preferred metal elements include titanium, germanium, antimony, aluminum and the like. Among these, titanium and germanium compounds are particularly preferable for optical resins because of their high reactivity and excellent transparency and color tone of the resulting resin. The amount of the polymerization catalyst used is 10 with respect to the produced polyester resin. ^-9 ~ 10 ^-3 Used in molar ratios.
Moreover, when manufacturing a polyester resin, in order to advance a polymerization reaction smoothly, after a transesterification reaction is complete | finished, it is desirable to use a phosphorus compound equimolar or more with a transesterification catalyst. Examples of phosphorus compounds include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and the like. Among these, trimethyl phosphate is particularly preferable. The amount of the phosphorus compound used is 10 with respect to the produced polyester resin. ^-9 ~ 10 ^-3 Used in molar ratios.
In the transesterification reaction, a dihydroxy component, a dicarboxylic acid component, and a copolymerization component used as needed are charged into a reaction vessel equipped with a heating device, a stirrer and a distillation pipe, and a reaction catalyst is added to normal pressure inert gas atmosphere. The temperature is increased while stirring, and the reaction is allowed to proceed while distilling off by-products such as methanol produced by the reaction. The reaction temperature is 150 ° C. to 270 ° C., preferably 160 ° C. to 260 ° C., and the reaction time is usually 3 to 7 hours.
The polymerization reaction is carried out, for example, using a product after completion of the transesterification reaction in a reaction vessel equipped with a heating device, a stirrer, a distilling tube, and a vacuum addition device. If these conditions are satisfied, the polymerization reaction can be continued in the same reaction vessel used in the transesterification reaction.
The polymerization reaction is performed, for example, after adding a catalyst to the reaction vessel containing the product after completion of the transesterification reaction, while gradually raising the temperature and reducing the pressure in the reaction vessel. The pressure in the tank is finally reduced from atmospheric pressure to 0.4 kPa or less, preferably 0.2 kPa or less. The temperature in the tank is raised from 220 to 230 ° C., and finally raised to 250 to 350 ° C., preferably 260 to 320 ° C. After reaching a predetermined torque, the reaction product is extruded from the bottom of the tank. to recover. In the usual case, the reaction product can be extruded into water as a strand, cooled and then cut to obtain a pellet-shaped polyester resin.
After the completion of the polymerization reaction, a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. may be provided.
(Polyester carbonate resin)
The polyester carbonate resin is a resin obtained by reacting a dihydroxy component, a dicarboxylic acid, and a carbonic acid diester component. In the present invention, the aforementioned BPEF is used as the dihydroxy component. The dihydroxy component, dicarboxylic acid component and carbonic acid diester component may each be a single component, or each of the dihydroxy component, dicarboxylic acid component and carbonic acid diester component may contain two or more compounds.
Dihydroxy components that can be used in the present invention with BPEF include aliphatic diols such as ethylene glycol, tricyclo [5.2.1.0. ^2,6 Decane dimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: Alicyclic diols such as 3,6-dianhydro-D-sorbitol, 1,4: 3,6-dianhydro-D-mannitol, 1,4: 3,6-dianhydro-L-iditol, 1,1′-biphenyl -4,4'-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bi (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-) 3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Methylphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane , Α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene) hydroxyphenyl) -1-phenylethane, bisphenol Aromatic diols such as A can be mentioned. You may use these individually or in combination of 2 or more types.
The dicarboxylic acid component in the polyester carbonate resin includes terephthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, ethylmalonic acid and other aliphatic dicarboxylic acids, isophthalic acid, monocyclic aromatic dicarboxylic acid such as tert-butylisophthalic acid, polycyclic aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, anthracene dicarboxylic acid and phenanthrene dicarboxylic acid, biphenyldicarboxylic acid such as 2,2′-biphenyldicarboxylic acid, Examples thereof include alicyclic dicarboxylic acids such as 1,4-cyclodicarboxylic acid and 2,6-decalin dicarboxylic acid. You may use these individually or in combination of 2 or more types. Of these, terephthalic acid is preferred. In addition, acid chlorides and esters are used as these derivatives.
