JPH04328122A - Polyester carbonate - Google Patents

Abstract

PURPOSE:To provide a polyester carbonate composed of specific structural units, exhibiting liquid crystal phase under decomposition, having excellent mechanical strength, transparency and thermal moldability and useful as molded article, etc. CONSTITUTION:This polyester carbonate is composed of the structural unit of formula I and the structural unit of formula II and/or the structural unit of formula III and has a reduced viscosity of 0.20-0.70 (measured at 25 deg.C) in chloroform at a concentration of 0.5g/dl). The polymer can be produced by mixing bis(trans-4-hydroxycyclohexyl)terephthalate with trans, trans-4,4'- bicyclohexanediol and/or trans-4-cyclohexanediol and reacting with trichloromethyl chloroformate in the presence of pyridine.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new polyester carbonate, and more particularly to a transparent polyester carbonate resin having a new ester structure.

0002

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

By the way, polycarbonate resin produced from bisphenol A has excellent properties such as excellent impact resistance, low moisture absorption, and is stable to heat, but it has the problem of poor chemical resistance. be. In recent years, expectations have increased for resins that are easy to mold and have excellent transparency and strength, which are insufficient for conventional polycarbonate resins, and resins that can be used even at high temperatures, and polyester carbonates with new structural units are desired.

0004

SUMMARY OF THE INVENTION An object of the present invention is to provide a new polyester carbonate resin having a new structural unit without sacrificing the advantages of the excellent polycarbonate resin.

[0005]

[Means for Solving the Problems] As a result of various studies in order to solve the above problems, the present inventors have developed trans-4-hydroxycyclohexyl terephthalate ester and trans-1,4-hydroxycyclohexyl ester as diol components. -Cyclohexanediol and trans,trans-4,4'-bicyclohexanediol have been found to yield a new polyester carbonate resin, and the present invention has been completed. The polyester carbonate of the present invention has the formula

[C4] Structural unit and formula shown in

[C5] Structural unit and/or formula represented by

[C6] It consists of the structural unit shown in

As the first aspect, formulas (1) and (2)
and reduced viscosity of 0.
20 to 0.70 (25°C, 0.5 g/dl, chloroform) polyester carbonate,

As a second aspect, formula (1) and formula (2)
) has a reduced viscosity of 0.20 to 0.
70 (25°C, 0.5g/dl, chloroform) polyester carbonate,

As a third aspect, formula (1) and formula (3
) has a reduced viscosity of 0.20 to 0.
70 (25° C., 0.5 g/dl, chloroform) of polyester carbonate.

The method for producing polyester carbonate of the present invention is as follows:

Bis(trans-4-hydroxycyclohexyl) terephthalate represented by the formula

[Chemical 8] Trans, trans-4,4'bicyclohexanediol and/or the formula

[Chemical formula 9] is mixed with trans-4-cyclohexanediol represented by the formula, and in the presence of pyridine, the formula

It consists of reacting with trichloromethyl chloroformate represented by the following formula. Phosgene may be used in place of trichloromethyl chloroformate in the above production method. The reaction temperature is 20~
The temperature is 100°C and the reaction time is not particularly limited, but is 1 to 5 hours. The amount of trichloromethyl chloroformate and phosgene used is equimolar to the total of the diol components or slightly in excess.

Bis(trans-4-hydroxycyclohexyl) terephthalate represented by formula (4) is represented by the following formula (
As shown in 8)

embedded image It is obtained by reacting terephthalic acid dichloride and excess trans-1,4-cyclohexanediol in the presence of pyridine.

[0011]

[Examples] 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. Note that the raw materials used in the examples were produced as follows.

