JPH06200005A - Aromatic polycarbonate copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer improved in hydrolysis resistance, heat stability, heat resistance, oxidation resistance, transparency and moldability by reacting a specified dihydric phenol with a carbonate precursor. CONSTITUTION:1mol of a dihydric phenol mainly consisting of a dihydric phenol comprising 15-99.5mol% 2,2-bis(4-hydroxy-phenyl)-1,1,1,3,3,3-hexafluoropropane and 85-0.5mol% 1,1-bis(4-hydroxyphenyl)-1-phenylethane is reacted with 1.05-1.50mol of a carbonate precursor at 0-40 deg.C for several min to 5 hr in the presence of an acid binder and an organic solvent to obtain an aromatic polycarbonate copolymer having a specific viscosity of 0.160-0.410 as determined in the solution of 0.7g of the copolymer in 100ml of methylene chloride at 20 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel aromatic polycarbonate copolymer. More specifically, it relates to a novel aromatic polycarbonate copolymer having excellent hydrolysis resistance, thermal stability, heat resistance and oxidation resistance, and having excellent transparency and moldability.

[0002]

2. Description of the Related Art Conventionally, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), which is known as a typical aromatic polycarbonate, is reacted with a carbonate precursor such as phosgene or diphenyl carbonate. The polycarbonate obtained from bisphenol A is excellent in transparency, heat resistance and mechanical properties.
Furthermore, it is widely used as an engineering plastic because it has many excellent properties such as good dimensional accuracy. However, in recent years, it is often used at a position closer to a heat source in consideration of lightness, thinness, shortness, and further higher heat resistance, heat stability, and oxidation resistance are required in addition to optical characteristics such as light transmittance. On the other hand, when a carbonate precursor is reacted with 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (hereinafter abbreviated as bisphenol AF), the heat resistance is excellent. It is known that an aromatic polycarbonate can be obtained (Japanese Patent Publication No. 3-12283). However, the polycarbonate derived from bisphenol AF is inferior in hydrolysis resistance and thermal stability to the polycarbonate derived from bisphenol A, its glass transition temperature does not reach 160 ° C., and its heat resistance is not sufficiently satisfactory.
In addition, 1,1-bis (4-hydroxyphenyl) -1-
Phenylethane (hereinafter abbreviated as bisphenol AP)
It is also known that an aromatic polycarbonate having excellent heat resistance can be obtained by reacting a carbonate precursor with the above (JP-A-60-8317). However, the polycarbonate derived from bisphenol AP is also inferior in thermal stability to the polycarbonate derived from bisphenol A, and neither copolymer having excellent hydrolysis resistance or thermal stability has been known at all.

[0003]

An object of the present invention is to provide an aromatic polycarbonate having excellent hydrolysis resistance, heat stability, heat resistance and oxidation resistance, and having good transparency and moldability. It is in. As a result of achieving the above object, the present inventor has conducted earnest research on improvement of hydrolysis resistance and thermal stability of polycarbonate from bisphenol AP, and as a result, a specific amount of bisphenol AF was added to bisphenol AP.
Aromatic polycarbonate copolymer of a specific molecular weight range copolymerized with, has particularly excellent hydrolysis resistance, heat resistance, thermal stability, oxidation resistance, yet excellent hue, transparency, moldability It has been found to have. The present invention has been completed based on this finding.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to bisphenol AF15-99.5 mol% and bisphenol AP85.
An aromatic polycarbonate copolymer obtained by reacting a carbonate precursor with a dihydric phenol mainly consisting of 0.5 mol% to 0.5 mol% thereof.
The present invention relates to an aromatic polycarbonate copolymer having a specific viscosity of 0.160 to 0.410 measured by dissolving 20 g of methylene chloride in 100 ml of methylene chloride at 20 ° C. The bisphenol AF used for producing the aromatic polycarbonate copolymer of the present invention is obtained by the reaction of hexafluoroacetone and phenol. If the amount of impurities in bisphenol AF is too large, the transparency and thermal stability of the copolymer obtained will decrease, so recrystallization treatment is preferable, and the amount of impurities is especially determined by liquid chromatography by repeating the recrystallization treatment. It is preferable that the purity is 99.98% or more, which is reduced to 0.02% or less by means of photography. In addition, bisphenol AP is obtained by the reaction of acetophenone and phenol. If the amount of impurities of bisphenol AP is too large, the transparency and thermal stability of the obtained copolymer will be deteriorated, so that recrystallization treatment is preferable. Particularly, recrystallization treatment is repeated to determine the amount of impurities by liquid chromatography. It is preferable that the purity is 99.95% or more, which is reduced to 0.05% or less by means of graphography. The ratio of bisphenol AF and bisphenol AP used was 15 for the former.
˜99.5 mol%, the latter is 85-0.5 mol%,
Particularly, the former is preferably 15 to 95 mol% and the latter is preferably 85 to 5 mol%. If the content of bisphenol AP is less than 0.5 mol%, the desired hydrolysis resistance cannot be obtained, and if it exceeds 85 mol%, it becomes difficult to obtain sufficient thermal stability. Bisphenol AP
Is 5 mol% or more, the hydrolysis resistance is further improved, and at the same time, excellent heat resistance can be obtained.