Examples of the carbonic diester component used in the production of the polyester carbonate resin include diphenyl carbonate, bischloroformate of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, di- A naphthyl carbonate etc. are mentioned, Especially, a diphenyl carbonate is preferable.
As a method for producing a polyester carbonate resin, a method used for producing a normal polyester carbonate resin is arbitrarily employed. Transesterification of a dihydroxy component with a dicarboxylic acid component and a carbonic acid diester component is preferably employed.
In the transesterification reaction, a diol and a dicarboxylic acid or a diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and reacted at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours.
In the transesterification reaction, a polymerization catalyst can be used to promote the reaction. As such a polymerization catalyst, an alkali metal compound, an alkaline earth metal compound or a heavy metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate. , Potassium stearate, lithium stearate, sodium salt of bisphenol A, potassium salt, lithium salt, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.
Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.
Other transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, and aluminum salts, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II ), Tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, acetic acid Lead (IV) titanium tetrabutoxide (IV) or the like is used.
These catalysts may be used alone or in combination of two or more. The amount of these polymerization catalysts used is 10 with respect to a total of 1 mol of diol and dicarboxylic acid. ^-9 ~ 10 ^-3 Used in molar ratios. These may be used alone or in combination of two or more. In the transesterification reaction, a diaryl carbonate having an electron-withdrawing substituent may be added at a later stage or after completion of the polycondensation reaction in order to reduce the hydroxy end group. Furthermore, an antioxidant or a heat stabilizer may be added to improve the hue.
In the polyester carbonate resin, the catalyst may be removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known acidic substance is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphorous esters such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorus Phosphate esters such as dioctyl acid and monooctyl phosphate, phosphones such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid , Phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and aromatics such as tetrabutylphosphonium dodecylbenzenesulfonate Organic halides such as aromatic sulfonates, stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride are preferably used. These deactivators are used in an amount of 0.01 to 50 times, preferably 0.3 to 20 times with respect to 1 mol of the catalyst. When the amount is less than 0.01 times the catalyst amount, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.
After deactivation of the catalyst, a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. may be provided.
(Pellet b value)
The thermoplastic resin obtained by the present invention has a b value of -1.0 to 10.0, preferably -1.0 to 7.0, more preferably -1.0 to 5.0, after the polymerization. It is preferable that it is the range of these. If the pellet b value is outside the above range, an optical component with good hue cannot be obtained, which is not preferable.
(Specific viscosity)
The thermoplastic resin obtained by the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.12 to 0.55 measured at 20 ° C. The thing of the range of 0.45 is more preferable. If the specific viscosity is less than 0.12, the molded product becomes brittle, and if it is higher than 0.55, the melt viscosity and the solution viscosity become high and handling becomes difficult.
(Melt viscosity)
The thermoplastic resin obtained by the present invention preferably has a melt viscosity of 30 to 300 Pa · s at 280 ° C. and a shear rate of 100 / sec, more preferably 30 to 200 Pa · s. When it is 300 Pa · s or more, handling is difficult in forming a molded product, which is not preferable.
(Number of gels)
In the thermoplastic resin obtained by the present invention, the number of gels is preferably 10 or less per 50 g of resin. More preferably, it is 5 or less, and more preferably 0. When gel exists in resin, when resin is used as a molded article or a film, it becomes a foreign material and is not preferable.

EXAMPLES Specific examples of the present invention will be described below with reference to examples, but the present invention is not limited to the following examples without departing from the gist thereof.
Purity of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF), phenoxyethanol content, multimer content, residual sulfur compound content, various powders used in Examples and the like The identification of the shape was measured by the following method. The specific viscosity of the resin, the resin pellet b value, and the resin melt viscosity were also measured by the following methods.