(1) Production of trans-1,4-cyclohexanediol (produced according to the method described in Olberg et al., Journal of the American Chemical Society, Vol. 66, p. 1097 (1944)) 2-liter Erlenmeyer flask ni 1,4-
Cis and trans mixture of cyclohexanediol 100
．． 0 g was suspended in 300 ml of pyridine and 3000 ml of toluene, and 270 g of acetic anhydride was added to this mixture at room temperature with stirring. The reaction was further carried out at room temperature for 12 hours. After adding 1 liter of toluene and 2 liters of water to this reaction solution, the mixture was washed three times with 5N hydrochloric acid, three times with 2N sodium hydroxide, and water until neutral, and dried over anhydrous sodium sulfate. Toluene was distilled off under reduced pressure, and the resulting crystals were recrystallized with ethanol to obtain trans-1,4
-Cyclohexane diacetate 39.7g (yield 46.
1%). Melting point 102.1-102.9°C, trans-1,4-cyclohexane diacetate 10.0 in a 500 ml three-necked flask equipped with a stirrer and a condenser.
g, barium hydroxide octahydrate 66.3g, water 100
ml and 300 ml of ethanol were added and reacted under reflux for 8 hours. The reaction solution was evaporated under reduced pressure and dried, and the remaining solid was boiled with 350 ml of acetone and filtered while hot. The filtrate was concentrated under reduced pressure and the precipitated crystals were recrystallized from acetone to obtain 4.0 g of trans-1,4-cyclohexanediol.
(yield: 69.6%). Melting point 140.7-141.
The temperature was 6°C.

(2) Transformer, transformer-4,4'-
Production of Bicyclohexanediol (Wiles et al., Journal of the American Chemical Society, Vol. 76, p. 1735, (1954)
240.4 g of an isomer mixture of 4,4'-bicyclohexanediol, 1200 ml of dioxane, and 720 ml of pyridine were placed in a 3-liter three-necked flask equipped with a stirrer and a condenser. 640.0 g of benzoyl chloride was added while stirring at room temperature. The mixture was reacted under reflux for 8 hours, dried under reduced pressure, and the remaining solid was dissolved in chloroform. The solution was washed three times with 2N potassium hydroxide, three times with 6N hydrochloric acid, and water until neutral, and dried over anhydrous sodium sulfate. After concentrating under reduced pressure, the precipitated crystals were recrystallized from toluene to obtain 150.5 g (yield 30.5%) of trans, trans-4,4'-bicyclohexane dibenzoate, melting point 1.
02.1~102.9℃, transformer, transformer-4 in a 3 liter three-necked flask equipped with a stirrer and a condenser.
, 4'-bicyclohexane dibenzoate 150.0g
, methanol 1800ml, potassium hydroxide 75.0g
, 150 ml of water was added, and the mixture was reacted under reflux for 5 hours. The reaction solution was poured into 1200 ml of water, the precipitated crystals were filtered, and then recrystallized with ethanol to obtain trans, trans-4,
4'-bicyclohexanediol 56.1 g (yield 74
．． 1%). The melting point was 215.5-216.3°C.

(3) Bis(trans-4) terephthalate
-Hydroxycyclohexyl) production: Transfer to a 300ml three-necked flask equipped with a condenser and stirrer-
23.5 g of 1,4-cyclohexanediol, 100 ml of N-methyl-2-pyrrolidone, and 16 ml of pyridine were added and stirred at 130°C. Add 10.1 g of terephthalic acid dichloride to this and 50 ml of N-methyl-2-pyrrolidone.
A solution dissolved in was added dropwise over 50 minutes, and the reaction was carried out for 4 hours. After the reaction was completed, the reaction solution was poured into 3 liters of water, extracted with 1.5 liters of ethyl acetate, and washed three times with 6N hydrochloric acid, three times with 2N sodium hydroxide, and with water until neutral. After drying the ethyl acetate layer over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure. Recrystallize with ethanol to obtain 5.3 g of bis(trans-4-hydroxycyclohexyl terephthalate) (melting point 189.6-190).
．． 6°C). The yield was 29.2%.

Next, the physical properties of the polyester carbonate resin obtained in the examples were measured by the following method. Reduced viscosity: 25°C using chloroform as a solvent, 0.
It was measured at a concentration of 5 g/dl. Melting point (Tm): Measured using a polarizing microscope equipped with a hot stage (FP-82 manufactured by Mettler) at a heating rate of 3°C per minute. Decomposition temperature (Td): TG/D manufactured by Seiko Electronics Co., Ltd.
Measured using a TA-220 model at a heating rate of 10°C per minute.
The temperature was set at a weight loss of 5%.