The dihydric phenol may be copolymerized with the copolymer of the present invention in a small amount (usually 10 mol% or less). Other dihydric phenols include, for example, bisphenol A, 4,4'-dihydroxybiphenyl, bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2
-Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis ( 3,5-dimethyl-
4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide and the like can be mentioned.

Examples of the carbonate precursor to be reacted with the dihydric phenol include phosgene and diphenyl carbonate. In order to produce the aromatic polycarbonate copolymer of the present invention, a method adopted when producing a polycarbonate from usual bisphenol A, for example, a reaction between a dihydric phenol and phosgene, or a dihydric phenol and a bisaryl carbonate is used. The transesterification reaction of is preferably used. Usually, the molar ratio of dihydric phenol and phosgene is preferably 1.05 to 1.50 mol of phosgene with respect to 1 mol of dihydric phenol. The reaction between the dihydric phenol and phosgene is usually carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. A catalyst such as a tertiary amine or a quaternary ammonium salt may be used to accelerate the reaction, and a molecular weight modifier such as phenol or pt may be used.
It is desirable to use a terminating agent such as ert-butylphenol. It is preferable that the reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually 10 or higher. On the other hand, in the transesterification reaction, the dihydric phenol and the bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed under reduced pressure at 120 to 350 ° C. The degree of pressure reduction is changed stepwise, and finally the phenols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours. Moreover, you may add a molecular weight regulator and antioxidant as needed.

The aromatic polycarbonate copolymer thus obtained is a novel aromatic polycarbonate copolymer. If the molecular weight is too small, the obtained molded product becomes brittle, and if it is too large, the melt fluidity deteriorates and it becomes difficult to obtain a good molded product.
The one having a specific viscosity of 0.160 to 0.410 measured by dissolving 7 g in 100 ml of methylene chloride at 20 ° C. is particularly preferable, and one having a specific viscosity of 0.165 to 0.340 is particularly preferable. The aromatic polycarbonate copolymer of the present invention is formed into a film or other molded article. As the molding method, any method commonly used for molding aromatic polycarbonates, such as an injection molding method, a compression molding method, an extrusion molding method, a solution casting method, or the like can be arbitrarily adopted. In the molding, the aromatic polycarbonate copolymer of the present invention may be molded as it is, but if necessary, for example, a heat stabilizer, an antioxidant, a light stabilizer, a colorant, an antistatic agent, a lubricant, You may shape | mold by adding additives, such as a mold release agent. Also,
The aromatic polycarbonate copolymer of the present invention may be used as a mixture with another polycarbonate or another thermoplastic resin.

In particular, it is preferable to blend at least one of phosphite-based, phenol-based, and organic sulfur-based antioxidants in the aromatic polycarbonate copolymer of the present invention. Examples of the phosphite-based antioxidant used here include triphenylphosphite, trisnonylphenylphosphite, and tris (2,4-di-ter).
t-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecyl-monophenylphosphite,
Dioctyl-monophenyl phosphite, diisopropyl-monophenyl phosphite, monobutyl-diphenyl phosphite, monodecyl-diphenyl phosphite, monooctyl-diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol-di-phosphite, 2,2
-Methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol-di-phosphite, bis (2,4)
-Di-tert-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-te)
rt-butylphenyl) -4,4-diphenylenephosphonite and other triesters of phosphorous acid, or diesters and monoesters in which the ester moiety is substituted with an alkyl group, a phenyl group, an alkylaryl group, etc. Or may be used in combination of two or more kinds. Among them, tris (nonylphenyl) phosphite, tris (2,4-)
Di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,
4-diphenylene phosphonite is preferred.