(1) BPEF purity, phenoxyethanol content, multimer content:
Using a mixture of eluent methanol / water in a column of chemco KROMASIL 5C18, column temperature 40 ° C., detector 254 nm, 0 min: methanol 60%, 0 → 20 min: methanol 60 → 95%, 20 → 40 min: methanol 100%, 40 → 47 min: HPLC analysis was performed with a gradient program of methanol 100 → 60%. The measurement was performed by dissolving 10 mg of the monomer in 10 ml of methanol / water (3: 2) and then filtering with a PTFE filter having a pore size of 0.2 μm. For the content of phenoxyethanol and multimers, the detected peak area was defined as the content rate.
(2) Identification of multimers (trimers, tetramers):
Using a mixed solution of 1 mM sodium iodide aqueous solution / 1 mM sodium iodide methanol solution in a column of chemco KROMASIL 5C18, 0 min: 60% of methanol, 0 → 20 min: methanol 60 → 95 at a column temperature of 40 ° C. and a detector at 254 nm. %, 20 → 40 min: methanol 100%, 40 → 47 min: methanol 100 → 60% after separation of each component by LC, identification of multimers by Bruker Daltonics microTOF focus type mass spectrum went. LC (liquid chromatography) measurement was performed by adjusting the sample concentration to 0.7 wt% and filtering with a PTFE filter having a pore size of 0.2 μm.
(3) Water content:
It quantified using Mitsubishi Chemical's automatic moisture vaporizer VA124S and coulometric titration moisture analyzer CA200.
(4) Toluene content:
1 g of BPEF was measured for 2 hours by HS-GC / MS heated at 200 ° C. Using a standard substance, a calibration curve for the peak area ratio and content was prepared, and the content was calculated.
(5) Sulfur content (S amount): Quantitative determination was performed using a Yanaco SQ-1 type / HSU-35 type and a Dionex ICS-2000 type automatic combustion halogen / sulfur analysis system.
(6) Angle of repose measurement: The angle of repose of BPEF was measured using a multifunctional physical property measuring instrument manufactured by Seishin Enterprise. The angle of repose was defined as the angle of repose of the powdery body formed in a state where the sample was naturally dropped on a Φ80 mm table from a height of 70 mm using a funnel.
(7) Powder SEM observation:
SEM observation was performed using S-3400N manufactured by HITACHI. The BPEF powder is pretreated by spraying and adhering the BPEF powder on the double-sided tape that is bonded to the measurement substrate, removing the powder that is not bonded by wind pressure using a dropper, and then E-made by HITACHI. Using 1030, a platinum sputtering process was performed for 100 to 20 seconds at a degree of vacuum of 10 to 15 Pa to prepare a measurement sample. Observation was performed at a measurement magnification of 100 times. Then, JTrim ver. 1.53C, the powdery body and the background are color-coded by image processing, and LIA32 for Win32 ver. The total area of the powder was calculated using 0.376β1. Furthermore, a powdery body having an area of 1.0 × 10 ⁴ μm ² or more is identified by visual observation using a scale, and becomes 1.0 × 10 ⁴ μm ² or more from the area ratio with the total area of the powdery body. The content of the powder was calculated in%.
(8) BPEF fluidity:
Using a conical bunker having a diameter of 2 m, a height of 3.2 m, and an inclination angle of 50 degrees, the fluidity of the powder was evaluated. The evaluation was classified according to ◎ which is not occluded, ○ which is not occluded but formation of a rat hole, and occlusion ×.
(9) BPEF transportability:
Using KSC-44 / 55NK manufactured by Kuma Engineering, a transportability test was performed at a transport distance of 3.5 m, a transport angle of 50 degrees, a screw rotation speed of 1500 rpm, and a transport speed of 4.0 m ³ / Hr. Evaluation is possible if it can be transported for 90 minutes or more, it can be transported ◎, it can be transported for 90 minutes, ○ if the powder is firmly fixed to the screw, ○, the equipment stops when the powder is fixed The case where the operation could not be performed for 90 minutes was classified as “no conveyance”.
(10) Resin pellet b value:
The resin pellet obtained after completion | finish of superposition | polymerization was put into the glass cell, and the pellet b value was measured using Nippon Denshoku Industries color difference meter SE-2000.
