JP2002265587A - Process for producing aromatic/aliphatic copolycarbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing an aromatic/aliphatic copolycarbonate useful for an optical material, scarcely occurring any foreign substance, and excellent in color hue. SOLUTION: The process for producing an aromatic/aliphatic copolycarbonate is characterized in subjecting an aromatic carbonic diester, an aliphatic dihydroxy compound to melt polymerization in the presence of an alkali metal and/or alkaline earth metal catalyst in a reaction system comprising two or more reactors connected to one another, wherein the flow velocity of the molten reaction mixture in the pipelines in the connecting parts is controlled to 0.004 m/s or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic-aliphatic copolymer polycarbonate resin which has excellent hue and hardly generates foreign matter 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, the method for producing this copolymerized polycarbonate is as follows: (1) Bischloroformate of BPA and T
(2) polycondensation of CDDM or TCDDM and BPA, (2) polycondensation of bischloroformate of TCDDM with BPA or BPA and TCDDM, (3) BP
Only the method of polycondensing a mixture of the bischloroformate of A with the bischloroformate of TCDDM with BPA and / or TCDDM is described. 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 phosgene method (chloroformate method) is known. In this transesterification method, since the reaction mixture is heated to a high temperature, there is a problem that superior properties such as transparency of the polycarbonate are impaired due to generation of insoluble foreign matters due to coloring and a branching reaction which is a side reaction. Was. In particular, in the case of polycarbonate used for optical applications such as various lenses, prisms, optical disk substrates, etc., coloring and foreign matters are not preferable in terms of products.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to produce an aromatic-aliphatic copolymer polycarbonate which is free of coloring, suppresses the occurrence of burns, and has excellent optical properties. It is assumed that.

[0004]

Means for Solving the Problems The present inventors have made intensive studies in view of the above circumstances, and as a result, have reached the present invention. That is, the present invention is as follows. (1) Aromatic carbonic acid diester, at least one aliphatic dihydroxy compound having an alicyclic structure, and at least one
And an aromatic dihydroxy compound of an alkali metal and / or
Or aromatic polymerizable by melt polymerization in a reaction system in which two or more reactors are connected in the presence of an alkaline earth metal catalyst
In the method for producing an aliphatic copolymerized polycarbonate, the flow rate of the molten reaction mixture in the pipe at the connection portion is set to 0.004.
A method for producing an aromatic-aliphatic copolymerized polycarbonate, which is at least m / s. (2) The method for producing an aromatic-aliphatic copolymer polycarbonate according to the above (1), wherein the flow rate of the reaction mixture is 0.008 m / s or more. (3) The reaction mixture in the pipe through which the molten reaction mixture passes has a weight average molecular weight of 10,000 or more.
The method for producing the aromatic-aliphatic copolymer polycarbonate according to (1). (4) The aromatic-aliphatic copolymer polycarbonate according to any one of the above (1) to (3), wherein the total of the average residence times in the pipe through which the molten reaction mixture passes is 2 hours or less. Manufacturing method. (5) The pipe through which the molten reaction mixture passes is a double-pipe inner pipe, and the temperature of the heat medium flowing through the outer pipe is set to substantially the same temperature as the reaction mixture in the reaction tank immediately before the pipe. )) The method for producing an aromatic-aliphatic copolymer polycarbonate according to any one of the above). (6) The piping through which the molten reaction mixture passes has an iron content of 6
The aromatic according to any one of the above (1) to (5), which is a cold drawn stainless steel pipe of 6% or less.
A method for producing an aliphatic copolymerized polycarbonate. (7) The piping through which the molten reaction mixture passes has an iron content of 6
The process for producing an aromatic-aliphatic copolymer polycarbonate according to any one of the above (1) to (5), wherein the inner surface of the stainless steel having a content of 6% or less is electropolished and finished. (8) As described in any one of (1) to (7) above, wherein the dihydroxy compound having at least one alicyclic structure is tricyclo (5.2.1.0 ^2,6 ) decanedimethanol. A method for producing an aromatic-aliphatic copolymerized polycarbonate. (9) The aromatic compound according to any one of the above (1) to (7), wherein the aromatic carbonic acid diester is diphenyl carbonate.
A method for producing an aliphatic copolymerized polycarbonate.