The phenolic antioxidant is a hindered phenolic compound having a bulky group in the ortho position with respect to the hydroxyl group of the phenolic compound, for example, triethylene glycol-bis [3- (3-tert-butyl). −
5-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-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, N-N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-
Butyl-4-hydroxy-benzylphosphonate-
Diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
3,9-bis {1,1-dimethyl-2- [β- (3-t
ert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10
-Tetraoxaspiro (5,5) undecane and the like are mentioned, and among them, pentaerythritol-tetrakis [3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate is preferred.

Examples of organic sulfur antioxidants include tetrakis [methylene-3- (hexylthio) propionate] methane, tetrakis [methylene-3- (decylthio) propionate] methane, tetrakis [methylene-].
3- (laurylthio) propionate] methane, tetrakis [methylene-3- (octylthio) propionate] methane, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3 , 3'-thiodipropionate,
Ditridecyl-3,3'-thiodipropionate, 2,
2-thio-diethylenebis [3- (3,5-di-ter
t-Butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6-tert-)
Butylphenol), 2-mercaptobenzimidazole, etc., among which tetrakis [methylene-3-
(Laurylthio) propionate] methane is preferred.
The blending amount of the antioxidant is 0.001 to 1.0 part by weight with respect to 100 parts by weight of the aromatic polycarbonate copolymer.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The parts and% in the examples are parts by weight and% by weight, and evaluation was carried out by the following method. Specific viscosity: 0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at 20 ° C. Hydrolysis resistance: 150 polymer in water vapor at 120 ° C
The decrease in molecular weight when kept for a period of time was shown by the retention rate of the specific viscosity. Heat resistance: The glass transition temperature was measured at a temperature rising rate of 10 ° C./minute using a DuPont DSC-910. Thermal stability: 3 g of the polymer was sealed in a test tube, degassed in vacuum, then heat-treated at 330 ° C. for 4 hours, dissolved in 200 ml of methylene chloride, and a quartz cell having an optical path length of 10 cm was used.
A spectrophotometer U made by Hitachi, Ltd. with a light transmittance of 0 nm
-3400. Oxidation resistance: 40 g of polymer in a constant temperature bath in an air atmosphere 2
After heating at 80 ° C. for 4 hours, it was dissolved in 400 g of methylene chloride and 860-280 was dissolved using a quartz cell with an optical path length of 25 cm.
The light transmittance in nm was measured with a spectrophotometer U-3400 and converted into light transmittance per 1 cm of the polymer.

Example 1 To a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 460 parts of ion-exchanged water and 52 parts of 48.5% sodium hydroxide aqueous solution were added, and nitrogen gas was bubbled for 30 minutes for deoxidation. Then add 0.14 parts of hydrosulfite,
After dissolving 42.4 parts of bisphenol AF having a purity of 99.98% and 36.6 parts of bisphenol AP having a purity of 99.98%, 300 parts of methylene chloride was added, and the mixture was stirred for 14 to 14
29.2 parts of phosgene was blown in at 16 ° C. over about 60 minutes. Then, 9.8 parts of 48.5% sodium hydroxide aqueous solution and 1.9 parts of p-tert-butylphenol were added,
After stirring to emulsify, 0.04 parts of triethylamine was added, and the reaction was completed by stirring at 30 ° C. for about 2 hours. After completion of the reaction, the organic phase was separated, acidified with hydrochloric acid and washed with water repeatedly to remove impurities, and then methylene chloride was evaporated to obtain a copolymer. The specific viscosity of the obtained copolymer was 0.
255, and the retention rate of specific viscosity by steam treatment is 84.
%, The glass transition temperature was 170 ° C., indicating high hydrolysis resistance and heat resistance, and the light transmittance after heat treatment was 80%, indicating excellent thermal stability. As shown by 1 (□) in FIG. 1, the oxidation resistance is remarkably excellent as compared with the polymer from bisphenol AP and the polymer from bisphenol A.

