JPH03273025A - Liquid crystal cyclohexane polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain the title resin improved in transparency, impact resistance, hygroscopicity and heat stability and having a low birefractive index by using a specified dihydric alcohol instead of a dihydric bisphenol. CONSTITUTION:A carbonic acid derivative such as phosgene is blown into a solution which is prepared by dissolving a dihydric alcohol of formula I (wherein (n) is 1 or 2) in an organic base such as pyridine or triethylamine and to which 1-10mol%, based on the dihydric alcohol, monohydric phenol is optionally added, and allowed to react to obtain a liquid crystal cyclohexane polycarbonate resin represented by formula II (wherein formula III is trans- cyclohexylene; (x) and (y) satisfy (x+y)=1, and x>=0.1) and having an m.p. of 280 deg.C or above and a decomposition point of 290 deg.C or above.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel liquid crystal cyclohexane polycarbonate resin, and more particularly to a polycarbonate resin with reduced birefringence and 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 phosgene. It is produced by reaction with carbonic acid derivatives such as

By the way, polycarbonate resin manufactured from bisphenol A has excellent properties such as excellent impact resistance, low hygroscopicity and stability against heat, but when used as an optical recording substrate, Aromatic polycarbonate resins, typified by polycarbonate resins produced from bisphenol A, contain aromatic sources with large anisotropy in their main chains, so they have extremely high properties for optical recording substrates (birefringence, which is the key point). It was difficult to reduce the

In order to solve this problem, in addition to reducing the molecular weight, attempts have been made to reduce molecular orientation during molding by examining molding conditions. However, since birefringence is caused by the material itself, it is extremely difficult to stably manufacture substrates with low birefringence, and a polycarbonate resin that is fully satisfactory as an optical recording substrate has yet to be found. It has not been.

(Problems to be Solved by the Invention) The object of the present invention is to solve the disadvantages when used as an optical recording substrate without impairing the advantages of polycarbonate resin, which has excellent impact resistance, moisture absorption, and heat resistance. An object of the present invention is to provide an excellent polycarbonate resin with improved birefringence.

[Means to solve all problems]

The present invention relates to the formula (I) % formula % c where -C)-u) lance cyclohexylene, Xgy
is a liquid crystalline cyclohexane polycarbonate resin represented by X−+#”1, which satisfies X≧0.1.

[Action and effect of the invention]

The polycarbonate resin of formula (I) of the present invention has a melting point of 28
It has excellent stability with a decomposition point of 290°C or higher at temperatures above 0°C.
Excellent transparency. In addition, since the polycarbonate resin of the present invention has a liquid crystal phase or water crystal structure, when the resin film is produced, when the resin solution is poured onto the surface of the substrate that has been rubbed, it forms a film that is more highly oriented than K. Can manufacture tubes.

The polymer of the present invention may also be used with other known resins such as polyethylene, polyglobylene, polymethyl methacrylate,
When mixed with ABS, polyamides, polyacrylates, polycarbonates, polyesters such as polyethylene terephthalate, or polyphenylene oxides, the mechanical strength of the mixed resin can be improved as a special feature of liquid crystal polymers.

Furthermore, the polycarbonate resin of the present invention is a resin with excellent impact resistance, hygroscopicity, and thermal stability, and has low birefringence because the birefringence attributable to the resin itself is extremely small compared to aromatic polycarbonate resins. It can be used for transparent resin applications such as optical recording substrates that require.

The method for producing the polycarbonate resin represented by the general formula (I) of the present invention is the same as the conventionally known method for producing polycarbonate resins, except that the dihydric alcohol represented by the general formula (I) is used instead of the divalent bisphenols. It can be done by the following method.

Formula (I) %formula%) Examples thereof are shown as (a) to (d).

(a) A method in which a dihydric alcohol represented by the above general formula (I) is dissolved in an organic base such as pyridine or triethylamine, and a carbonic acid derivative such as phosgene is bubbled into the solution to cause a reaction.

(b) Reacting the dihydric alcohol represented by the above general formula (I) with a carbonic acid derivative such as phosgene in the presence of an inert solvent such as methylene chloride, chlorobenzene, or toluene and an acid acceptor such as pyridine. Method.

(c) A method of reacting a dihydric alcohol represented by the above general formula 1) with a carbonic acid diaryl ester in the presence of a transesterification catalyst such as a metal oxide.

