JPH051143A - Copolymer of fluorine-containing carbonate of bicyclohexylene diester - Google Patents

Abstract

PURPOSE:To provide the subject copolymer containing a bicyclohexylene diester structural unit and a carbonate structural unit containing bisphenol AF unit, having excellent transparency and thermal stability and moldable by thermoforming. CONSTITUTION:The objective copolymer of a fluorine-containing carbonate of a bicyclohexylene diester is a random copolymer composed of (A) the structural unit of formula I and (B) the structural unit of formula II and having a reduced viscosity of 0.05-1.50 (25 deg.C, 0.5g/dl, chloroform). The amounts of the components A and B are preferably 5-95mol% and 95-5mol% respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing carbonate copolymer of bicyclohexylene diester. More specifically, it is obtained by randomly binding carbonates of dihydroxyethyl ester of bicyclohexanedicarboxylic acid and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane. It relates to a carbonate copolymer.

[0002]

2. Description of the Related Art Polycarbonate is a polymer having a carbonic acid ester structure in its structural unit, and is usually a divalent phenol such as 2,2-bis (4'-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A). It is a plastic produced by reaction with a carbonic acid derivative such as phosgene, and has excellent properties such as excellent impact resistance, small hygroscopicity, and heat stability. In recent years, along with the development of applications of resins, polycarbonates having a novel structural unit have been studied. For example, JP-A-1-172
No. 424 discloses polycarbonates obtained from 1,4-cyclohexanediol or 4,4′-bicyclohexanediol, but there is no description regarding their melting points and there is no thermoformability.

In view of the above problems, an object of the present invention is to provide a novel carbonate copolymer having a thermoformable structural unit having a cyclohexylene group.

[0004]

[Means for Solving the Problems]
A carbonate copolymer having a cyclohexylene group was presented to -72689, and further studies were conducted to reach the present invention. The fluorine-containing carbonate copolymer of bicyclohexylene diester of the present invention comprises hydroxyethyl ester of bicyclohexanedicarboxylic acid and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3.
It is a copolymer in which 3-hexafluoropropane is irregularly linearly carbonate-bonded. That is,

The fluorine-containing carbonate copolymer of bicyclohexylene diester of the present invention has the formula

[Chemical 3] Structural unit shown by and formula

[Chemical 4] And a reduced viscosity of 0.05 to 1.
It is a carbonate copolymer of 50 (25 ° C., 0.5 g / dl, chloroform). Preferably, the structural unit represented by the formula (1) is 5 to 95 mol% and the structural unit represented by the formula (2) is 95 to 5 mol%.

The carbonate copolymer of the present invention has a reduced viscosity of 0.05 to 1.50 (25 ° C., 0.5 g / dl, chloroform), a melting point of 50 to 250 ° C., and a decomposition temperature of 270 ° C. or more. It is a resin.

The method for producing the carbonate copolymer of the present invention has the formula

[Chemical 5] The dihydroxyethyl ester of bicyclohexanedicarboxylic acid represented by

[Chemical 6] 2,2-bis (4-hydroxyphenyl)-
1,1,1,3,3,3-hexafluoropropane was mixed in 1,2-dichloroethane and the formula was calculated in the presence of pyridine.

[Chemical 7] The reaction is performed with trichloromethyl chloroformate represented by Besides 1,2 dichloroethane as the solvent, methylene chloride, chlorobenzene, toluene, etc.,
As the dehydrochlorinating agent, trimethylamine, triethylamine, or the like can be used in addition to the above pyridine. The reaction temperature is 150 to 220 ° C., and the reaction time is not particularly limited, but 1
~ 5 hours are preferred.

The carbonate copolymer of the present invention can be obtained by melting it by appropriately selecting the production conditions. All of them are excellent in transparency and thermal stability, and can be applied alone or in a mixture with various melting points to a field requiring thermoformability. Thus, the carbonate copolymers of the present invention are useful by themselves, but other known resins such as polyethylene, polypropylene, polymethylmethacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyethylene. It is also possible to improve the mechanical strength and thermoformability of these resins by mixing with polyesters such as terephthalate or polyphenylene oxides.

[0009]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The bis (2-hydroxyethyl) 4,4'-bicyclohexanedicarboxylate used in the examples was produced as follows.

