JP2002322264A - Method for producing aromatic-aliphatic copolymerized polycarbonate - Google Patents

Abstract

[PROBLEMS] To provide a method for producing an aromatic-aliphatic copolymer polycarbonate excellent in heat stability that maintains high transparency and good hue even under high temperature and long time polymerization conditions. . An aromatic-aliphatic copolymer polycarbonate obtained by melt polycondensation of an aromatic carbonate diester, a dihydroxy compound having an alicyclic structure and an aromatic dihydroxy compound in the presence of an alkali metal and / or alkaline earth metal catalyst. In the production of 5,7-di-t-butyl-3-
(3,4-dimethylphenyl) -3H-benzofuran-
Add 2-one.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for producing an aromatic-aliphatic copolymerized polycarbonate resin having excellent hue and heat stability by transesterification.

[0001]

2. Description of the Related Art A polycarbonate obtained by interfacial polymerization of 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 resistant to polycarbonate. Because of its excellent mechanical properties such as impact resistance, 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 does not have sufficient performance to be widely used for applications such as optical recording materials and optical lenses. For the purpose of solving such a drawback of the BPA-type polycarbonate, a copolymerized polycarbonate of BPA and tricyclo (5.2.1.02,6) decanedimethanol (hereinafter, referred to as TCDDM) has been proposed (Japanese Unexamined Patent Publication (KOKAI) No. 2000-133873). No. 64-66234). However, the method for producing this copolymerized polycarbonate is:
Polycondensation of bischloroformate of BPA with TCDDM or TCDDM and BPA, bischloroformate of TCDDM with BPA or BPA and TC
Polycondensation with DDM, a mixture of bischloroformate of BPA and bischloroformate of TCDDM and B
It merely describes a method for polycondensing PA and / or TCDDM. 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 another production method, a transesterification method in which a carbonic acid diester and a dihydroxy compound are polycondensed in a molten state 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.

[0002]

DISCLOSURE OF THE INVENTION The present invention relates to a transesterification method for an aromatic-aliphatic copolymer polycarbonate having excellent heat stability which maintains high transparency and good hue even under high temperature and long time polymerization conditions. It is intended to provide a method of manufacturing with.

[0003]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that 5,7-di-t-butyl-3- (represented by the following structural formula (I) By adding 3,4-dimethylphenyl) -3H-benzofuran-2-one, an aromatic compound having extremely excellent thermal stability can be obtained.
The inventors have found that an aliphatic copolymerized polycarbonate can be obtained, and have completed the present invention.

[0004]

Embedded image

That is, the present invention provides an aromatic-aliphatic dimer of an aromatic dicarbonate and an alicyclic dihydroxy compound and an aromatic dihydroxy compound by melt polycondensation in the presence of an alkali metal and / or alkaline earth metal catalyst. In producing the copolymerized polycarbonate, 5,7-di-t-butyl-3- represented by the above structural formula (I) is used.
(3,4-dimethylphenyl) -3H-benzofuran-
It is intended to provide a method for producing an aromatic-aliphatic copolymerized polycarbonate characterized by adding 2-one.

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

[0007]

Embedded image (In the formula, Ar is a monovalent aromatic group, and Ar may be the same or different.)

The aromatic carbonic diester represented by the above general formula (III) includes diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, bispropyl phenyl carbonate, bisoctyl phenyl carbonate, bisnonyl phenyl carbonate, bismethoxy phenyl carbonate , Bisethoxyphenyl carbonate and the like are exemplified, and diphenyl carbonate is particularly preferred. The chlorine content is 1 ppm.
The following is preferred. Aromatic carbonic diester is
0.97 to 1.
It is preferably used in an amount of 2 mol, particularly preferably from 0.99 to 1.10 mol.

The 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 . ^0,8 ] pentadecanedimethanol, pentacyclo [9.2.1.
14, ^7,. 0 ^2,10 . 0 ^3,8 ] pentadecane dimethanol, 2,6-decalin dimethanol or 1,4
-Cyclohexanedimethanol and the like. Among these, in particular, tricyclo (5.2.1.0 ^2,6 )
Decane dimethanol is preferred. These dihydroxy compounds having an alicyclic structure have a carbonyl group content of 1.0 mg / g or less in terms of KOH, preferably 0.5 mg or less, more preferably 0.1 m or less, as an impurity.
g or less is used. Further, it is preferable that the content of each of chlorine and metal ions is 1 ppm or less.