[0005] In the present specification, "reaction mixture"
Is a mixture containing mainly an aromatic dihydroxy compound, a dihydroxy compound having at least one alicyclic structure and an aromatic carbonic acid diester, in the presence of a transesterification catalyst or the like, subjected to a melt polycondensation reaction to obtain an aromatic-aliphatic copolymer polycarbonate. Means a mixture at the time when the polycondensation reaction in the step of producing the polycondensation reaction starts and ends or when the polycondensation reaction is proceeding.

Hereinafter, the present invention will be described in detail. The aromatic dihydroxy compound used in the reaction of the present invention is a compound represented by the following general formula (II).

[0007]

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(In the above formula (II), X is

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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. )

As the aromatic dihydroxy compound represented by the general formula (II), for example, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 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) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1 Bisphenols such as -bis (4-hydroxyphenyl) cyclohexane;
4'-dihydroxydibiphenyl, 3,3 ', 5,5'
Biphenols such as -tetramethyl-4,4'-dihydroxybiphenyl; bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) Ether and bis (4-hydroxyphenyl) ketone. Among these, 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ) is particularly preferred. Also,
Two or more aromatic dihydroxy compounds represented by the formula (II) can be used in combination.

The aliphatic dihydroxy compound having an alicyclic structure used in the reaction of the present invention includes, for example, tricyclo (5.2.1.0 ^2,6 ) decanedimethanol, β,
β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol (spiroglycol), pentacyclo [9.
2.1.1 ^3,9 . 0 ^2,10 . 0 ^4,8 ] pentadecanedimethanol, pentacyclo [9.2.1.1 ^4,7 . 0 ^2,10 . 0
^3,8 ] pentadecane dimethanol, 2,6-decalin dimethanol or 1,4-cyclohexane dimethanol. Among these, in particular, tricyclo (5.2.1.0 ^2,6 ) decane dimethanol (hereinafter TC)
DDM) is preferred. The aliphatic dihydroxy compound having an alicyclic structure has a carbonyl group content of 1.0 mg / g or less, preferably 0.5 mg / g or less, more preferably 0.1 mg / g or less in terms of KOH, as impurities. Things are used. Further, it is preferable that the content of each of chlorine and metal ions is 1 ppm or less.

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

[0013]

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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 (III) 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 diester is preferably used in an amount of 0.97 to 1.2 mol, particularly preferably 0.99 to 1.10, per 1 mol of the total of the dihydroxy compound.
It is a molar amount.

In the present invention, an alkali metal compound or an alkaline earth metal compound is used as a catalyst. Such compounds include organic acid salts such as alkali metals and alkaline earth metals, inorganic salts, oxides, hydroxides,
A hydride or an alkoxide is preferably used,
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, and cesium acetate. , Lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, hydrogen hydrogen phosphate 2 Sodium, hydrogen phosphate 2
Potassium, dilithium hydrogen phosphate, sodium diphosphate, potassium diphosphate, lithium diphosphate, disodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, phenol Sodium salt, potassium salt, cesium salt, lithium salt and the like can be mentioned.

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 10 ^-9 to 10 ^-3 mol, preferably 1 to ³ mol, per mol of the total of the dihydroxy compound.
Used in an amount of 0 ^-7 to 10 ^-5 mol

In the aromatic-aliphatic copolymer polycarbonate of the present invention, the structural unit (A) derived from the aromatic dihydroxy compound used as a raw material and the structural unit (B) derived from the aliphatic dihydroxy compound having an alicyclic structure are used. The molar ratio (A) / (B) is preferably from 90/10 to 10/90, more preferably from 80/20 to 20/80.
Is preferred. That is, the molar ratio (A) /
When (B) is lower than 10/90, the heat resistance is inferior, and when it is higher than 90/10, the photoelastic constant, the water absorption, etc. increase, and the balance between the refractive index and the Abbe number deteriorates. Absent.

