JP2002249577A - Manufacturing method of aromatic series - aliphatic series copolycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an aromatic series - aliphatic series copolycarbonate useful for an optical material or the like, having excellent color shade. SOLUTION: In the manufacturing method of the aromatic series - aliphatic series copolycarbonate comprising melt polymerizing an aromatic carbonic acid diester, at least one of aromatic dihydroxy compounds and tricyclo (5. 2. 1. 0<2> ,<6> ) decanedimethanol (hereinafter abbreviated as TCDDM) represented by structural formula (1) in the presence of an alkali metal and/or an alkaline earth metal catalyst, the TCDDM to be used is continuously distilled and purified under conditions of a substantially oxygen-free inert atmosphere, <=4 of a theoretical plate number, <=190 deg.C of an overhead temperature, and <=5 of a reflux ratio, in the presence of an alkaki metal compound or an alkaline earth metal compound, and the aldehyde group content in the TCDDM is <=0.5 mg to 1 g of the TCDDM in terms of KOH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic-
The present invention relates to a method for producing an aliphatic copolymerized polycarbonate resin by a transesterification method.

[0002]

2. Description of the Related Art A polycarbonate obtained by interfacially polymerizing an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter, referred to as BPA) and phosgene in the presence of an acid binder is: Because of its excellent mechanical properties such as impact resistance, and also excellent heat resistance and transparency, it is used as an optical material for various lenses, prisms, optical disk substrates, and the like. However, polycarbonate using only BPA as the aromatic dihydroxy compound has a large photoelastic constant and relatively low melt fluidity, resulting in a large birefringence of the molded product. Since the Abbe number indicating the degree of dispersion is as low as 30, and the balance between the refractive index and the Abbe number is poor, it has a drawback that it does not have sufficient performance to be widely used for applications such as optical recording materials and optical lenses. is there. For the purpose of solving the above-mentioned drawbacks of BPA-polycarbonate, a copolymer polycarbonate of BPA and tricyclo (5.2.1.0 ^2,6 ) decane dimethanol (hereinafter, referred to as TCDDM) has been proposed. Kaisho 64-662
No. 34). However, this method for producing a copolycarbonate comprises: (1) polycondensation of bischloroformate of BPA with TCDDM or TCDDM and BPA; (2) bischloroformate of TCDDM and BPA
Polycondensing PA or BPA and TCDDM,
(3) a mixture of bischloroformate of BPA and bischloroformate of TCDDM with BPA and / or TC
It merely describes a method of polycondensing with DDM. In the production of such a copolymer of an aliphatic dihydroxy compound and an aromatic dihydroxy compound, the production process is complicated by a two-stage reaction in which a bischloroformate of the dihydroxy compound is produced and then polycondensed with the dihydroxy compound. As a result, there is a disadvantage that the manufacturing cost is increased. As a method for producing polycarbonate, a transesterification method in which a carbonic acid diester and a dihydroxy compound are polycondensed in a molten state other than the solution method (chloroformate) is known. However, in this production method, the polymerization conditions are high temperature and long time, so it is easy to color, and the catalyst remaining in the polymer causes deterioration of the polymer physical properties. Particularly, in the polycarbonate containing an aliphatic structure, the tendency is increased. It was remarkable.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a transesterified aromatic-aliphatic copolymerized polycarbonate having high transparency and good hue.

[0004]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies. As a result, the distillation purification of TCDDM was carried out under specific conditions and in a continuous manner, and the aldehyde group in TCDDM was obtained. Is 1g of TCDDM in KOH conversion
It has been found that an aromatic-aliphatic copolymer polycarbonate having an excellent hue can be obtained by melt polycondensation using TCDDM having a concentration of 0.5 mg or less, and completed the present invention.

That is, the present invention provides an aromatic carbonic acid diester and at least one aromatic dihydroxy compound, and tricyclo (5.2.1.0) represented by the following structural formula (I).
^2,6 ) TCDDM used in a method for producing an aromatic-aliphatic copolymer polycarbonate by melt-polymerizing decane dimethanol (hereinafter abbreviated as TCDDM) in the presence of an alkali metal and / or alkaline earth metal catalyst, Continuous distillation in the presence of an alkali metal compound or an alkaline earth metal compound under an inert gas atmosphere substantially free of oxygen under the conditions of four or less theoretical plates, a top temperature of 190 ° C. and a reflux ratio of 5 or less. Purified, and characterized in that the content of aldehyde groups in TCDDM is 0.5 mg or less based on 1 g of TCDDM in terms of KOH, to produce an aromatic-aliphatic copolymer polycarbonate having an excellent hue. The present invention provides a method for producing an aromatic-aliphatic copolymerized polycarbonate.