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

[0011]

Embedded image (In the above formula (IV), X is

[0012]

Embedded image Wherein R ₃ and R ₄ are a hydrogen atom, a carbon atom of 1
10 to 10 alkyl groups or phenyl groups, 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. Also,
m and n represent the number of substituents and are integers from 0 to 4. )

Examples of the aromatic dihydroxy compound represented by the general formula (IV) 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) propane, 2, Bisphenols such as 2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane and 1,1-bis (4-hydroxyphenyl) cyclohexane; '
Biphenols such as -dihydroxydibiphenyl and 3,3 ', 5,5'-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, 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ) is particularly preferred. Further, two or more aromatic dihydroxy compounds can be used in combination.

In the aromatic-aliphatic copolymeric polycarbonate of the present invention, the molar ratio of the structural unit (A) derived from the aromatic dihydroxy compound and the structural unit (B) derived from the alicyclic aliphatic dihydroxy compound used as the raw materials is used. (A) /
(B) is preferably from 90/10 to 10/90, and more preferably from 80/20 to 20/80. That is, the molar ratio of this structural unit (A) / (B)
Is less than 10/90, the heat resistance is remarkably reduced, and 90 /
If it is higher than 10, the photoelastic constant and the water absorption increase, and the balance between the refractive index and the Abbe number deteriorates.

In the present invention, when producing an aromatic-aliphatic copolymerized polycarbonate, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H represented by the structural formula (I) is used. -Add benzofuran-2-one. The amount of the aromatic-aliphatic copolymerized polycarbonate 1
0.005 to 0.1 part by weight, preferably 0.01 to 0.08 part by weight, more preferably,
0.02 to 0.05 parts by weight. If the amount is less than 0.005 parts by weight, the desired effect cannot be obtained. If the amount is more than 0.1 parts by weight, various physical properties including optical properties are deteriorated, which is not appropriate. .

The 5,7-di-t- compound represented by the structural formula (I)
The timing of addition of butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one is not limited, but preferably 30% or more of the theoretical amount of by-produced aromatic monohydroxy compound is distilled. At the time of release, more preferably,
It is preferable to add at the time when 30% to 80% is distilled off, and it is also effective to add it in plural times.

In the present invention, an alkali metal compound and / or an alkaline earth metal compound is used as a catalyst.
Examples of such a compound include alkali metal salts, organic acid salts such as alkaline earth metals, inorganic salts, oxides, hydroxides,
A hydride or an alkoxide is preferably used,
These compounds can be used alone or in combination.

As the alkali metal compound, for example, 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 10 ^-9 to 10 ^-3 mol, per mol of the dihydroxy compound.
It is used in an amount of ^10-7 to ^10-5 mol.

In general, in the transesterification method, an acidic deactivator is added for the purpose of inactivating the catalyst used after the completion of the polymerization. Examples of the deactivator include phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphoric acid, phenylphosphine, phenylphosphinic acid, phenylphosphonic acid, diphenylphosphate, diphenylphosphite, diphenylphosphine, diphenylphosphine oxide, diphenylphosphine. 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 phosphate Phosphorus-containing acidic compounds such as
p-toluenesulfonic acid, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, p-toluenesulfonic acid
Aromatic sulfonic acid compounds such as pentyl toluenesulfonate, hexyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, phenethyl p-toluenesulfonate, and naphthyl p-toluenesulfonate; .

The amount of the deactivator to be added is 1/5 to 1 of the neutralization equivalent to the alkali metal and / or alkaline earth metal catalyst.
The amount is 20 times, preferably １ ／ to 10 times, and if it is less than this, the desired effect cannot be obtained, and if it is excessive, the heat resistance and mechanical properties deteriorate, which is not appropriate.

It is also effective to add a phosphonium salt of an aromatic sulfonic acid in combination with a deactivator, for example, tetrabutylphosphonium benzenesulfonate, tetrabutylphosphonium p-toluenesulfonate, butylbenzenesulfonic acid. Tetrabutylphosphonium salt, tetrabutylphosphonium octylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetramethylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, etc. No.

The amount of the phosphonium phosphonium salt of aromatic sulfonic acid is determined by the amount of aromatic-aliphatic copolymerized polycarbonate 10
0.0001 to 0.03 parts by weight, preferably 0.001 to 0.01 parts by weight with respect to 0 parts by weight. If less than this, the desired effect cannot be obtained. Physical properties deteriorate and are not suitable.