As the 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 neutralization equivalent 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, tetrabutylphosphonium benzenesulfonate, tetrabutylphosphonium p-toluenesulfonate, tetrabutylphosphonium butylbenzenesulfonate, 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 oils, 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 are no particular restrictions on the timing of addition, the method of addition, and the form of addition, but it is preferable that the addition be carried out simultaneously with the addition of the catalyst deactivator or after the addition of the catalyst deactivator.

The timing of adding these catalyst deactivators, additives and the like 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 re-melting and mixing after cooling and pelletizing 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 300 ° C. under reduced pressure may be provided. For this purpose, paddle blades, lattice blades, eyeglass blades, etc. A horizontal stirring device having a stirring blade having excellent surface renewability, a multi-vent twin screw extruder, or a thin film evaporator is preferably used.

In the method of adding a catalyst deactivator or other additives in the present invention, when a multi-vent twin screw extruder is used, the temperature of the molten resin is preferably from 230 ° C to 30 ° C.
It is desirable to control the temperature at 0 ° C, more preferably within the range of 240 ° C to 270 ° C. When the temperature is lower than this temperature, the additive is not dispersed, and the effect is not exhibited. On the other hand, if it is higher than this, thermal deterioration is accelerated and causes coloring.

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 being mixed into the product. In that case, it is effective to install a raw material filter, mount a cooling water filter used for pelletizing, or mount a polymer filter at the outlet of the extruder to prevent foreign matter from entering.

The weight average molecular weight of the aromatic-aliphatic copolymer polycarbonate obtained by the method of the present invention is 30,000.
~ 200,000, preferably 50,000.
The range is from 0 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 carried out from the dihydroxy compound and the diaryl compound in the presence of a catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure while heating in the presence of a catalyst. The reaction is carried out in two or more stages,
The polymerization vessel used for the reaction is not particularly limited. For example, a stirred tank reactor, a thin film evaporation reactor, a biaxial horizontal stirring reactor,
Using a painted wall reactor, a surface renewal type twin-screw kneading reactor, etc.
A polymerization vessel using these alone or in combination is used. The polymerization can be performed either in a batch system or a continuous system. As a device for adding a stabilizer, a deactivator and the like as an additive while the polycarbonate is in a molten state after completion of the polymerization, it is also a preferable method to use an extruder or the like in combination with a polymerization device.

In the transesterification reaction according to the present invention, as in the reactor, the iron content of the pipe material through which the reaction mixture flows is 66.
It is preferable that the content be not more than weight%. It is preferable to use nickel, Hastelloy, stainless steel, etc.,
In particular, SUS316 and SUS3, which are relatively inexpensive and easy to process
Stainless steel such as 16L and SUS310S is preferable, and SUS316, SUS316L and SUS310S are preferable.
It is more preferable that the substrate is subjected to electrolytic polishing. In the case of SUS304, SUS430, and the like having a high iron content, the stability of the oxide film is low, so that the reaction mixture is dissolved with iron, which causes coloring and foreign matter. The use of a cold drawn stainless steel pipe having a smooth wall surface is preferable in that the flow becomes smooth and the generation of coloring and foreign substances is suppressed.

[0038]

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)
And the molecular weight in terms of polystyrene (weight average molecular weight: M
w). Chloroform was used as a developing solvent. (2) Solution hue (YI value) 9.0 g of a sample was dissolved in 90 ml of methylene chloride, and 5.
The YI value (yellow index) was measured using a 0 cm quartz glass cell. A spectrocolor meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as a color difference meter. (3) Foreign substance analysis 1 g of the sample was dissolved in 100 ml of methylene chloride from which dust had been removed in advance, and the number of foreign substances of 10 μm or more was determined using a particle counter KL-28B (manufactured by Lyon).