In a 300 ml eggplant-shaped flask equipped with a condenser, 4,4'-bicyclohexanedicarboxylic acid 29.8 was added.
g (0.1 mol), thionyl chloride (60 ml) and pyridine (0.5 ml) were added and the reaction was carried out at 80 ° C for 7 hours.
Excess thionyl chloride was distilled off under reduced pressure to obtain 36.2 g of 4,4'-bicyclohexylenedicarbonyldichloride.
Next, in a 500 ml three-necked flask equipped with a condenser and a stirrer, 78.0 g (1.3 mol) of ethylene glycol was added.
l), 30 ml of pyridine and 100 ml of dioxane were added, and the mixture was stirred at 80 ° C. In addition to this, 4,
4'-bicyclohexylene dicarbonyl dichloride 3
A solution prepared by dissolving 6.2 g (0.1 mol) in 300 ml of dioxane was added dropwise over 30 minutes to carry out a reaction for 120 minutes. After completion of the reaction, this reaction solution was poured into 5 liters of water, followed by extraction with 3 liters of ethyl acetate, and the obtained extract was washed 3 times with 2N sodium hydroxide and further with water until it became neutral. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 34.16 g of bis (2-hydroxyethyl) 4,4'-bicyclohexanedicarboxylate. This was used without purification.

The physical properties of the carbonate copolymers obtained in the examples were measured by the following methods. Melting point (Tm): A hot stage (FP-82 manufactured by METTLER CORPORATION) was attached to a polarizing microscope and measured at a temperature rising rate of 3 ° C. per minute. Glass transition temperature (Tg): DSC manufactured by Seiko Instruments Inc.
It was measured with a -200 type at a temperature rising rate of 5 ° C. per minute. Decomposition temperature (Td): TG / DTA manufactured by Seiko Instruments Inc.
It was measured at a temperature rising rate of 10 ° C./min using a −220 type, and was set to a temperature at which the weight loss was 5%. Reduced viscosity (ηred): Calculated by the following formula 1.

[Equation 1] (Here, η is a Ubbelohde viscometer and the concentration of 0.5g / dl in chloroform is 25.0 ± 0.0.
It is a value measured at 1 ° C., η _o is a measurement value of the same dissolution at the same temperature using an Ubbelohde viscometer, and C is a concentration of 0.5 g / dl).

Example 1 A 100 ml three-necked flask equipped with a condenser and a stirrer was charged with 0.68 of bis (2-hydroxyethyl) bis (4,4'-bicyclohexanedicarboxylate).
g (2.0 mmol), 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 2.69 g (8.0 mmol), 1 ml of pyridine and 1,2 -Dichloroethane (hereinafter referred to as DCE) 5
Then, this solution was stirred at a temperature of 90 ° C. with a mantle heater, and a solution prepared by dissolving 1.09 g (5.5 mmol) of trichloromethyl chloroformate in 2 ml of DCE was added dropwise over 20 minutes under reflux. The reaction was carried out for 3 hours as it was. The obtained reaction solution was allowed to cool to 50 ° C., poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtered product was washed with hot methanol and then dried to obtain 3.14 g (yield 84.1) of the carbonate copolymer of the present invention.
%)was gotten. This polymer has a glass transition temperature of 114
C., melting point 167 to 196.degree. C., decomposition temperature 348.degree. C., and reduced viscosity was 0.26. When a chloroform solution of this resin was cast on a glass plate and dried, a transparent polyester carbonate film was obtained. Further, this resin was placed on a glass plate, melted at 220 ° C., and allowed to cool, whereby a transparent film was formed on the glass plate.

(Examples 2 and 3) Bis (2-hydroxyethyl) 4,4'-bicyclohexanedicarboxylate and 2,2-bis (4-hydroxyphenyl) -1,1,1,3 as dihydric alcohol Various carbonate copolymers were prepared in the same manner as in Example 1 except that 3,3,3-hexafluoropropane was used in various ratios. The results are shown in Table 1 together with the results of Example 1.

[0014]

[Table 1]

[0015]

INDUSTRIAL APPLICABILITY The present invention uses, as dihydric alcohols, hydroxyalkyl esters of bicyclohexanedicarboxylic acid and 2,2-bis (4-hydroxyphenyl) -1,1.
A feature is that a novel carbonate copolymer is provided by using 1,1,3,3,3-hexafluoropropane. It is characterized by having a cyclohexylene group as a structural unit and fluorine as a side chain. The properties of the resin can be improved by mixing it with another known resin having thermoformability.

Claims (2)

[Claims] 1. The formula: Structural unit and formula: The reduced viscosity is 0.05 to 1.50 (25 ° C., 0.5 g / d, which is a random copolymer composed of the structural unit represented by
l, chloroform) a fluorine-containing carbonate copolymer of bicyclohexylene diester. 2. A fluorine-containing carbonate of bicyclohexylene diester according to claim 1, which comprises 5 to 95 mol% of the structural unit represented by the formula (1) and 95 to 5 mol% of the structural unit represented by the formula (2). Copolymer.