(11) Number of gels:
50 g of the obtained thermoplastic resin was dissolved in methylene chloride, filtered through a 20 μm mesh silk screen, the residue on the silk screen was irradiated with light having a wavelength of 254 nm, and the emitted gel was counted using a color 3D laser microscope. And the number of gels.
(12) Resin melt viscosity:
Using a nozzle with a diameter of 1 mm and a length of 10 mm, a melt viscosity at 280 ° C. and a shear rate of 100 / sec was measured with a Capirograh 1D manufactured by Toyo Seiki Seisakusho.
(13) Injection molding method:
The obtained thermoplastic resin was vacuum-dried at 100 ° C. for 4 hours, then pelletized using a vented φ30 mm twin screw extruder, and heat-dried at 100 ° C. for 8 hours. Thereafter, a lens having a thickness of 0.6 mm, a convex curvature radius of 5 mm, a concave curvature radius of 4 mm, and a φ5 mm using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature of Tg + 110 ° C. and a mold temperature of Tg-10 ° C. And a molded piece having a width of 2.5 cm, a length of 5 cm, and a thickness of 1 mm was injection molded.
(14) Formability:
The lens filling failure after molding and each molding failure were confirmed visually. Evaluation is based on the number of defective moldings when 100 shots are molded, and the molding defect rate is less than 1% (◎), 1-5% (○), and more than 5% (×). did.
Synthesis example 1
(Reaction process)
In a glass reactor equipped with a stirrer, a condenser tube and a burette, 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and 1070 g (7.78) may be abbreviated as “PhE”. Mol) was added (PhE / fluorenone = 4), and 2.3 g of β-mercaptopropionic acid was added and stirred. While maintaining the reaction temperature at 50 ° C., 570 g of 98% by weight sulfuric acid was added over 60 minutes. It was dripped. After completion of the dropwise addition, the mixture was stirred and azeotropically dehydrated for 5 hours under toluene reflux while removing water produced by the reaction.
(Neutralization process)
After the completion of the synthesis reaction, 920 g of a 48 wt% aqueous sodium hydroxide solution was added dropwise to the reaction mixture while maintaining the temperature at 80 ° C.
(Washing process)
After the dropwise addition, 3.5 kg of toluene and 1.0 kg of water were added and washed at 85 ° C. After removing the aqueous phase, the organic phase was further washed 5 times with 85 ° C. water.
(Concentration process)
By concentrating the obtained organic layer under reduced pressure, toluene and excess 2-phenoxyethanol were removed, and BPEF was crystallized.
(Decolorization process)
Crystallized BPEF was completely dissolved in methanol, 100 g of activated carbon (NoritSX Plus) was added, stirred for 1 hour, and decolorized with activated carbon. Then, methanol was removed and BPEF was solidified.
(Preliminary crystallization process)
25 g of BPEF obtained after the decolorization step was weighed, 500 g of toluene was added, and the mixture was heated to 90 ° C. to obtain a uniform solution of 5 wt% solute. While stirring this solution, it was cooled to 30 ° C. at a rate of 2 ° C. per minute to obtain BPEF crude crystals.
This BPEF crude crystal had a purity of 98.5% by HPLC, the residual PhE amount was 0.2%, and the residual multimer amount was 0.8%.
(Crystallization process)
25 g of the obtained BPEF crude crystals were weighed, 500 g of toluene was added, and the mixture was heated to 90 ° C. to obtain a uniform solution of 5 wt% solute. The solution was cooled to 30 ° C. at a rate of 2 ° C. per minute while stirring. The deposition start temperature was 45 ° C.
The precipitated crystals were taken out by filtration and dried under reduced pressure at 1.0 KPa for 6 hours at 70 ° C. in a container rotary swing dryer to obtain BPEF (1). Thereafter, the bag was stored in an aluminum moisture-proof bag.
Synthesis example 2
BPEF (2) was obtained in the same manner as in Synthesis Example 1, except that the amount charged was 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and PhE 803 g (5.84 mol).
Synthesis example 3
BPEF (3) was obtained in the same manner as in Synthesis Example 1 except that the amount charged was 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and 2140 g (15.56 mol) of PhE.
Synthesis example 4
The amount charged is 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and 1070 g (7.78 mol) of PhE, and 70 ° C., 0.5 hour, 1.0 KPa in a container rotary rocking dryer. BPEF (4) was obtained in the same manner as in Synthesis Example 1 except that drying under reduced pressure was performed.
Comparative Synthesis Example 1
A glass reactor equipped with a stirrer, a condenser tube and a burette was charged with 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and 653 g (3.8 mol) of phenoxyethanol (PhE) (PhE / fluorenone = BPEF (5) was obtained in the same manner as in Synthesis Example 1 except that 1.96).
Comparative Synthesis Example 2
The amount charged was 1080 g of toluene, 350 g (1.94 mol) of fluorenone having a purity of 99.5% and PhE1070 g (7.78 mol) (PhE / fluorenone = 4), and the concentration step and the decolorization step were not performed in the purification step. BPEF (6) was obtained in the same manner as in Synthesis Example 1 except that methanol was used as the solvent in the crystallization step.
Synthesis Examples 1 to 4 have a low content of multimers as impurities. Furthermore, the angle of repose is small, and the amount of water and the amount of residual solvent are small and good.
Comparative Synthesis Examples 1 and 2 have many trimers and tetramers. Further, Comparative Synthesis Example 2 has a large angle of repose, inferior fluidity and transportability, reduces the amount charged into the reaction kettle when used as a resin raw material, and decreases production efficiency.

Example 1 Polycarbonate (PC) resin 21.0 kg of BPEF (1) obtained in Synthesis Example 1, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “Bis-A”) 2 .81 kg, diphenyl carbonate (may be abbreviated as “DPC” hereinafter) 13.17 kg, sodium hydrogen carbonate 7.5 × 10 ⁻² g are placed in a 60 L reaction kettle equipped with a stirrer and a distiller, and nitrogen substitution is performed. Then, the mixture was heated to 215 ° C. under a nitrogen atmosphere of 101 kPa and stirred for 20 minutes. After complete dissolution, it was adjusted to 20 kPa over 15 minutes and held at 215 ° C. and 20 kPa for 20 minutes to conduct a transesterification reaction. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and held at 240 ° C. and 16 kPa for 10 minutes. Then, it adjusted to 13 kPa over 10 minutes, and hold | maintained at 240 degreeC and 13 kPa for 70 minutes. Then, it adjusted to 1.3 kPa over 10 minutes, and hold | maintained at 240 degreeC and 1.3 kPa for 10 minutes. Furthermore, it was made 130 Pa or less over 40 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 240 ° C. and 130 Pa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. The pellet was colorless and transparent.
Example 2 Polyester (Pest) Resin 17.97 kg of BPEF (1) in Synthesis Example 1, 11.70 kg of dimethyl terephthalate (hereinafter may be abbreviated as “DMT”), ethylene glycol (hereinafter abbreviated as “EG”) 2.39 kg, titanium tetrabutoxide 2.06 × 10 ⁻² g was placed in a 60 L reaction kettle equipped with a stirrer and a distiller, and was purged with nitrogen three times, and then at 220 ° C. under a nitrogen atmosphere of 101 kPa. Heat and stir for 20 minutes. After complete dissolution, methanol removal was performed at 220 ° C. After almost distilling, 17.1 ml of trimethyl phosphate and 1.85 ml of 0.5% aqueous solution of germanium oxide were added and the temperature was raised to 280 ° C. over 60 minutes and the vacuum was raised over 150 minutes. The polymerization reaction was carried out with stirring for 3 hours under the condition of 13.3 Pa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. The pellet was colorless and transparent.
Example 3 Polyester carbonate (PEC) resin 21.05 kg of BPEF (1) in Synthesis Example 1, 2.33 kg of DMT, 8.23 kg of DPC, 20.4 × 10 ⁻¹ g of titanium tetrabutoxide were added to a reaction kettle equipped with a stirrer and a distillation apparatus. And heated to 180 ° C. under a nitrogen atmosphere and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 kPa over 20 minutes, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, and a transesterification reaction was performed. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 130 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 130 Pa or less. Thereafter, the produced resin was extracted while pelletizing. The pellet was colorless and transparent.