[0006] TCDDM, which is one of the raw materials of the aromatic-aliphatic copolycarbonate in the present invention, has the property of being thermally weak and easily decomposed, has a low heat history, and is rapidly purified by distillation. Desirably, the distillation conditions include an inert gas atmosphere substantially free of oxygen (preferably under a high degree of reduced pressure of 133 Pa or less), 4 or less theoretical plates, preferably 3 or less, and a top temperature of 190 ° C.
It is preferable to carry out the reaction at a temperature of 185 ° C. or less, a reflux ratio of 5 or less, preferably 3 or less. It is not preferable that an impurity component is generated. The distillation system is preferably a continuous system. In the case of a batch system, a large amount of distillation is performed at one time, so that the residence time in the storage tank is long. In addition, when the distilled and purified TCDDM is temporarily or long-term stored on a stainless steel drum or the like. At room temperature, the viscosity is high, and usually, the liquid is heated and sent by a pump or the like, so that heat history is required. On the other hand, in the case of the continuous type, the residence time in the TCDDM storage tank can be shortened by setting the distillation purification rate to the minimum necessary for stably performing the polymerization reaction, thereby producing a polycarbonate having an excellent hue. It is effective to do.

Further, the content of aldehyde groups in TCDDM is 0.5 mg / kg of TCDDM in terms of KOH.
Or less, preferably 0.3 mg or less, more preferably 0.1 mg or less by using TCDDM,
A polycarbonate having an excellent hue can be obtained. Further, as the other impurity components, those having an individual content of 1 ppm or less for chlorine and all metal ions are preferable.

[0008] The content of the carbonyl group contained as an impurity in TCDDM is quantified by measuring an absorption spectrum at 430 nm of a reaction product obtained by reacting the carbonyl group with 2,4-dinitrophenylhydrazine. The detection limit is 0.005 mg / g. A more detailed measurement method is described below. That is, after dissolving 40 mg of TCDDM in 5 ml of methanol, 1 ml is collected in a test tube. To this test tube, 1 ml of 2,4-dinitrophenylhydrazine saturated methanol solution after recrystallization twice and 2 drops of concentrated hydrochloric acid were added, and the tube was sealed, heated at 100 ° C. for 5 minutes, and then allowed to cool naturally. To room temperature. Further, 5 ml of methanol and 4 ml of a 10 wt% KOH aqueous solution were added to prepare a measurement solution. Here, all methanol used had a carbonyl compound content below the detection limit. As a blank, methanol subjected to the same operation as the above-mentioned measurement solution was used, a difference spectrum was measured with a self-recording spectrometer, and the concentration was calculated by a calibration curve using benzaldehyde as a reference substance.

In the present invention, at the time of TCDDM distillation, an alkali metal compound or an alkaline earth metal compound is used. Specific examples of such an alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, and potassium acetate. , Cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride,
Sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium bisphenol A, disodium salt of bisphenol A, potassium salt Cesium salt, dilithium salt, phenol sodium salt, potassium salt, cesium salt, lithium salt and the like are used. Among them, potassium hydroxide is particularly preferred.

[0010] Further, as the alkaline earth metal compound,
Specifically, magnesium hydroxide, calcium hydroxide,
Strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, phenyl phosphate Magnesium or the like is used. These alkali metal compounds or alkaline earth metal compounds are preferably used in an amount of 200 to the polycyclic diol.
5,000 ppm, particularly preferably 500-200 ppm.
Used in an amount of 0 ppm.

These alkali metals or alkaline earth metals are added as solids. Alternatively, there is no problem even if it is added in the form of a solution. T of TCDDM continuous distillation unit
As a material of a portion to be brought into contact with the CDDM liquid or vapor, glass lining, nickel, chromium, stainless steel, etc. are preferable because of excellent polymer hue after polymerization, but from the viewpoint of durability and cost, stainless steel is industrially used, particularly SUS.
Those having an iron content of 66% or less, such as 316, SUS316L and SUS310S, are suitable, and it is also effective to perform surface treatment such as buffing and electrolytic polishing.

