JP3141475B2 - Fluorine-containing polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing polycarbonate having a cyclohexane ring.

[0002]

2. Description of the Related Art Polycarbonate is a synthetic resin widely used industrially, and is usually 2,2-bis (4'-).
It is produced by reacting a diol component such as a dihydric phenol represented by (hydroxyphenyl) propane (commonly called bisphenol A) with a carbonic acid derivative such as phosgene. Polycarbonate produced from bisphenol A has excellent properties such as excellent impact resistance, creep resistance, dimensional stability, and high-frequency insulation properties, and has low hygroscopicity and is stable to heat. With the active development of resin applications, expectations for the development of polycarbonates having new structures and new structures have been increasing. For example, a conventional polycarbonate has a large anisotropic aromatic ring in its main chain,
It has been difficult to reduce birefringence, which is an important property of the optical recording substrate. To solve this problem,
JP-A-1-172424 discloses a polycarbonate made of 1,4-cyclohexanediol or 4-4'-bicyclohexanediol, but the melting point and the like are not clear. Further, since this polymer is a mixture of cis and trans forms, there is a disadvantage that the physical properties of the obtained resin are not constant.

Accordingly, the present applicants have disclosed Japanese Patent Application Laid-Open No. 3-27571.
7 and JP-A-3-259920, in order to keep the physical properties of the resin constant, 2,2-bis (4'hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (hereinafter referred to as bisphenol- AF is abbreviated.) Trans-, trans-4-4'-bicyclohexanediol and trans-1,4-cyclohexanediol have been disclosed as fluorine-containing polycarbonates. There was a problem with sex. Also, this resin has liquid crystal properties, but those showing liquid crystal properties are generally not suitable for optical resin materials because of their large birefringence.

[0004]

An object of the present invention is to provide a novel fluorine-containing polycarbonate having a cyclohexane ring in a structural unit. Mixing with other known resins having reduced birefringence, for example, polyethylene, polypropylene, polymethyl methacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyesters such as polyethylene terephthalate, or polyphenylene oxides. To obtain a resin to which new properties can be added.

[0005]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, as a diol component, bisphenol-AF and trans-1,4
A novel polycarbonate was found to be obtained by using -cyclohexanedimethanol, and the fluorinated polycarbonate of the present invention was completed.

The fluorinated polycarbonate of the present invention has the formula [1]

Embedded image And a structural unit represented by the formula [2]

Embedded image Are irregularly arranged in a linear manner.

In one embodiment, the reduced viscosity is 0.2 to 2.0.
dl / g (25 ° C., 0.5 g / dl chloroform) polycarbonate. The content ratio of the structural unit represented by the formula [1] to the structural unit represented by the formula [2] is not particularly limited.

The reduced polycarbonate of the present invention has a reduced viscosity of 0.2 to 2.0 dl / g (25 ° C., 0.5 g / dl chloroform). Further, the melting point is 110-200 ° C.,
And a resin having a decomposition temperature of 320 to 370 ° C. and excellent in heat resistance. Further, it is a polycarbonate having a low birefringence because it can be thermoformed and formed into a film and does not show a liquid crystal phase.

The method for producing the polycarbonate of the present invention is represented by the formula [3]

Embedded image A bisphenol-AF represented by the formula [4]

Embedded image Is mixed with trans-1,4-cyclohexanedimethanol represented by the formula (5) in the presence of an acid acceptor such as pyridine.

Embedded image Is to react with trichloromethyl chloroformate represented by

In the above process, phosgene may be used instead of trichloromethyl chloroformate. Reaction temperature is 20 ~
The reaction time at 100 ° C. is not particularly limited, but is 1 to 5 hours. The mixing ratio of the diol component of bisphenol-AF and trans-1,4-cyclohexanedimethanol is not particularly limited, and a mixture in a desired ratio may be used. The amounts of trichloromethyl chloroformate and phosgene used are equimolar or slightly excessive with respect to the total of the diol components. Further, in the presence of a transesterification catalyst such as a metal oxide, the above diol and diaryl carbonate are reacted with 2
It can also be produced by a method of reacting at 00 to 300 ° C. for 4 to 10 hours. In these methods, a molecular weight modifier can be added as needed from 1 to 10 mol% based on the diol.

