JPH0457826A - Fluoro polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain a fluoro polycarbonate resin improved in impact resistance, hygroscopicity, heat resistance, thermoformability and transparency and having a skeleton comprising specified repeating units. CONSTITUTION:2,2-Bis(4-hydroxyethoxyphenyl)-1,1,1,3,3,3-hexafluoropro- pane of formula I is mixed with 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3-hexafluoropropane of formula II to obtain a dihydric alcohol mixture. The mixture is allowed to react with a carbonic acid derivative (e.g. phosgene) in an inert solvent in the presence of an acid acceptor (e.g. pyridine) and optionally a molecular weight modifier to obtain the title resin having a skeleton comprising repeating units of formula III (wherein (x) and (y) satisfy (x + y)= 1, and 1 >= x >=0.1).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel fluorine-containing polycarbonate resin having excellent transparency.

[Conventional technology]

Polycarbonate resin is a synthetic resin that is widely used industrially, and is usually made of a dihydric phenol such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as bisphenol A) and a carbonic acid derivative such as phosgene. It is produced by a reaction with

By the way, polycarbonate resin produced from bisphenol A has excellent properties such as excellent impact resistance, low hygroscopicity, and stability against heat. However, in recent years, polycarbonate resins with excellent transparency and easy thermoforming have been required for the entire center of optical disks.

In order to meet these demands, resins with excellent transparency and a melting point in the range of about 100°C to 220°C are prepared singly or mixed with various other resins.

(Problems to be Solved by the Invention) An object of the present invention is to provide a polycarbonate resin that has excellent impact resistance, moisture absorption, and heat resistance, and is suitable for completely improving thermoformability. All we have to offer is superior resin.

[Means for solving problems]

The present invention is based on the formula (I) CF, 0 CF3 0 (in the formula, x+7 is a number satisfying x+y=1, and 1≧
It is a fluorine-containing polycarbonate resin whose entire skeleton is a repeating unit represented by the formula (X≧0.1).

(Actions and Effects of the Invention) Some of the polycarbonate resins of the present invention have about 100%
It has a melting point of about 200°C and a decomposition temperature of 35°C.
It is 0°C or higher and is thermally stable.

In addition, the resin contains fluorine-containing resin and has a small refractive index for light, and has excellent transparency, as well as excellent impact resistance and moisture absorption. These polycarbonate resins can be mixed with other known resins, such as polymers such as polyethylene, polypropylene, polymethyl methacrylate, polyacrylates, polycarbonates, and polyethylene terephthalates, to modify their optical properties and aging properties. It is a useful power.

[Manufacture of compounds]

The method for producing the polycarbonate resin represented by the general formula (I) of the present invention is to use the following dihydric alcohol monomer 01) in a molar ratio according to xt7 of the formula (I). , a conventionally known method for producing polycarbonate resins can be used.

CF3 2.2-bis(4-hydroxyethoxyphenyl)-1
, 1,1,3,3,3-hexafluoropropane (abbreviation BEAF) CF.

CF3 2.2-bis(4-hydroxyphenyl)-1゜1.1
．． 3,3.3-hexafluoropronoprono (abbreviated as BAF)
) BEAF (I) is obtained by reacting commercially available BAF ([) and dibrominated ethanol with anhydrous potassium carbonate in N,N-dimethylformamide (DMF).

Further, typical examples of known polycarbonate resin manufacturing methods include (a) dihydric alcohols represented by the above general formulas (I) and (I) in an organic base such as pyridine or triethylamine; A method in which a carbonic acid derivative such as phosgene is injected into the solution to cause a reaction.

(b) In the presence of an inert solvent such as methylene chloride, chlorobenzene, toluene, etc. and an acid acceptor such as pyridine, dihydric alcohols represented by the above general formulas (I) and (I) and phosgene, etc. A method of reacting with carbonic acid derivatives.

(e) A method of reacting a dihydric alcohol represented by the above general formula (I) with a carbonic acid diaryl ester in the presence of a transesterification catalyst such as a metal oxide.

(d) Dihydric alcohols represented by the above general formulas (I) and (I) and trichloromethylchloride in the presence of an inert solvent such as dichloroethane, methylene chloride, chlorobenzene, toluene, etc. and an acid acceptor of pyridine. How to react with rolf olmato.

etc.

In either method, monohydric phenol such as phenol, p-tert-butylphenol, p-cumylphenol, etc. may be added as a molecular weight regulator in an amount of 1 to 10 mol% based on the dihydric alcohol. good.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

Example 1 Production of (+)2.2-bis(4-hydroxyethoxy7enyl)-1,1,1,3,3,3-hexafluoropropane (BEAF): Attach a cooler and a stirrer. BAF (manufactured by Central Glass, mpl 59)
, 7-161.4°C) 29.7 LI (0.09mo
l), 2-bromoethanol44. Of (0,35
rnol), anhydrous carbon a potassium 150. The reaction was carried out at 80"C for 30 hours using MF 500S/ as a solvent. After the reaction was completed, an oily substance was separated when the reaction solution was poured into 60% of water.
After extraction with 1, the extract was washed with 2N-NaOH three times and with water until neutral. After drying the vinegar-based ether layer over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure.

The remaining oil was distilled under reduced pressure (boiling point 264-273°C/8.
5aHg) to produce 2,2-bis(4-hydroxyethoxyphenyl)-1,1,1,3,3,3-hexafluoropropane (BEAF) 18.79 (yield 50.0%)
) got 1.

(II) Production of poly[2,2-bis(4-ethyleneoxyphenyl)-1,1,1,3,3,3-hexafluoropropane carbonate] 100g? Place the BEA obtained in (I) in a three-loaf flask.
1.271 (3 mmol) of F, 72 ml of viridi, and 10 g of 1,2-dichloroethane (DCE) were added and stirred. Then, the temperature was raised to 90°C using a mantle heater, and 0.33% of trichloromethyl chloroformate was added under reflux.
f (I, 7 mmol) ff1 DcE Solution IIj dissolved in 3 txl was added dropwise over 20 minutes, and then
The reaction was carried out for 0 minutes. The reaction solution was allowed to cool to 50°C, then poured into 300 ml of methanol, and the precipitate was filtered off. The material was washed in hot methanol and dried. Yield: 1.14F (yield: 84.4%).

This polymer has a melting point of 109-125°C, a glass transition temperature of 91°C, a decomposition temperature of 357'C, and a reduced viscosity of 0.2
It was 0.

Examples 2 to 6 Various polycarbonates were produced in the same manner as in Example 1 using BEAF and BAFt-ffi in different ratios as diol components.

These results are shown in Table 1.

Table 81) -1,1,1,3,3,3-hexafluoropropane 2) Chloroform as total solvent 25°C, 0.5f/dl
The flkrl was measured.

8) Attach a hot stage to the polarizing microscope and heat at 3°C per minute.
Measured at a heating rate of .

4) Measurement was carried out using a TG/DTA-220 model manufactured by Seiko Electronics Co., Ltd. at a heating rate of 10° C. per minute.

J! 1) Measurement was performed using a DSC-200 model manufactured by Seiko Electronics Co., Ltd. at a heating rate of 5° C. per minute.

that's all

Claims (1)

[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, x and y are numbers satisfying x+y=1, and 1 ≧x≧
0.1) A fluorine-containing polycarbonate resin whose skeleton is a repeating unit represented by: