JPH0457827A - Fluoro propyleneoxybicyclohexylene polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain the title resin lowered in birefringence and improved in transparency and thermoformability without detriment to its impact resistance, hygroscopicity and heat resistance by using specified repeating structural units. CONSTITUTION:A dihydric alcohol of formula I, II or III is allowed to react with phosgene and trichloromethyl chloroformate in the presence of an acid acceptor (e.g. pyridine) and optionally a molecular weight modifier in an inert solvent (e.g. dichloroethane) to obtain a fluoro propyleneoxy-bicyclohexylene polycarbonate resin having repeating structural units of formula IV (wherein formula V is trans cyclohexylene; (x + y + z) = 1, and 0.1 <= x, y or z <=0.9).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new polycarbonate resin, and particularly to a fluorine-containing propylene oxybicyclohexylene polycarbonate resin having excellent transparency and thermoformability.

[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 phosgene. It is produced by reaction with carbonic acid derivatives. By the way, polycarbonate resin manufactured from bisphenol A has excellent properties such as excellent impact resistance, low hygroscopicity, and is stable to heat. However, when using it as an optical recording substrate, bisphenol Aromatic polycarbonate resins, typified by the polycarbonate resin produced from A, contain aromatic rings with large anisotropy in their main chains, so they reduce birefringence, which is extremely important as a property of optical recording substrates. was difficult.

In order to solve this problem, attempts have been made to reduce the molecular orientation during molding by reducing the molecular weight and examining molding conditions. However, since birefringence is caused by the material itself, it is difficult to stably manufacture transparent substrates with low birefringence, and polycarbonate resins that are fully satisfactory as optical recording substrates have yet to be found. Not served. In addition, since conventional polycarbonate resins have relatively high melting points, they have had the problem of poor thermoformability depending on their use.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a polycarbonate resin that has low birefringence, excellent transparency, and improved thermoformability without impairing the advantages of polycarbonate resin, which has excellent impact resistance, moisture absorption, and heat resistance. It is in.

[Means for solving problems]

The present invention is based on the formula (■ C.F.

C.F.

...... (I) Indicates that x+y+z=1 and 0.1≦X≦0.9.0.1≦
It is a fluorine-containing propylene oxybicyclohexylene polycarbonate resin having a repeating structural unit represented by y≦0.9, 0.1≦2≦0.9.

As a method for producing the polycarbonate resin represented by the formula (I) of the present invention, dihydric alcohols represented by the following formulas (I[), (m) and (■) are used instead of the dihydric bisphenols ( a) Method of dissolving in pyridine, triethylamine, etc. and reacting with phosgene; (b) Method of dissolving phosgene or trichloromethyl chloroformate in the presence of an inert solvent such as dichloroethane, methylene chloride, chlorobenzene, or toluene and an acid acceptor such as pyridine. Conventionally known methods such as a method of reacting with a carbonic acid diaryl ester in the presence of a transesterification catalyst (ufc) or a method of reacting with a carbonic acid diaryl ester in the presence of a transesterification catalyst can be used.

Note that the dihydric alcohol represented by formula (II), ie, 2.
2-bis(4-■-hydroxypropoxyphenyl)
-1,1,1,3,3,3-hexafluoropropane is 2,2-bis(4-hydroxyphenyl)-1゜1,
1.3.3.Produced by reacting 3-hexafluoropropane (III) and 3-bromopropanol in the presence of anhydrous potassium carbonate in N,N-dimethylformamide (abbreviated as DMF) .

C.F.

(III) C.F.

C.F.

(II) In any of the above methods (a) to (c), a monohydric phenol with a mole ratio of 1 to 10 molar relative to the dihydric alcohol is used as a molecular weight modifier, such as phenol, p-tert-butylphenol, p- Addition of cumylphenol or the like may be carried out optionally depending on necessity.

Although the polycarbonate resin of the present invention is useful in itself, it can be mixed with other known resins such as polyethylene, polypropylene, polymethyl methacrylate, polyacrylates, polycarbonates, polyethylene terephthalate, etc. to improve the optical properties of these resins. It is also possible to improve properties and thermoformability.

[For production]

The polycarbonate resin represented by formula (I) of the present invention maintains the impact resistance, hygroscopicity, and thermal stability inherent to polycarbonate resins, and also has a low melting point with excellent thermoformability depending on the proportion of raw material dihydric alcohol used. (about 120~250℃
).

Furthermore, in addition to lowering the birefringence and improving transparency, which are unique to fluorine-containing resins, the decomposition temperature is 290° C. or higher, which improves heat resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these Examples. In addition, the physical properties of the polycarbonate obtained in the examples were measured according to the following.