As the packing material for the distillation column, a mesh such as merappak or throughr packing or a plate type is preferable because it has a small pressure loss and a large surface area, and stainless steel having an iron content of 66% or less such as SUS316 and SUS310S is preferred. Is preferred.

The aromatic carbonic diester used in the present invention is a compound represented by the following general formula (II).

[0014]

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(Wherein Ar is a monovalent aromatic group;
May be the same or different. )

The aromatic carbonic diester represented by the general formula (II) is, for example, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, bispropylphenyl carbonate, bisoctylphenyl carbonate, bisnonylphenyl carbonate, bismethoxyphenyl. Substituted diphenyl carbonates such as carbonate and bisethoxyphenyl carbonate are exemplified, but diphenyl carbonate is particularly preferred. The chlorine content is preferably 1 ppm or less. The aromatic carbonic acid diester is preferably used in an amount of 0.97 to 1.2 mol, particularly preferably 0.99 to 1.10.
It is a molar amount.

The aromatic dihydroxy compound used in the reaction of the present invention is a compound represented by the following general formula (III).

[0018]

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(In the above formula (III), X is

Embedded image

Wherein R ₃ and R ₄ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ₃ and R ₄ may combine to form a ring. R
₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen, and R ₁ and R ₂ may be the same or different. Further, m and n represent the number of substituents and are integers of 0 to 4. )

Examples of the aromatic dihydroxy compound represented by the general formula (III) include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis ( 4-hydroxy-
3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2
-Bis (4-hydroxy-3,5-dimethylphenyl)
Bisphenols such as propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane and 1,1-bis (4-hydroxyphenyl) cyclohexane ;
4,4′-dihydroxydibiphenyl, 3,3 ′, 5
Biphenols such as 5'-tetramethyl-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide,
Bis (4-hydroxyphenyl) ether, bis (4-
(Hydroxyphenyl) ketone and the like. Among these, in particular, 1,1-bis (4-hydroxyphenyl)
Cyclohexane (hereinafter referred to as BPZ) is preferred. Further, two or more aromatic dihydroxy compounds represented by the formula (III) can be used in combination.

In the present invention, an alkali metal compound or an alkaline earth metal compound is used as a catalyst for the polymerization reaction. Such compounds include organic acid salts such as alkali metals and alkaline earth metals, inorganic salts, oxides,
Hydroxides, hydrides, alkoxides and the like are preferably used, and these compounds can be used alone or in combination.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate,
Potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate,
Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, phosphoric acid Dipotassium hydrogen, dilithium hydrogen phosphate, phenylphosphoric acid 2
Sodium, bisphenol A disodium salt, 2 potassium salt, 2 cesium salt, 2 lithium salt, phenol sodium salt, potassium salt, cesium salt, lithium salt and the like.

Further, as the alkaline earth metal compound,
For example, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate,
Examples include barium hydrogen carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate and the like.

These catalysts are used in an amount of from 10 ^-9 to 10 ^-3 mol, preferably from 1 to ⁹ mol, per mol of the dihydroxy compound.
It is used in an amount of ^0-7 to ^10-5 mol.

As a catalyst deactivator, for example, phosphoric acid,
Phosphorous acid, hypophosphorous acid, phenylphosphoric acid, phenylphosphine, phenylphosphinic acid, phenylphosphonic acid,
Diphenyl phosphate, diphenyl phosphite, diphenyl phosphine, diphenyl phosphine oxide,
Diphenyl phosphinic acid, monomethyl acid phosphate, monomethyl acid phosphite, dimethyl acid phosphate, dimethyl acid phosphite, monobutyl acid phosphate, monobutyl acid phosphite, dibutyl acid phosphate, dibutyl acid phosphite, monostearyl acid phosphate, distearyl acid Phosphorus-containing acidic compounds such as phosphate, p-toluenesulfonic acid, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfonic acid
-Propyl toluenesulfonate, butyl p-toluenesulfonate, pentyl p-toluenesulfonate, hexyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, phenethyl p-toluenesulfonate, p- Aromatic sulfonic acid compounds such as naphthyl toluenesulfonate are exemplified.

The amount of the phosphorus-containing acidic compound or aromatic sulfonic acid compound to be added is 1/5 to 20 times the equivalent of neutralization with respect to the alkali metal and / or alkaline earth metal catalyst.
The amount is preferably 1/2 to 10 times the amount. If the amount is less than this, the desired effect cannot be obtained. If the amount is excessive, the heat resistance and mechanical properties decrease, which is not appropriate.