Further, additives such as an antioxidant, an ultraviolet absorber and a release agent can be added according to the use and purpose.

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 (mono, dinonylphenyl) 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, 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 the amount is less than 0.005 parts by weight, the desired effect cannot be obtained. If the amount is more than 0.1 parts by weight, heat resistance and mechanical properties are deteriorated, 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 paraffins, synthetic paraffins, silicone oil, polyethylene waxes, beeswax, monoglyceride stearate, monoglyceride palmitate, pentaerythritol tetra Examples thereof include fatty acid esters such as stearate, and these may be used alone or in combination of two or more.

In addition, flame retardants, antistatic agents, pigments, dyes and the like can be used alone or in combination.

The timing of adding these catalyst deactivators, additives and the like is not limited. Generally, after the completion of the polycondensation reaction, the resin is added while the resin is in a molten state, or the resin is once cooled into pellets and then re-melted. A method of mixing is adopted.

There is no particular limitation on the method of addition.
Examples thereof include a method of directly charging and mixing into a polymerization apparatus, and a method of kneading using a single-screw or twin-screw extruder. When using an extruder, the temperature of the molten resin should be
It is desirable to control the temperature in the range of 300 ° C., preferably 240 ° C. to 270 ° C. If the temperature is lower than this, the additive is not sufficiently dispersed, so that the effect is not exhibited. If the temperature is higher than this, thermal deterioration of the resin is promoted and coloring is caused.

When a vent-type extruder is used under reduced pressure, low-boiling compounds such as monomers remaining in the polymer can be devolatilized and removed together with the addition and kneading of the additives. In that case, the addition of a devolatilizing aid such as water is also effective for removing low boiling compounds.

Examples of the form of the additive include a method of adding it as it is without dilution, a method of adding it after diluting it in a soluble solvent, and a method of adding it in the form of a master batch, but there is no particular limitation.

The weight average molecular weight of the aromatic-aliphatic copolymer polycarbonate used in the present invention is from 20,000 to
It is preferably 200,000, more preferably 40,000 to 120,000.

The transesterification according to the present invention can be carried out by a known melt polycondensation method. That is, a polycondensation reaction is carried out using the above-mentioned raw materials and catalyst while removing a monohydroxy compound by-produced by a transesterification reaction under normal pressure or reduced pressure while heating.

The reaction is generally carried out in two or more stages. Specifically, the first-stage reaction is performed at 120 to 26.
0 ° C., preferably 0.1 to 180 ° C.
The reaction is carried out for 5 hours, preferably for 0.5 to 3 hours. Next, the reaction temperature is increased while increasing the degree of pressure reduction of the reaction system, and the reaction of the aromatic dihydroxy compound, the aliphatic dihydroxy compound and the aromatic carbonic acid diester is performed.
The polycondensation reaction is performed at a temperature of 200 to 300 ° C. under a reduced pressure of mHg or less. Such a reaction may be a continuous type or a batch type. As a 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 having excellent surface renewability, such as a paddle blade, a grid blade, and a spectacle blade, is 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 this 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.

[0039]

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)
Using styrene conversion molecular weight (weight average molecular weight: Mw)
Was measured. 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.
Using a 0 cm quartz glass cell, the YI value (Yellow
Index) was measured by Nippon Denshoku Industries Co., Ltd.
A spectrocolor meter SE-2000 manufactured by KK was used.

(3) Retention stability (dYI value) A 2.0 g sample was placed in a test tube, and 1 was prepared using DRY BLOCK BATH AL-301 manufactured by SCINICS.
After drying at 20 ° C. under a nitrogen flow for 2 hours, a retention test was performed at 260 ° C. under a nitrogen flow for 2 hours. After returning the sample to room temperature, it was dissolved in 20 ml of methylene chloride, and 5.5 c
The YI value was measured using an m-quartz glass cell, and the difference (dYI) from the YI value of methylene chloride alone was evaluated. The color difference meter is a spectrocolor meter SE manufactured by Nippon Denshoku Industries Co., Ltd.
-2000 was used.

(4) Mold Hue and Light Transmittance After drying the sample at 100 ° C. for 4 hours or more, the molding temperature was set to 240 using an injection molding machine (manufactured by Yamashiro Seiki Industry Co., Ltd.).
A 2 mm-thick molded piece was manufactured at a temperature of 115 ° C. and a mold temperature of 115 ° C., and the YI value and the light transmittance were measured with a color difference meter. The color difference meter is a spectrocolor meter S manufactured by Nippon Denshoku Industries Co., Ltd.
E-2000 was used.