Glass transition temperature: Seiko Electronics Industries Co., Ltd. DSC-200
Measured using a mold at a heating rate of 5°C per minute.

Decomposition temperature: TG/DTA-220 manufactured by Seiko Electronics Co., Ltd.
Measured using a mold at a heating rate of 10°C per minute, weight loss 5%
The temperature was set to .

Melting point: Polarizing microscope with hot stage (FP manufactured by Mettler)
-82) and measured at a heating rate of 3°C per minute.

Reduced viscosity: 25°C using chloroform as a solvent, 0.51
Measured at a concentration of 7di.

Example 1, t! 1. II: 2,2-bis(4-0 propyleneoxyphenyl) -1,1,1,3,3,3-hexafluoropropane-2,2-bis(4-phenylene) -
1,1,1,3°3.3-hexafluoropropane-trans,trans-4,4'-bicyclohexylene carbonate] was produced according to 1), U) and 111) below.

1) Preparation of 2.2-bis(4-0-hydroxypropoxyphenyl)-1,1,1,3,3,3-hexafluoropropane 2. Into 103 500IIL flasks equipped with a condenser and a stirrer. 2-bis(4-hydroxyphenyl)-1
,1,1,3,3,3-hexafluoropropane51.
8g (0,151Ll), 3-bromopropertool 86
0 g (0.62 m) and 200 y of anhydrous potassium carbonate were added, and the reaction was carried out at 80° C. for 30 hours using 300 m of DMF as a solvent. After the reaction was completed, the reaction solution was poured into 5 liters of water, and an oily substance separated out. This oily substance is mixed with 900% ethyl acetate.
After extraction with m1, the extracted ethyl acetate layer was diluted with 2N-Na
The mixture was washed with OH water three times and with water until neutral, then dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure.

The remaining oil was distilled under reduced pressure (boiling point 246-257"C/
6.5 Hg) and 2,2-bis(4-ω-hydroxypropoxyphenyl)-1,1,1,3,3,3-hexafluoropropane33. ON (yield 47.3%)
I got it.

l) Preparation of trans,trans-4,4'-bicyclohexanediol Trans,cis mixed 4,4'-bicyclohexanediol was reacted with benzoyl chloride in dioxane in the presence of pyridine to obtain a dibenzoate mixture. From this mixture, trans-4,4'-bicyclohexane dibenzoate was obtained by recrystallization. This trans,trans isomer is hydrolyzed with an aqueous potassium hydroxide solution and then recrystallized.
°C) was produced (A, L, Wilds, eta
l,, J, Am, Chem, Soc,, 76
1735 (1954)).

1it) Polycondensation reaction content: 2゜2 obtained in 1) in three 1001il flasks.
-Bis(4-■-hydroxypropoxyphenyl) -
1,1,1,3,3,3-hexafluoropropane0.
95 g (2.1 mmol), 2.2-bis(4-
hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 0.201 (0.6 mmol
) and II) trans,trans-4,4'-bicyclohexanediol 0.061 (0-3 mmol
), 0.61 Ll of pyridine, and 51 Ll of 1,2-dichloroethane (abbreviated as EDC) were added and stirred. The reaction solution thus obtained was reacted at room temperature for 90 minutes while maintaining the trichloromethyl chloroformate concentration at 0.33.

After cooling this reaction solution to 50°C, methanol 30°C
01, and the precipitate deposited was filtered.

The filtrate was washed in hot methanol, then dried and polymer 1.20. ! i' (yield 93.0%) was obtained.

The physical properties of this polymer include a reduced viscosity of 041, a glass transition temperature of 77°C, a melting point of 128-169°C, and a decomposition temperature of 321°C.
It was ℃.

Examples 2 to 5 2.2-bis(4-■-hydroxypropoxyphenyl) -1,1,1,3,3,3-hexafluoropropane% 2.2-bis(4-hydroxyphenyl) as diol component A polycondensation reaction was carried out in the same manner as in Example 1, except that -1,1,1,3,3,3-hexafluoropropane and trans,trans-4,4'-bicyclohexanediol were used in various proportions, Various polycarbonates were produced.

These results are shown in Table 1 together with the results of Example 1.

〔Effect of the invention〕

As explained above, the polycarbonate resin of the present invention is
Due to the cyclohexylene ring and fluorine content effect, it has excellent transparency and low birefringence, and by adjusting the proportion of raw material dihydric alcohol, it has a low melting point with excellent ripening shape and heat resistance. It is particularly useful as an optical resin material for optical recording substrates and the like.

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, ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼ indicates trans cyclohexylene, and x + y + z = 1 and 0.1≦x
≦0.9, 0.1≦y≦0.9, 0.1≦z≦0.9).