Further, aromatic sulfonate phosphonium salts can also be preferably used. For example, benzenesulfonic acid tetrabutylphosphonium salt, p-toluenesulfonic acid tetrabutylphosphonium salt, butylbenzenesulfonic acid tetrabutylphosphonium salt, octylbenzene Examples include tetrabutylphosphonium sulfonic acid salt, tetrabutylphosphonium dodecylbenzenesulfonic acid salt, tetramethylphosphonium dodecylbenzenesulfonic acid salt, tetraethylphosphonium dodecylbenzenesulfonic acid salt, and tetrahexylphosphonium dodecylbenzenesulfonic acid salt.

The amount of the phosphonium aromatic sulfonate added is from 1 to 300 ppm, preferably from 10 to 100 ppm, based on the aromatic-aliphatic copolymerized polycarbonate. If the amount is less than this, the desired effect cannot be obtained. If the amount is excessive, the heat resistance and mechanical properties are lowered, which is not appropriate.

In the present invention, it is desirable to add various known additives to the aromatic-aliphatic copolymerized polycarbonate together with the above-mentioned specific compound as long as the physical properties are not impaired.

Examples of the antioxidant include triphenyl phosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite and tris (2 -Methyl-4-ethylphenyl) phosphite,
Tris (2-methyl-4-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di-t-butylphenyl) phosphite, tris ( 2,4-di-t-butyl-
5-methylphenyl) phosphite, tris (monodinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di- Phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-
Phosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butyl-5-methylphenyl) pentaerythritol-di-phosphite 2,2-methylenebis (4,6-dimethylphenyl) octyl phosphite, 2,2-methylenebis (4-t-butyl-6-
Methylphenyl) octyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (4,6-dimethylphenyl) hexyl phosphite, 2,2-methylenebis Phosphite compounds such as (4,6-di-t-butylphenyl) hexyl phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) stearyl phosphite, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Benzene, triethylene glycol-bis [3- (3-
t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4.
8,10-tetraoxaspiro [5,5] undecane,
1,1,3-tris [2-methyl-4- (3,5-di-
Hindered phenol compounds such as [t-butyl-4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane. These may be used alone or in combination of two or more.

The amount of these antioxidants to be added is
0.005 to 0.1 parts by weight, preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the aliphatic copolymerized polycarbonate.
0.08 parts by weight, more preferably 0.01 to 0.0
If it is less than 5 weight, the desired effect cannot be obtained, and if it is excessive, the heat resistance and mechanical properties decrease, which is not appropriate.

As the ultraviolet absorber, for example, 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t- Butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-
5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole ,
2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]], 2- (4,6-diphenyl-1 , 3,5-Triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-dihydroxobenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy −
2'-carboxybenzophenone, dimethyl succinate-
1- (2-hydroxyethyl) -4-hydroxy-2,
2,6,6, -tetramethylpiperidine polycondensate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,
6, -tetramethyl-4-piperidyl) sebacate and the like. These may be used alone or in combination of two or more.

As the release agent, those generally used may be used. For example, natural and synthetic paraffins, silicone oil, polyethylene waxes, beeswax, monoglyceride stearate, monoglyceride palmitate, pentaerythritol tetrastearate And the like, and these may be used alone or in combination of two or more.

Other flame retardants, antistatic agents, pigments, dyes and the like can be used alone or in combination as required. There is no particular limitation on the timing of addition, the method of addition, and the form of addition, but it is preferable to add the catalyst simultaneously with or after the addition of the catalyst deactivator.

The timing of adding these catalyst deactivators, additives, etc. to the aromatic-aliphatic copolymerized polycarbonate is not limited. For example, a method in which the resin is added after the polycondensation reaction is completed while the resin is in a molten state, Alternatively, a method of once cooling, pelletizing, and then re-melting and mixing may be mentioned. The method of addition is not particularly limited, and examples thereof include a method of directly charging and mixing into a polymerization vessel and a method of kneading using a single-screw or twin-screw extruder. Examples of the form of addition include a method of adding the compound as it is without diluting, a method of adding the compound after dilution with a soluble solvent, and a method of adding the compound in the form of a master batch, but are not particularly limited.

