JPH0733863A - Optically active polyester carbonate resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin composed exclusively of a specific recurring unit, having excellent heat-resistance, thermo-formability (and transparency) and useful as a material for improving the mechanical strength and thermo- formability of other resins and as various molding materials. CONSTITUTION:This resin is composed exclusively of the recurring unit of the formula I or composed of the recurring unit of the formula I and the recurring unit of the formula II and preferably contains 30.0-95.5mol% of the recurring unit of the formula I and 70.0-0.5mol% of the recurring unit of the formula II. The resin composed exclusively of the recurring unit of the formula I is produced by the polycondensation of (R)-(+)-3-methyladipic acid bis(trans-4- hydroxycyclohexyl) ester and the resin composed of the recurring units of the formula I and the formula II is produced by mixing (R)-(+)-methyladipic acid bis(trans-4-hydroxycyclohexyl) ester with 4,4'-dihydroxybiphenyl and reacting the mixture with trichloromethyl chloroformate in the presence of an acid acceptor.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel optically active polyester carbonate resin.

[0002]

2. Description of the Related Art Polycarbonate resin is a synthetic resin which is widely used industrially and is usually 2,2-bis (4
-Hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) and a carbonic acid derivative such as phosgene. A polycarbonate resin produced from bisphenol A is a plastic having excellent impact resistance, small hygroscopicity, and heat stability. In recent years, along with the development of applications for resins, expectations for the development of polycarbonate resins having unprecedented structures and characteristics have increased. Polyester carbonate resin is one of them, and it is a polymer that combines the good properties of polycarbonate resin and polyester resin.

In addition to polycarbonate resins, new polymers have been developed, and one of them is an optically active polymer having a chiral component in the polymer chain. Among them, many polymers using optically active 3-methyladipic acid as a chiral component are disclosed. Japanese Unexamined Patent Publication (Kokai) No. 62-45621 discloses a cholesteric liquid crystalline polyester composed of 1,4-cyclohexanedicarboxylic acid, (R)-(+)-3-methyladipic acid and chlorohydroquinone and a film thereof. The thermal properties are not clear.

The applicants of the present invention have disclosed in Japanese Patent Application Laid-Open No. 3-103430 that trans-1,4-cyclohexanedicarboxylic acid, (R)-(+)-3-methyladipic acid, and trans-1,4-cyclohexanediol. Alternatively, a cholesteric liquid crystalline polyester composed of trans, trans-4,4′-bicyclohexanediol is further described in JP-A-3-182521 and trans-1,4.
-Disclosed cholesteric liquid crystalline polyesters using terephthalic acid or isophthalic acid instead of cyclohexanedicarboxylic acid. However, in these optically active polymers, since the respective monomers are randomly bonded, the bonding mode may be non-uniform.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel optically active polyester carbonate resin having a repeating unit which has not existed in the past.

[0006]

As a result of various studies to solve the above-mentioned problems, the present inventors have found that as a diol component, (R)-(+)-3-methyladipate bis (trans- It was found that a novel optically active polyester carbonate resin can be obtained by using 4-hydroxycyclohexyl) and 4,4′-dihydroxybiphenyl, and completed the present invention. That is, the present invention provides the formula (1) [1]

[0007]

[Chemical 3]

An optically active polyester carbonate resin consisting only of the repeating unit represented by the formula (2), the repeating unit represented by the formula (1) and the formula [2]

[0009]

[Chemical 4]

The optically active polyestercarbonate resin comprising the repeating unit represented by the formula (3) has a final composition of 0.5 to 95.5 mol% of the repeating unit represented by the formula [1] and is represented by the formula [2]. Repeating units are 95.5-0.
It is 5 mol% and is an optically active polyester carbonate resin as described in (2). The optically active polyester carbonate resin of the present invention has a reduced viscosity of 0.20 or more (25
℃, 0.5g / dl chloroform, 50 if insoluble
° C, 0.5 g / dl p-chlorophenol), melting point 206.0 ° C or higher, and decomposition temperature 289.9 to 30.
It has a physical property value of 5.2 ° C. Further, it is possible to make a transparent film by adjusting the diol component.

The optically active polyester carbonate resin of the present invention has the formula [3]

[0012]

[Chemical 5]

Bis (trans-4-hydroxycyclohexyl) of (R)-(+)-3-methyladipate represented by the formula [4]

[0014]

[Chemical 6]

This is mixed with 4,4'-dihydroxybiphenyl represented by the following formula (4) in the presence of an acid acceptor to give a compound of formula [5]

[0016]

[Chemical 7]

It can be produced by reacting with trichloromethyl chloroformate (phosgene dimer) represented by:

[0018]

[Chemical 8]

Further, as used herein, (R)-(+)-
Bis (trans-4-hydroxycyclohexyl) 3-methyladipate has the formula (R)-
It is obtained by reacting (+)-3-methyladipic acid dichloride with excess trans-1,4-cyclohexanediol in the presence of pyridine.