Example 1 A first vertical stirring polymerization tank (reaction conditions: 1.33 × 10 ⁴ Pa, 205) in a nitrogen gas atmosphere substantially free of oxygen.
Potassium hydroxide as a catalyst so that the molar ratio of the raw materials (diphenyl carbonate / (BPZ + TCDDM)) at 1.0 ° C. and a stirring speed of 160 rpm is 1.01.
l) with respect to 6 μmol, and diphenyl carbonate and B
PZ and a certain ratio (diphenyl carbonate / BPZ)
(Molar ratio) = 2.02).
At a flow rate of 4.3 kg / h, it is continuously supplied to the first polymerization tank, and at the same time, TCDDM is continuously supplied at a flow rate of 15.2 kg / h, and the average residence time in the first polymerization tank is 60 minutes. The liquid level was kept constant while controlling the opening of a valve provided in the reaction mixture discharge line at the bottom of the tank so that By restricting the valve opening width, the liquid was sent to the next tank at a substantially constant flow rate. Polymerization liquid (prepolymer) discharged from the tank bottom
The second, third and fourth vertical polymerization tanks and the fifth
Was supplied to a horizontal polymerization tank (Eyeglass wing polymerization machine (trade name) manufactured by Hitachi, Ltd.). Average residence time is 2nd
The liquid level was controlled so that the fourth vertical polymerization tank was 60 minutes each and the fifth horizontal polymerization tank was 90 minutes, and at the same time, phenol by-produced was distilled off. The material of each polymerization vessel is made of SUS316L which has been subjected to electrolytic polishing, and the pipe through which the reaction mixture passes is made of SUS316L which has been cold drawn. The polymerization conditions in each of the second to fifth polymerization tanks are as follows:
Second polymerization tank (220 ° C., 2.00 × 10 ³ Pa, stirring speed 160 rpm), third polymerization tank (230 ° C., 40 Pa, stirring speed 60 rpm), fourth polymerization tank (240 ° C., 40 Pa,
The stirring speed is 20 rpm), the fifth horizontal polymerization tank (245 ° C., 40
Pa, stirring speed 5 rpm). Polymer discharged from the fifth horizontal polymerization tank is introduced into a molten state continuously 3 vented biaxial extruder (46 mm ^twin screw extruder Ltd. Kobe Steel), the nearest vent of the resin supply port Before the mouth, 2 wt. %
, And devolatilized at each vent, and then cooled with water and pelletized.

The inner pipe of the double pipe installed between the first and second polymerization tanks has an inner diameter of 15 mm and a length of 4 m, and is provided between the second and third polymerization tanks, between the third and fourth polymerization tanks, and between the fourth and fourth polymerization tanks. Between the fifth polymerization tank and the fifth
The inner tube between the polymerization tank and the additive addition device has an inner diameter of 15 mm and a length of 4 m, an inner diameter of 15 mm and a length of 2 m, an inner diameter of 25 mm and a length of 3 m, and an inner diameter of 38 mm and a length of 6 m. The pipes connecting the tanks were all double pipes, and the temperature of the heat medium flowing through the double pipe outer pipe was controlled at ± 2 ° C. with respect to the temperature of the reaction mixture in the reaction tank immediately before the pipes.

Under the above-mentioned apparatus and operating conditions, continuous operation was performed for 100 hours. After 100 hours, the flow rate was measured at the first to fifth polymerization tanks and at the outlet of the extruder, and sampling was performed. Tables 1 and 2 show the evaluation results of the samples. Table 1 also shows the average flow rate and the average residence time of the reaction mixture in the pipe in this example. The composition of the master batch of the additives is Iupilon S-3000 (trade name; Mitsubishi Gas Chemical)
Based on flakes of polycarbonate manufactured by Tokyo Chemical Industry Co., Ltd.
(PTSB) is 9 times the neutralization equivalent of sodium hydroxide [27 μmol / mol (BPZ and T
Tris (2,4-di-t-butyl) phosphite (Asahi Denka Kogyo) with respect to 100 parts by weight of the aromatic-aliphatic copolymerized polycarbonate.
300p, manufactured by Adekastarb 2112)
pm, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (trade name: HP-136; manufactured by Ciba Specialty Chemicals Co., Ltd.)
Is 100 ppm, 1,6-hexanediol-bis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX25
9; 300p by Ciba Specialty Chemicals Co., Ltd.)
pm, monoglyceride stearic acid (trade name: S-100
A: manufactured by Riken Vitamin Co., Ltd.), 400 ppm, 2,2′-
Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] (trade name: LA, manufactured by Asahi Denka Kogyo KK)
-31) is 1000 ppm, a toning agent (manufactured by Mitsubishi Chemical Corporation;
(Diaresin Blue-G, trade name) was adjusted to 0.3 ppm. The results are shown in Table 1.