After deactivation of the catalyst, a step of degassing and removing low-boiling compounds in the polymer at a temperature of 200 to 280 ° C. under reduced pressure may be provided. For this purpose, paddle blades, lattice blades, spectacle blades, etc. A horizontal stirrer equipped with a stirring blade having excellent surface renewability, a multi-vent type twin screw extruder, or a thin film evaporator is preferably used.

When the resin of the present invention is used for optical applications, it is desirable to manufacture the resin in an environment such as a clean room or a clean booth in order to prevent foreign substances from entering the product. In that case, installation of a raw material filter, mounting of a cooling water filter used during pelletization, or mounting of a polymer filter at the outlet of the extruder are effective to prevent foreign matter from entering, and have a low viscosity. A raw material filter for filtering fluid and a filter for cooling water are 1 μm or less, and a polymer filter for filtering high viscosity resin is 1 μm.
0 μm or less, preferably 5 μm or less is suitably used.

The cooling water used for pelletizing is 5 μm
Ion-exchanged water or distilled water passed through the following filter is preferable, and cooling is usually performed at a temperature of 20 ° C to 80 ° C.

In the aromatic-aliphatic copolymer polycarbonate of the present invention, the molar ratio (A) / (B) of the structural unit (A) derived from the aromatic dihydroxy compound and the structural unit (B) derived from TCDDM used as a raw material is used. ) Is 90 / 10-1
0/90, preferably 80/90.
/ 20 to 20/80 are preferred. That is, when the molar ratio (A) / (B) of this constituent unit is lower than 10/90, the heat resistance is poor, and when it is higher than 90/10, the photoelastic constant, the water absorption, and the like increase, and the refractive index and The balance of Abbe number is deteriorated, which is not preferable as an optical material.

The aromatic-aliphatic copolymer polycarbonate used in the present invention has a weight average molecular weight of 30,000 to 2
It is preferably 0.00000, more preferably 50,000 to 120,000.

The transesterification according to the present invention can be carried out by a known melt polycondensation method. That is, melt polycondensation is performed using the above-described raw materials and a catalyst while removing by-products by transesterification under heating or normal pressure or reduced pressure. The reaction is generally carried out in two or more stages.

Specifically, the reaction of the first stage is usually carried out in 12
0 to 260 ° C, preferably 180 to 240 ° C.
The reaction is carried out for up to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is increased while increasing the degree of vacuum of the reaction system to carry out the reaction of the aromatic dihydroxy compound, the aliphatic dihydroxy compound and the aromatic carbonic diester.
The polycondensation reaction is performed at a temperature of 200 to 300 ° C. under a reduced pressure of 33 Pa or less. Such a reaction may be a continuous type or a batch type. As the reaction apparatus used for performing the above reaction, a tank type, an extruder type, or a horizontal type stirring apparatus equipped with a stirring blade excellent in surface renewability such as a paddle blade, a lattice blade, an eyeglass blade, or the like is used.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

(1) Weight average molecular weight (Mw) GPC (Shodex GPC system 11)
The molecular weight was measured as a polystyrene equivalent molecular weight (weight average molecular weight: Mw). Chloroform was used as a developing solvent. (2) Solution hue (YI value) 9.0 g of sample was dissolved in 90 ml of methylene chloride,
The YI value (yellow index) was measured using a 5.0 cm quartz glass cell. The color difference meter was Nippon Denshoku Industries Co., Ltd.
A spectrocolor meter SE-2000 manufactured by KK was used.