Example 1 6038.0 g of BPZ, 4416.5 g of TCDDM,
10025.5 g of diphenyl carbonate, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3
2.33 g of H-benzofuran-2-one (trade name: HP-136, manufactured by Ciba Specialty Chemicals) and 0.1 wt% sodium hydroxide aqueous solution as a catalyst were added to BPZ and T
1.5 × 10 ⁻⁶ mol based on the total molar amount of CDDM
/ Mol was charged into a 50 L polymerization vessel made of nickel, purged with nitrogen three times, heated to 180 ° C., and stirred and dissolved at normal pressure for 30 minutes. Next, the degree of pressure reduction is 150 mmH
g, the reaction was carried out at a polymerization temperature of 210 ° C. for 1 hour, the pressure was reduced to 15 mmHg, the polymerization temperature was changed to 230 ° C., and the reaction was carried out for 1 hour.
The reaction was performed for 2 hours under the condition of ° C. After the completion of the reaction, the produced polycarbonate was taken out under a nitrogen atmosphere and made into pellets. The weight average molecular weight of the obtained polycarbonate is 5
The solution hue was 3,7 and the YI value was 1.07. Then, the polycarbonate pellets were dried in a vacuum dryer for 1 hour.
After drying for 12 hours under the conditions of mmHg and 90 ° C., 0 parts by weight based on 100 parts by weight of butyl p-toluenesulfonate (manufactured by Tokyo Chemical Industry) and 6 times the neutralization equivalent of sodium hydroxide used as a catalyst. 0.03 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (trade name: ADK STAB 2112, manufactured by Asahi Denka) was added and mixed in the form of a master batch, and then kneaded with a twin-screw kneading extruder. Re-pelletized. The residence stability dYI value of the obtained pellets was 2.10. The pellets were dried at 100 ° C. for 4 hours, and then dried for 2 m using an injection molding machine.
An m-thick molded piece was produced. The hue of the molded piece is YI value 1.3
0, the light transmittance was 90.8%.

Example 2 6038.0 g of BPZ, 4416.5 g of TCDDM, 10025.5 g of diphenyl carbonate and a 0.1 wt% aqueous sodium hydroxide solution as a catalyst were mixed with BPZ and TCD.
1.5 × 10 ⁻⁶ mol / m with respect to the total molar amount of DM
was charged into a 50-L polymerization vessel made of nickel so that the pressure of the mixture became ol, and the atmosphere was replaced with nitrogen three times.
Stir and dissolve for minutes. Next, the polymerization reaction was started under the conditions of a degree of reduced pressure of 150 mmHg and a polymerization temperature of 210 ° C., and when 35% of the theoretically produced phenol was distilled off, one end was obtained.
The inside of the polymerization vessel was returned to normal pressure with nitrogen, and 2.33 g of 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one was added. Thereafter, the reaction was carried out at a reduced pressure of 15 mmHg and a polymerization temperature of 230 ° C. for 1 hour, and finally, the reaction was carried out at 0.2 mmHg and 240 ° C. for 2 hours. After the completion of the reaction, the produced polycarbonate was taken out under a nitrogen atmosphere and made into pellets. The weight average molecular weight of the obtained polycarbonate was 57,600, and the solution hue was a YI value of 0.98. Next, the polycarbonate pellets were treated in the same manner as in Example 1,
Physical properties were evaluated. Table 1 shows the results of the physical property evaluation.

Example 3 A polymerization reaction was carried out in the same manner as in Example 2 to obtain polycarbonate pellets having a weight average molecular weight of 57,800 and a solution hue of YI value 0.97. The polycarbonate pellets were dried in a vacuum dryer at 1 mmHg and 90 ° C. for 12 hours.
After drying for an hour, 0.03 parts by weight of tris (2,4-di-butyl) is added to 100 parts by weight of butyl p-toluenesulfonate and 100 parts by weight of polycarbonate, which is 6 times the neutralization equivalent of sodium hydroxide used as a catalyst. t-butylphenyl) phosphite and 0.02 parts by weight of 5,7-di-t-butyl-
3- (3,4-Dimethylphenyl) -3H-benzofuran-2-one was added and mixed in the form of a master batch,
The mixture was kneaded and repelletized by a shaft kneading extruder. Table 1 shows the results of evaluating the physical properties of the obtained pellets.