Example 2 The procedure of Example 1 was repeated, except that the pipe through which the reaction mixture passed was subjected to cold drawing and the inner surface of the pipe was further subjected to electrolytic polishing. The results are also shown in Table 1.

Example 3 An inner diameter of 80 mm and a length of 3 provided between the first and second polymerization tanks
m, and an inner diameter of 65 m between the second and third polymerization tanks.
m, and the length was 1.5 m. The results are also shown in Table 1.

Example 4 A molten mixture prepared by mixing diphenyl carbonate and BPZ at a fixed ratio (diphenyl carbonate / BPZ (molar ratio) = 2.02) was placed in a first polymerization tank at 27.2 kg / h.
6. At the same time, TCDDM was supplied at a flow rate of 7.
The same operation as in Example 1 was performed, except that the water was continuously supplied at a flow rate of 6 kg / h. The results are also shown in Table 1.

Comparative Examples 1, 2, 3 The piping between the third and fourth polymerization tanks was 65 mm in inner diameter and 2 m in length.
A pipe between the fourth and fifth polymerization tanks has an inner diameter of 65 mm, a length of 3 m,
The pipe between the fifth polymerization tank and the extruder has an inner diameter of 65 mm and a length of 6 m
The procedure was performed in the same manner as in Example 1, except that The results are shown in Table 2.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

According to the present invention, it is possible to produce an aromatic-aliphatic copolymer polycarbonate excellent in hue with almost no generation of foreign matter, and the present invention is extremely effective industrially.

 ──────────────────────────────────────────────────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 AC02 AD01 AE04 BB09A BB09B BB12A BB13A BB13B BD05A BD07A BD09A BE05A BF14A BF30 BG08X BH02 DB07 DB11 DB13 HC05A JA091 JA121 JA261 JA301 JB171 JB201 JC571 JC731 JF021 JF031 JF041 JF051 JF131 JF141 JF151 JF161 KE02 KE02KE

Claims (9)

[Claims] 1. An aromatic carbonate diester and at least one aliphatic dihydroxy compound having an alicyclic structure and at least one aromatic dihydroxy compound in the presence of an alkali metal and / or an alkaline earth metal catalyst. In the method for producing an aromatic-aliphatic copolymerized polycarbonate which is melt-polymerized in a reaction system in which the above reactors are connected, the flow rate of the molten reaction mixture in the pipe at the connection portion is set to 0.004 m / s or more. Aromatic
A method for producing an aliphatic copolymerized polycarbonate. 2. The process for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein the flow rate of the reaction mixture is 0.008 m / s or more. 3. The process for producing an aromatic-aliphatic copolymerized polycarbonate according to claim 1, wherein the weight average molecular weight of the reaction mixture in the pipe through which the molten reaction mixture passes is 10,000 or more. 4. The sum of the average residence times in the pipe through which the molten reaction mixture passes is less than 2 hours.
4. The method for producing the aromatic-aliphatic copolymer polycarbonate according to any one of the above items 3. 5. The pipe through which the molten reaction mixture passes is a double-pipe inner pipe, and the temperature of the heating medium flowing through the outer pipe is substantially the same as the temperature of the reaction mixture in the reaction tank immediately before the pipe.
5. The method for producing an aromatic-aliphatic copolymer polycarbonate according to any one of the above items 4. 6. The aromatic-fat according to claim 1, wherein the pipe through which the molten reaction mixture passes is a cold drawn stainless steel pipe having an iron content of 66% or less. For producing aromatic copolymer polycarbonate. 7. The aromatic pipe according to claim 1, wherein the pipe through which the molten reaction mixture passes is stainless steel whose inner surface having an iron content of 66% or less is electropolished and finished. A method for producing an aliphatic copolymerized polycarbonate. 8. The dihydroxy compound having at least one alicyclic structure is tricyclo (5.2.1.0 ^2,6 )
8. Any one of claims 1 to 7, which is decandimethanol.
The method for producing an aromatic-aliphatic copolymerized polycarbonate described in the above item. Embedded image 9. The method for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein the aromatic carbonic acid diester is diphenyl carbonate.