[0020]

[Chemical 9]

With respect to the final composition of the polyester carbonate resin of the present invention, it is desirable that the repeating unit represented by the formula [2] is 70.0 mol% or less. Formula [2]
When the repeating unit represented by is 70.0 mol% or more, when the polyester carbonate is heated, the polyester carbonate is melted while being decomposed, which causes difficulty in melt molding.
Further, since the solubility is remarkably lowered, it is difficult to perform an operation of dissolving polyester carbonate in a solvent to form a film.

In the above production method, phosgene may be used instead of trichloromethyl chloroformate. At this time, it is desirable that the amount of trichloromethyl chloroformate used is 1/2 times or slightly in excess of the total amount of the diol component, and the amount of phosgene used is 1 times or more in excess of the diol component. The reaction temperature is 20 to 100 ° C., and the reaction time is not particularly limited, but is preferably 1 to 5 hours.

Examples of the solvent include halogenated hydrocarbons such as 1,2-dichloroethane (hereinafter sometimes referred to as DCE) and chlorobenzene, aromatic hydrocarbons such as benzene and toluene, and ethers such as tetrahydrofuran and dioxane. it can. Specific examples of the acid acceptor include tertiary amines such as pyridine, triethylamine and N-methylmorpholine, and inorganic bases such as sodium hydroxide. Further, the polyester carbonate resin of the present invention,
In the presence of a transesterification catalyst such as a metal oxide, the diol component represented by the above formulas [3] and [4] and a carbonic acid diaryl ester such as diphenyl carbonate are reacted under high temperature and high vacuum conditions for 4 to 10 hours. It can also be manufactured by a method. In these methods, if necessary, a molecular weight modifier may be added in an amount of 1 to 10 mol% based on the diol.
Examples of the molecular weight modifier include monohydric phenols such as phenol, p-tert-butylphenol and p-cumylphenol. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0024]

EXAMPLES The physical properties of the polyester carbonate resins obtained in the examples were measured by the following methods. Reduced viscosity: measured using an Ubbelohde viscometer with chloroform as a solvent at 25 ° C. and a concentration of 0.5 g / dl. When the polyester carbonate resin is insoluble in chloroform, p-chlorophenol is used as a solvent at 50 ° C. and 0.5
It was measured at a concentration of g / dl. Melting point (Tm): hot stage (Mettler FP-
82) was used to measure at a temperature rising rate of 10 ° C./min. Decomposition temperature (Td): 1 per minute using a differential thermogravimetric simultaneous measurement device (TG / DTA-220 type manufactured by Seiko Denshi Kogyo KK)
The temperature is raised at a rate of 0 ° C, and the temperature at which the weight loss reaches 5% is T
d. Glass transition temperature (Tg): Measured with a differential scanning calorimeter (DSC-200 manufactured by Seiko Instruments Inc.) at a temperature rising rate of 20 ° C. per minute.

Example 1 Production of polyester carbonate consisting of repeating unit represented by the formula [1]: 1) bis (trans-4-hydroxycyclohexyl) bis (R)-(+)-3-methyl adipate, formula [3 〕Manufacturing of. To a 500 ml three-necked flask equipped with a condenser and a stirrer, tetrahydrofuran (THF) 200 ml, pyridine 3
0 ml was added, 30.9 g (0.26 mol) of trans-1,4-cyclohexanediol was added thereto, and about 7
Heat to 0 ° C. and stir under reflux. In addition, (R)-
(+)-3-Methyl adipic acid dichloride 13.0 g
A solution prepared by dissolving (0.07 mol) in 50 ml of THF was added dropwise over 30 minutes, heated to about 70 ° C., and reacted under reflux for 5 hours. After the reaction was completed, the reaction solution was added to 1 liter of water,
It was extracted with 1.5 l of ethyl acetate, and then the organic layer was washed with 3N hydrochloric acid three times, 1N sodium hydroxide three times, and further with water. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the remaining syrup was purified by a silica gel column (heptane: ethyl acetate = 5: 1) to give a pale yellow syrup (R )-(+)-3-Methyl adipate bis (trans-4-hydroxycyclohexyl) 5.80 g (yield 24.7%) was obtained. The structure of this compound was confirmed by IR and NMR and used as it was for polymerization. 2) Polycondensation reaction 1.06 g (3.0 mmol) of bis (trans-4-hydroxycyclohexyl) (R)-(+)-3-methyladipate in a 100-ml three-necked flask, pyridine 1
ml and DCE (5 ml) were added and stirred, and then 0.33 g of trichloromethyl chloroformate (1.
A solution of 7 mmol) dissolved in 2 ml of DCE was added dropwise over 20 minutes, and the reaction was continued for 3 hours. The obtained reaction solution was allowed to cool and then poured into 300 ml of methyl alcohol, and the deposited precipitate was collected by filtration. 50 with this precipitate
ml of methyl alcohol was placed in a 100 ml eggplant flask, refluxed for 1 hour while maintaining at about 70 ° C. in a water bath, and the precipitate was collected by filtration while hot. After repeating this operation three times, the taken-out precipitate was dried to obtain 0.94 g (yield 82.4%) of a polyester carbonate resin. The structure of this polymer was confirmed by IR spectrum. Regarding the physical properties of this polyester carbonate resin, the reduced viscosity is 0.35 and the melting point is 216.0-23.
The temperature was 6.4 ° C, the decomposition temperature was 289.9 ° C, and the glass transition temperature was 167.1 ° C. Also, a chloroform solution of this polymer was cast on a glass plate and dried to obtain a transparent polyester carbonate film. Also, a transparent polyester carbonate film was obtained by placing a polymer on a glass plate, heating at 250 ° C., melting and cooling.