Example 4 6038.0 g of BPZ, 4416.5 g of TCDDM, 10025.5 g of diphenyl carbonate and 0.1 as a catalyst.
BPZ and TCDDM with 1wt% sodium hydroxide aqueous solution
1.5 × 10 ⁻⁶ mol / mol based on the total molar amount of
Then, the mixture was charged into a 50-L polymerization vessel made of nickel, purged with nitrogen three times, heated to 180 ° C., and stirred and dissolved at normal pressure for 30 minutes. Then, the reaction was carried out for 1 hour under the conditions of a degree of reduced pressure of 150 mmHg and a polymerization temperature of 210 ° C. After further changing the degree of reduced pressure to 15 mmHg and changing the polymerization temperature to 230 ° C., and reacting for 1 hour, finally 0.2 mmHg and 240 ° C. The reaction was performed under the conditions for 2 hours. After the completion of the reaction, the produced polycarbonate was taken out under a nitrogen atmosphere and made into pellets. The weight average molecular weight of the obtained polycarbonate was 58,100, and the solution hue was YI value of 1.22. Next, the polycarbonate pellets were treated in the same manner as in Example 3,
Physical properties were evaluated. Table 1 shows the results of the physical property evaluation.

Example 5 A method similar to that of Example 2 except that 23.3 g of 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one was added. Produced polycarbonate. The weight average molecular weight of the obtained pellet is 5
The solution hue was 6,800 and the YI value was 0.96. Next, the polycarbonate pellets were treated in the same manner as in Example 1 to evaluate physical properties. Table 1 shows the results of the physical property evaluation.

Comparative Example 1 A polycarbonate was prepared in the same manner as in Example 1 except that 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one was not added. Manufactured. The weight average molecular weight of the obtained pellet was 57,90.
0, solution hue was 1.20 YI value. Next, the polycarbonate pellets were treated in the same manner as in Example 1 to evaluate physical properties. Table 1 shows the results of the physical property evaluation.

[0050]

According to the present invention, when an aromatic-aliphatic copolymerized polycarbonate is produced by a transesterification method,
By adding 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, an aromatic-aliphatic copolymer having excellent hue and heat stability can be obtained. Polycarbonate can be produced, and is an extremely effective method industrially.

[0051]

[Table 1]

Continued on front page F term (reference) 4J002 CG021 EL096 FD066 GP01 GS02 4J029 AA09 AB04 AC02 AD01 AE04 AE05 BB12A BB12B BD10 BE05A BE05B BF14A BF14B BH02 DB11 DB13 HC05A HC05B 5D029 KA08

Claims (6)

[Claims] An aromatic-aliphatic copolymer by melt polycondensation of an aromatic carbonic acid diester, a dihydroxy compound having an alicyclic structure and an aromatic dihydroxy compound in the presence of an alkali metal and / or alkaline earth metal catalyst. In producing polycarbonate, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one represented by the following structural formula (I) is added. For producing an aromatic-aliphatic copolymerized polycarbonate. Embedded image 2. The 5,7-di-formula represented by the above structural formula (I)
t-butyl-3- (3,4-dimethylphenyl) -3H
-Benzofuran-2-one in an amount of from 0.005 to 0.5% based on 100 parts by weight of the aromatic-aliphatic copolymerized polycarbonate.
The method for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein 1 part by weight is added. 3. When the aromatic monohydroxy compound by-produced by the melt polycondensation is distilled out in an amount of 30% or more of the theoretical production amount, the 5,7-di-t-type compound represented by the above structural formula (I) is obtained. Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one was used in an amount of from 0.005 to 0.5% based on 100 parts by weight of the resulting aromatic-aliphatic copolymerized polycarbonate.
3. The method for producing an aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein 1 part by weight is added. 4. The aromatic-aliphatic copolymer polycarbonate according to claim 1, wherein the aromatic dihydroxy compound is 1,1-bis (4-hydroxyphenyl) cyclohexane. Manufacturing method. 5. A dihydroxy compound having an alicyclic structure,
Tricyclo represented by the following structural formula (II) (5.2.
1.0 ^2,6 ) Decane dimethanol, The process for producing an aromatic-aliphatic copolymerized polycarbonate according to any one of claims 1 to 4, characterized in that: Embedded image 6. The method according to claim 1, wherein the aromatic carbonic diester is diphenyl carbonate.
The method for producing an aromatic-aliphatic copolymerized polycarbonate according to the above item. [0001]