Example 1 Production of polyester carbonate consisting of a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3): In a 100 ml three-necked flask, terephthalate was added. Acid bis(trans-4-hydroxycyclohexyl) 0.22 g (0.6 mmol), trans, trans-4,4'-bicyclohexanediol 0.
12g (0.6mmol), trans-1,4-cyclohexanediol 0.21g (1.8mmol), pyridine 1ml and 1,2-dichloroethane (hereinafter referred to as DC
Add 5 ml of chloroformate (referred to as E) and stir, then maintain this solution at 90°C with a mantle heater and dropwise add a solution of 0.33 g (1.7 mmol) of trichloromethyl chloroformate dissolved in 2 ml of DCE under reflux over 20 minutes. Then, the reaction was continued for 3 hours. After cooling the obtained reaction solution to 50°C, methanol 3
The precipitate was filtered. The filtrate was washed in hot methanol and then dried to give a
g (yield: 84.8%) of polyester carbonate was obtained. This polyester carbonate has a reduced viscosity of 0
．． 50, melted with decomposition at a decomposition temperature of 295°C and a melting point of 295-297°C. A chloroform solution of this polymer was cast on a glass plate and dried to obtain a transparent polyester carbonate film.

Examples 2 to 3 The procedures were carried out except for changing the component ratios of bis(trans-4-hydroxycyclohexyl) terephthalate, trans, trans-4,4'-bicyclohexanediol, and trans-1,4-cyclohexanediol. It was carried out according to Example 1. Table 1 shows the component ratio and the physical property values of the obtained polyester carbonate.

Example 4 Production of polyester carbonate consisting of structural units represented by formula (1) and structural units represented by formula (2): 1
0.55 g (trans-4-hydroxycyclohexyl terephthalate) in a 00 ml three-necked flask.
5 mmol), trans, trans-4,4'-bicyclohexanediol 0.3 g (1.5 mmol), pyridine 1 ml and 1,2-dichloroethane (hereinafter referred to as DC
Add 5 ml of chloroformate (referred to as E) and stir, then maintain this solution at 90°C with a mantle heater and dropwise add a solution of 0.33 g (1.7 mmol) of trichloromethyl chloroformate dissolved in 2 ml of DCE under reflux over 20 minutes. Then, the reaction was continued for 3 hours. The obtained reaction solution was allowed to cool and
After the mixture was cooled to 0°C, it was poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to obtain 0.81 g (yield: 84.8%) of polyester carbonate. The physical property values are shown in Table 1.

Example 5 Production of polyester carbonate consisting of structural units represented by formula (1) and structural units represented by formula (3): 100
Bis(trans-terephthalate) in a ml three-necked flask.
4-hydroxycyclohexyl) 0.55g (1.5m
mol), trans-1,4-cyclohexanediol 0.18 g (1.5 mmol), pyridine 1 ml and 1,2-dichloroethane (hereinafter referred to as DCE) 5 m
Then, the solution was kept at 90°C with a mantle heater, and under reflux, a solution of 0.33 g (1.7 mmol) of trichloroformate dissolved in DCE was added dropwise over 20 minutes.ゝThe reaction was carried out for 3 hours. The resulting reaction solution was allowed to cool to 50° C., then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to a zero.
77 g (yield 91.7%) of polyester carbonate was obtained. The physical property values are shown in Table 1.

[0020]

[Table 1]

[0021]

Effects of the Invention The polyester carbonate of the present invention melts with decomposition at about 300°C and can be used at high temperatures. Furthermore, a film with excellent transparency can also be produced. Another feature is that it exhibits a liquid crystal phase while decomposing. Thus, although the polyester carbonate of the present invention is useful in itself, it can also be used with other known resins such as polyethylene, polypropylene, polymethyl methacrylate, ABS, polyamides, polyacrylates, etc.
By mixing with polycarbonates, polyesters such as polyethylene terephthalate, or polyphenylene oxides, it is possible to improve the mechanical strength and thermoformability of these resins and to impart new properties.

Claims (4)

[Claims] 1. A polyester carbonate comprising a structural unit represented by the formula [Formula 1], a structural unit represented by the formula [Formula 2], and/or a structural unit represented by the formula [Formula 3]. 2. A reduced viscosity of 0.20 consisting of structural units represented by formulas (1), (2) and (3) according to claim 1.
~0.70 (25°C, 0.5g/dl, chloroform)
of polyester carbonate. [Claim 3] Formula (1) and formula (2) according to claim 1
) has a reduced viscosity of 0.20 to 0.
70 (25° C., 0.5 g/dl, chloroform) polyester carbonate. [Claim 4] Formula (1) and formula (3) according to claim 1
) has a reduced viscosity of 0.20 to 0.
70 (25° C., 0.5 g/dl, chloroform) polyester carbonate.