Example 1 Using the TCDDM distillation step (apparatus) shown in FIG.
CDDM distillation was performed. Using a SUS316L stainless steel continuous distillation apparatus, two TCDDMs were collected from the tank.
At a rate of 0.0 kg / h, and 25 wt% KOH
% Methanol solution at a rate of 40 g / h continuously to the lower part of the first distillation column (102),
a, into the second distillation column (103) while removing light boiling components under the conditions of three theoretical plates, a top temperature of 180 ° C., and a reflux ratio of 3.
It was sent at a rate of 6.0 kg / h and was further fed to the second distillation column (10
3) Distillation purification under the same conditions as the first distillation column (102),
Heavier than lower part, purified TCDDM from upper part 15.2k
Feed at a rate of g / h to a TCDDM storage tank (104) controlled at 80 ° C. The filler used at this time was a through-seal packing manufactured by Sumitomo Heavy Industries, Ltd. TCDD
The aldehyde group content of TCDDM sampled from the M storage tank (104) was 0.1 mg per 1 g of TCDDM in terms of KOH. The polycondensation reaction was performed using the polycondensation reaction step (apparatus) shown in FIG. In the polycondensation reaction, a 130 L capacity first reaction tank (203a) equipped with a Max blend blade (reaction conditions: 13329 Pa, 205 ° C.,
Sodium hydroxide is used as a catalyst and BPZ (mo) so that the raw material molar ratio (diphenyl carbonate / (BPZ + TCDDM)) at a stirring speed of 160 rpm is 1.01.
l), and diphenyl carbonate and BPZ are added at a fixed ratio (diphenyl carbonate / B
PZ (molar ratio) = 2.02) and the molten mixture was mixed at a flow rate of 54.3 kg / h through a 0.6 µm raw material filter (manufactured by Nippon Seisen Co., Ltd.) with a Coriolis flow meter. The first reaction tank (203a) while controlling the opening of the valve
And TCDDM distilled at the same time by the above-mentioned method from the storage tank (201).
at a flow rate of h and a 0.2 μm raw material filter (manufactured by Nippon Pall Co., Ltd.) while continuously controlling the opening degree of the valve with a Coriolis flow meter, and the first reaction tank (203a)
The liquid level was kept constant while controlling the opening degree of the valve provided in the polymer discharge line at the bottom of the tank so that the average residence time in the tank was 60 minutes. The polymerization liquid (prepolymer) discharged from the bottom of the tank is continuously supplied to the second and third reaction tanks (203b, 203b) each having a capacity of 130L and equipped with a max blend blade.
c) and a continuous reaction vessel (203d) having a capacity of 130L and a double helical ribbon blade, and successively supplied to a fourth reaction vessel (203d), followed by a horizontal reactor (204) (glass wing polymerization machine (trade name) manufactured by Hitachi, Ltd.) Withdrawal screw (221) provided at the discharge part of the horizontal reactor so that the average residence time is 90 minutes.
And the number of rotations of the gear pump (222) was adjusted, and the mixture was continuously introduced into an extruder (205) equipped with a polymer filter (manufactured by Nippon Pall Co., Ltd., filtration accuracy: 5 μm). The resin thus obtained was cooled with pure water filtered through a 0.2 μm filter and pelletized. 2nd-4th
A reaction tank (203b to 203d) and a horizontal polymerization machine (20
The reaction conditions in 4) are respectively the second reaction tank (220 ° C.,
1999 Pa, stirring speed 160 rpm, third reaction tank (230 ° C., 40 Pa, stirring speed 60 rpm), fourth reaction tank (240 ° C., 40 Pa, stirring speed 20 rpm), horizontal polymerization machine (245 ° C., 40 Pa, stirring speed 5 rpm) And The average residence time of the second to fourth reaction tanks (203 b to 203 d) is 60 minutes for the second reaction tank and 45 minutes for the third reaction tank 45.
And the fourth reaction tank 45 minutes. The liquid level of each tank is controlled by adjusting the valve opening of the second reaction tank (203b) provided in the polymer discharge line at the bottom of the tank, and by controlling the third and fourth reaction tanks. (203c, 203d) was performed by adjusting the rotation speed of a gear pump provided in the polymer discharge line at the bottom of the tank. At the same time, phenol by-produced was distilled off. As the extruder (204), a 3-vent 46 mm twin-screw extruder (manufactured by Kobe Steel Ltd.) was used. Before the first vent, a master batch of the additive was added to the polymer at 2 wt% with respect to the polymer using a side feed compactor. Added in proportions. The composition of the master batch is based on flake-like Iupilon S-3000 (trade name; polycarbonate manufactured by Mitsubishi Gas Chemical Co., Ltd.), and butyl p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter, pTSB) Is 9 times the neutralization equivalent of sodium hydroxide [27 μmol /
mol (based on the total mol of BPZ and TCDDM)],
And bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (manufactured by Asahi Denka Kogyo Co., Ltd.) based on 100 parts by weight of the aromatic-aliphatic copolymerized polycarbonate. Name PEP-36) is 4
00 ppm, 5,7-di-t-butyl-3- (3,4-
Dimethylphenyl) -3H-benzofuran-2-one (trade name: HP-136; manufactured by Ciba Specialty Chemicals Inc.) is 100 ppm, and octadecyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate (AO-50, manufactured by Asahi Denka Kogyo KK)
Is 300 ppm, pentaerythritol tetrastearate (manufactured by NOF CORPORATION) is 300 ppm, 2,2′-
Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] (manufactured by Asahi Denka Kogyo Co., Ltd .; trade name L)
A-31) is 1000 ppm, a toning agent (Mitsubishi Chemical Corporation)
(Resin name: Diaresin Blue-G) was prepared at 0.3 ppm. The weight average molecular weight (Mw) of the obtained polycarbonate was 57,400, and the YI value was 0.9.