(d) A dihydric alcohol represented by the above general formula (I) and trichloromethyl chloroformate in the presence of an inert solvent such as dichloroethane, methylene chloride, chlorobenzene, toluene, etc. and an acid acceptor such as pyridine. How to react.

In either method, 1 to 10 mol% of monohydric phenol, such as phenol, p-tert-butylphenol, p-cumylphenol, etc., is added to the dihydric alcohol as a molecular weight regulator. It's okay.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to examples below, but the invention is not limited to these examples in any way. The raw materials used in the examples were produced as follows.

(I)) Production of lance-1,4-cyclohexanediol: Orbab et al., Journal of the American Chemical Society, Volume 66, Page 1097 (I9
44), trans and cis mixed 1,4-cyclohexane diol was reacted with acetic anhydride to form acetate, and trans-1,4-cyclohexane diacetate was produced by recrystallization. The trans body was hydrolyzed with barium hydroxide water to produce trans-1,4-cyclohexanediol. Melting point 140.7-141.6
″'C.

01) Production of trans, trans-4,4'-bicyclohexanediol: Wiles et al., Journal of the American Chemical Society, Vol. 76, p. 1735 (I95
4) Trans. by the method described in K.

cis-mixed 4.4'-bicyclohexanediol is reacted with benzoyl chloride in dioxane in the presence of pyridine,
Dibenzoate. Trans,trans-4,4'-bicyclohexane dibenzoate was produced by recrystallization. After hydrolysis with an aqueous potassium hydroxide solution, recrystallization was performed to produce the desired trans,trans-4,4'-bicyclohexanediol (melting point: 215.5-2163°C).

The glass transition temperature is determined by DSC-200 manufactured by Seiko Electronics Co., Ltd.
The decomposition temperature was measured using a TG/DTA-220 model manufactured by Seiko Electronics Co., Ltd. at a heating rate of 10°C per minute. In addition, the liquid crystal transition temperature was measured by attaching a polarizing microscope to a hot stage (FP-82 manufactured by Mettler) at a heating rate of 3°C per minute, and the reduced viscosity was measured using chloroform as a solvent at 25°C and 0.5°C. The concentration of dll'i was measured.

Example 1 Preparation of poly(trans, trans-4,4'-bicyclohexylene carbonate) Trans, trans-4,4'-bicyclohexanediol 0.59F (8
, 0 mmol), 72 ml of viridi, and 50 sJ'e of 1,2-dichloroethane (DCE) were added and stirred.

Then, heat to 90℃ with a mantle heater and reflux 1)
ri o o Methyl chloroformate o, 33f (L, 7m
A solution dissolved in rnol ) t D CE 5 we was added dropwise over 20 minutes, and the reaction was continued for 90 minutes.

After cooling the reaction solution to 50°C, methanol 3
A precipitate t-F3 was obtained by pouring 00M1K.

This filtrate was washed in hot methanol and dried.

Yield 0.511! (Yield 76.1%).

This polymer was insoluble in chloroform, with a glass transition temperature of 145" and a melting point of 323°C.

Examples 2 to 6 Various polycarbonates were produced in the same manner as in Example 1 using trans, trans-4゜4'-bicyclohexanediol, trans-1゜4-cyclohexanediol and trans-1゜4-cyclohexanediol as diol components in various proportions. .

These results are shown in Table 1.

Table 1 Notes to Table 1 1) BCDO:) Indicates lance, trans-4,4'-bicyclohexanediol.

CDO: ) Lance-1,4-cyclohexanediol school.

2) 10.5 dl/25°C using chloroform as a solvent
The density of f was measured in V.

3) 5 degrees per minute with Seiko Electronics & DSC-200 type
It was measured at the temperature increase rate of C.

4) Polarizing microscope with hot stage (FP- manufactured by Mettler)
82) was attached, and measurements were taken at a heating rate of 3°C per minute.

5) Measurement was carried out using a model TG/DTA-220 manufactured by Seiko Electronics Co., Ltd. at a heating rate of 10° C. per minute, and the temperature was set at a temperature at which the N sound decreased by 5%.

〔Effect of the invention〕

As is clear from the above explanation, the polycarbonate A4 finger of the present invention exhibits a liquid crystalline phase structure, and is composed only of cyclohexylene rings, so it has low birefringence and is stable up to high temperatures. Therefore, it is also effective as a component of a mechanically strong resin composition.

that's all

Claims (1)

[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is transcyclohexylene, x, y are x+y= A liquid crystal cyclohexane polycarbonate resin represented by the formula 1 and x≧0.1.