Example 2 Production of Polyester Carbonate Consisting of Repeating Unit of the Formula [1] and Repeating Unit of the Formula [2]: (R)-(+) in 100 ml Three-necked Flask
0.75 g (2.10 mmol) of bis (trans-4-hydroxycyclohexyl) -3-methyl adipate,
4,4'-dihydroxybiphenyl 0.17 g (0.9
0 mmol), 1 ml of pyridine and 5 ml of DCE were added and stirred, and then this solution was heated to 90 ° with a mantle heater.
While maintaining the temperature at 0 ° C, under reflux, 0.33 g (1.7 mmol) of trichloromethyl chloroformate was added to 2 ml of DCE.
The solution dissolved in was added dropwise over 20 minutes, and the reaction was continued for 3 hours. The obtained reaction solution was allowed to cool and then poured into 300 ml of methyl alcohol, and the deposited precipitate was collected by filtration. 1 of this precipitate and 50 ml of methyl alcohol
Place in a 00 ml eggplant flask and use a water bath for about 7
The mixture was refluxed for 1 hour while maintaining the temperature at 0 ° C, and the precipitate was collected by filtration while hot. After repeating this operation 3 times, 0.79 g (yield 78.4%) of the taken-out precipitate was dried.
A polyester carbonate resin of The structure of this polymer was confirmed by IR spectrum. Regarding the physical properties of this polyester carbonate resin, the reduced viscosity is 0.44, the melting point is 206.0 to 244.1 ° C., and the decomposition temperature is 293.5.
C, and no glass transition temperature was observed.

Examples 3-5 (R)-(+)-3-methyl adipate bis (trans-4-hydroxycyclohexyl), and 4,4'-
A polycondensation reaction was performed according to Example 2 except that the molar ratio of the diol component of dihydroxybiphenyl was changed to obtain a polyester carbonate resin. Table 1 shows the molar ratio of the diol component and the physical properties of the obtained polyester carbonate resin.

[0028]

[Table 1]

[0029]

The optically active polyester carbonate resin of the present invention has a novel structure and decomposes at about 300 ° C. and is excellent in heat resistance and thermoformability. It is also possible to form a film having excellent transparency by adjusting the diol component. Thus, the polyester carbonate resins of the present invention are useful by themselves, but other known resins such as polyethylene, polypropylene, polymethylmethacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyethylene terephthalate. It is considered possible to add the new properties while improving the mechanical strength and thermoformability of these resins by mixing with such polyesters or polyphenylene oxides.

Claims (4)

[Claims] 1. A formula [1]: An optically active polyester carbonate resin consisting only of the repeating unit represented by. 2. A repeating unit represented by the formula [1] and a formula [2] An optically active polyester carbonate resin comprising a repeating unit represented by: 3. The final composition is such that the repeating unit represented by the formula [1] is 30.0 to 95.5 mol% and the repeating unit represented by the formula [2] is 70.0 to 0.5 mol%. The optically active polyester carbonate resin according to claim 2. 4. A reduced viscosity of 0.20 or more (25 ° C., 0.
5 g / dl chloroform, if insoluble, 50 ° C., 0.
5 g / dl p-chlorophenol), The optically active polyester carbonate resin according to any one of claims 1 to 3.