Example 4 Polyester carbonate resin Polymerization was conducted in the same manner as in Example 3 except that BPEF (2) in Synthesis Example 2 was used. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. The pellet was colorless and transparent.
Comparative Example 1 Polyester carbonate resin 21.05 kg of BPEF (5) obtained in Comparative Synthesis Example 1, 2.33 kg of DMT, 8.23 kg of DPC and 20.4 × 10 ⁻¹ g of titanium tetrabutoxide were reacted with a stirrer and a distillation apparatus. After putting into a kettle and performing nitrogen substitution three times, the pressure reduction degree was adjusted to 20 kPa over 20 minutes, and then the temperature was raised to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 130 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 130 Pa or less. Thereafter, the produced resin was extracted while pelletizing. The pellets were colored yellow.
Comparative Example 2 Polyester carbonate resin BPEF (6) 11.05 kg, DMT 2.33 kg, DPC 8.23 kg in Comparative Synthesis Example 2 were placed in a reaction kettle equipped with a stirrer and a distillation apparatus, and heated to 180 ° C. under a nitrogen atmosphere. Stir for 20 minutes. After complete dissolution, polymerization was carried out in the same manner as in Comparative Example 1 except that 10.0 kg of BPEF (6) obtained in Comparative Synthesis Example 2 and 20.4 × 10 ⁻¹ g of titanium tetrabutoxide were added to the reaction vessel. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. The pellets were colored yellow.
The resins of Examples 1 to 4 have a low melt viscosity, excellent molding fluidity, a good hue, a small number of gels, and can be suitably used for optical molded products and films.
In Comparative Examples 1 and 2, the content of trimers and tetramers in BPEF is large, the melt viscosity of the resin is high, and the molding fluidity is low. In addition, the number of gels in the resin is large. Furthermore, Comparative Example 2 is inferior in production efficiency because it is necessary to charge the raw material in two steps. Furthermore, the hue deteriorated due to the influence of oxygen at the time of preparation.

The invention's effect

According to the production method of the present invention, a thermoplastic resin having a good hue, excellent molding fluidity and little by-product of gel can be obtained. The thermoplastic resin obtained by the present invention can be used for various optical materials such as optical lenses, prisms, optical disks, optical fibers, and optical films.

The thermoplastic resin obtained by the present invention has a good hue, excellent molding fluidity, and can suppress the by-product formation of gels. It is extremely useful as an optical member such as a substrate, an optical card, a liquid crystal panel, a headlamp lens, and an OPC binder.

Claims

A method of producing a thermoplastic resin by reacting (i) a dihydroxy component and (ii) a carbonic acid diester component, a dicarboxylic acid component or a mixture thereof, wherein the dihydroxy component has a purity of 98% or more and the following formula (1 The content of the multimer (1) represented by) is less than 0.5% and 0.01% or more, and the content of the multimer (2) represented by the following formula (2) is 0.5%. Less than, 0.01% or more, and 9,9-bis (4-) wherein the total content of the multimer (1) and the multimer (2) is less than 1.0% and more than 0.02%. (2-Hydroxyethoxy) phenyl) fluorene is used, The manufacturing method of the said thermoplastic resin characterized by the above-mentioned.
The manufacturing method according to claim 1, wherein the thermoplastic resin is a polycarbonate resin, a polyester resin, or a polyester carbonate resin.
The water content of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is 1.0% by weight or less, and the toluene content is 1.0% by weight or less. Manufacturing method.
The manufacturing method according to any one of claims 1 to 3, wherein the thermoplastic resin pellet has a b value of -1.0 to 10.0.
The method according to any one of claims 1 to 4, wherein the thermoplastic resin has a melt viscosity of 300 Pa · s or less at 280 ° C and a shear rate of 100 / sec.
An optical molded product formed using the thermoplastic resin obtained by the production method according to any one of claims 1 to 5.