As the molecular weight modifier, monohydric phenol,
For example, phenol, p-tert-butylphenol, p-cumylphenol and the like can be mentioned.
Examples of the solvent include halogenated hydrocarbons such as dichloromethane and chlorobenzene, aromatic hydrocarbons such as benzene and toluene, and ether-based tetrahydrofuran and dioxane. Specific examples of acid acceptors other than pyridine include tertiary amines such as triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene, inorganic bases such as sodium hydroxide, and phosgene. Examples of the carbonate derivative include phosgene dimer, and examples of the diaryl carbonate include diphenyl carbonate.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Next, the physical properties of the polycarbonate obtained in the examples were measured by the following methods. Reduced viscosity (dl / g): 25 ° C using chloroform as a solvent,
It was measured at a concentration of 0.5 g / dl. Melting point (Tm): Measured at a temperature rise of 3 ° C./min with a hot stage (FP-82 manufactured by Mettler) attached to a polarizing microscope. Decomposition temperature (Td): TG / DT manufactured by Seiko Denshi Kogyo
The temperature was measured at a temperature rise rate of 10 ° C./minute using an A-220 model, and the temperature at which the weight loss was 5% was measured. Glass transition temperature (Tg): DS manufactured by Seiko Denshi Kogyo
The measurement was performed at a heating temperature of 5 ° C./min using a Model C-200. Birefringence: The retardation was measured using a polarizing microscope at 546 nm by the Senarmont Convenator method.

[0014]

【Example】

Example 1 Production of a polycarbonate comprising a structural unit represented by the formula [1] and a structural unit represented by the formula [2]: 100 ml
0.91g of bisphenol-AF in a three-necked flask
(2.70 mmol), 0.04 g (0.30 mmol) of trans-1,4-cyclohexanedimethanol, 1 ml of pyridine and 5 ml of 1,2-dichloroethane (hereinafter referred to as DCE) were stirred and then stirred. The solution was kept at 90 ° C. with a mantle heater, and a solution of 0.33 g (1.7 mmol) of trichloromethyl chloroformate dissolved in 2 ml of DCE was added dropwise over 20 minutes under reflux, and the reaction was allowed to proceed for 3 hours. The resulting reaction solution was allowed to cool and then methanol (300 ml)
And the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to obtain 0.85 g (82.7% yield) of polycarbonate. The structure of this polymer was confirmed by an IR spectrum. This polycarbonate had a reduced viscosity of 0.20 dl / g and a melting point of 174.1 to
The glass transition temperature was 198.0 ° C and the decomposition temperature was 372.3 ° C. When a chloroform solution of this polymer was cast on a glass plate and dried, a transparent polycarbonate film was obtained. Also, a good film was obtained by placing the polymer on a glass plate, heating to 200 ° C., melting and cooling.

Examples 2 to 5 The procedure of Example 1 was repeated except that the component ratios of bisphenol-AF and trans-1,4-cyclohexanedimethanol were changed. Table 1 shows the component ratios and the physical properties of the obtained polycarbonate.

[0016]

[Table 1]

[0017]

The fluorinated polycarbonate of the present invention comprises:
High decomposition temperature allows use at high temperatures. Further, a film having excellent transparency can be produced. Further, the fluorinated polycarbonate of the present invention exhibits excellent transparency due to the effect of the cyclohexane ring contained in the polymer chain, and is particularly useful as an optical resin material for optical recording substrates and the like. It is also possible to improve the properties of these resins by mixing them with other known resins and to add new properties.

Claims (2)

(57) [Claims] [Claim 1] Formula [1] And a structural unit represented by the formula [2] A fluorine-containing polycarbonate in which the structural units represented by are irregularly arranged linearly. 2. A reduced viscosity of 0.2 to 2.0 dl / g (at 25 ° C.,
0.5 g / dl chloroform).