Example 2 Example 1 except that the amount of bisphenol AF used was 25.4 parts and the amount of bisphenol AP used was 51.2 parts.
A copolymer was obtained in the same manner as in. The specific viscosity of this copolymer is 0.263, the specific viscosity retention by steam treatment is 88%, and the glass transition temperature is 173 ° C., which shows high hydrolysis resistance and heat resistance, and the light transmittance after heat treatment. Also showed excellent thermal stability of 79%. The oxidation resistance is also 2 in Fig. 1.
As shown by (◯), it is remarkably excellent as compared with the polymer from bisphenol AP and the polymer from bisphenol A.

Example 3 Example 1 except that the amount of bisphenol AF used was 83.7 parts and the amount of bisphenol AP used was 0.73 part.
A copolymer was obtained in the same manner as in. This copolymer had a glass transition temperature of 159 ° C., a specific viscosity of 0.242, a high retention rate of specific viscosity by steam treatment of 79% and high hydrolysis resistance, and a light transmittance of 84% after heat treatment. And showed excellent thermal stability.

Comparative Example 1 A homopolymer of bisphenol AP was obtained in the same manner as in Example 1 except that the amount of bisphenol AP used was 73.1 parts without using bisphenol AF. This homopolymer had a specific viscosity of 0.301 and a glass transition temperature of 179 ° C., which showed high heat resistance, but the light transmittance after heat treatment was as low as 69%, which was inferior in thermal stability, and also showed high resistance to oxidation. 1 to 3
It was inferior as shown by (+).

Comparative Example 2 A homopolymer of bisphenol AF was obtained in the same manner as in Example 1 except that the amount of bisphenol AF used was 84.7 parts without using bisphenol AP. This homopolymer has a glass transition temperature of 158 ° C. and a specific viscosity of 0.19.
1, the retention of specific viscosity by steam treatment is 69%, which is poor in hydrolysis resistance, and the light transmittance after heat treatment is 71%, which is also low and thermal stability is poor.

Comparative Example 3 Polycarbonate made from bisphenol A having a specific viscosity of 0.279 [Panlite AD-55 manufactured by Teijin Chemicals Ltd.]
03] was evaluated. The glass transition temperature was as low as 149 ° C., and the heat resistance was inferior, and the oxidation resistance was also inferior as shown by 4 (⋄) in FIG.

[0018]

The aromatic polycarbonate copolymer of the present invention is a novel one, and is particularly excellent in hydrolysis resistance, heat resistance, thermal stability and oxidation resistance, and also excellent in transparency and moldability. Therefore, it is extremely useful as a material for various optical devices such as headlamp lenses, various lenses, prisms, optical waveguides, connectors, optical fibers, optical disks, liquid crystal panels, etc., where high heat resistance, optical characteristics and water resistance are required. .

[Brief description of drawings]

FIG. 1 is a chart showing the spectral light transmittance of a polymer solution after heat treatment for showing the oxidation resistance of the polymer.

[Explanation of symbols]

1 Spectral light transmittance of the aromatic polycarbonate copolymer of the present invention (Example 1) (50 mol% of bisphenol AF and 50 mol% of bisphenol AP) 2 Aromatic polycarbonate copolymer of the present invention (Example 2) (30 mol of bisphenol AF) %, Bisphenol AP 70 mol%) 3 Spectral light transmittance of polycarbonate from bisphenol AP (Comparative Example 1) 4 Spectral light transmittance of polycarbonate from bisphenol A (Comparative Example 3)

Claims (1)

[Claims] 1. 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 15-99.5 mol% and 1,1-bis (4-hydroxyphenyl) ) -1-Phenylethane 85-0.5 mol%
It is an aromatic polycarbonate copolymer obtained by reacting a carbonate precursor with a dihydric phenol mainly comprising a dihydric phenol consisting of 0.7 g of the aromatic polycarbonate copolymer dissolved in 100 ml of methylene chloride and having a specific viscosity measured at 20 ° C. Is 0.
An aromatic polycarbonate copolymer characterized in that it is 160 to 0.410.