Comparative Example 1 The distillation conditions were set at 6 theoretical plates, the top temperature was 200 ° C., the reflux ratio was 6, and 600 kg of distilled and purified TCDDM was kept in a storage tank at room temperature under a nitrogen atmosphere for 2 weeks, and then again at 80 ° C.
A polycarbonate was produced in the same manner as in Example 1, except that the temperature was raised to ° C and the polycondensation reaction was performed. The aldehyde group content of TCDDM sampled from the TCDDM storage tank was 1.4 mg / g TCDDM in terms of KOH.
Met. The weight average molecular weight (Mw) of the obtained polycarbonate was 57000, and the YI value was 1.7.

[0048]

According to the present invention, an aromatic-aliphatic copolymer polycarbonate having an excellent hue can be produced, and the present invention is an industrially extremely effective method.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an example of a TCDDM distillation process used to practice the present invention.

FIG. 2 is a schematic view of an example of a polycondensation reaction step used for carrying out the present invention.

[Explanation of symbols]

 101 TCDDM tank 102 First distillation column 103 Second distillation column 104 TCDDM storage tank 105, 108 Gear pump 106, 107 Liquid feed pump 109, 110, 111 Heat exchanger 112, 115 TCDDM introduction line 113 KOH introduction tube 114 Light boiling discharge Line 116 Heavy matter discharge line 117 Purified TCDDM introduction line 118 Vacuum line 119 First reaction tank 201 TCDDM storage tank 202 Raw material preparation tank 203a to 203d Vertical reaction tank 204 Horizontal polymerization machine 205 Extruder 206 Weight feeder 207 Side feed compactor 208 Water tank 209 Strand cutter 210 Pellet sorter 211, 219, 220, 222, 223 Gear pump 212 Liquid feed pump 213 Max blend blade 214 Double helical blade 21 ～218 control valve 221 extracts the screw 224, 225 raw material Filter 226 polymer filter 227 flow meter 229 TCDDM circulation line 230 material circulation line 231 by-product was distilled off line 232 vent line 233 spectacle blade 234 product pellets

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Sasaki 2-4-1, Hinagahigashi, Yokkaichi City, Mie Prefecture Inside the Yokkaichi Plant of Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Toshihiro Nomura 2-4-1, Hinagahigashi, Yokkaichi-shi, Mie Prefecture F-term (reference) 4J029 AA09 AB04 BD05A BD09A HC05A JF021 JF031 JF041 JF051 JF121 JF131 JF141 JF151 JF161 KE05

Claims (5)

[Claims] 1. An aromatic carbonic acid diester and at least one aromatic dihydroxy compound, and tricyclo (5.2.1.0 ^2,6 ) decanedimethanol (hereinafter TCDDM) represented by the following structural formula (I): Abbreviation) in the presence of an alkali metal and / or alkaline earth metal catalyst, in a process for producing an aromatic-aliphatic copolymerized polycarbonate, the TCDDM used is an inert gas atmosphere substantially free of oxygen. Under a condition where the number of theoretical plates is 4 or less, the overhead temperature is 190 ° C. or less, and the reflux ratio is 5 or less, continuous distillation purification is performed in the presence of an alkali metal compound or an alkaline earth metal compound, and the aldehyde group in TCDDM is The content is 0.5 m / kg of TCDDM in terms of KOH.
g or less, the process for producing an aromatic-aliphatic copolymerized polycarbonate. Embedded image 2. TCDDM of a continuous TCDDM distillation apparatus
Material of liquid or vapor contact part is 66% iron content
The method for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, which is the following stainless steel. 3. The process for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein the filler used for continuous distillation of TCDDM is a mesh or a plate. 4. The aromatic-aliphatic copolymer according to claim 1, wherein the at least one aromatic dihydroxy compound is 1,1-bis (4-hydroxyphenyl) cyclohexane. Production method of polycarbonate. 5. The method for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein the aromatic carbonic acid diester is diphenyl carbonate.