JPH03103430A - Optically active cyclohexane polyester - Google Patents

Abstract

PURPOSE:To provide an optically active liquid crystal polymer expressed by a specific formula, moldable by melt-molding, exhibiting cholesteric liquid crystal nature at a specific temperature and giving a molded article having high mechanical strength. CONSTITUTION:The objective polyester is expressed by formula (* represents asymmetric carbon; l+m=x+y=1). The polyester can be produced by reacting (R)-(+)-3-methyladipic acid chloride derived from (R)-(+)-3-methyladipic acid with 1-trans-1,4-cyclohexanedicarboxylic acid chloride derived from trans-1,4- cyclohexanedicarboxylic acid, trans-1,4-cyclohexanediol and trans-trans-4,4'- biscyclohexanediol in 1,2,4-trichlorobenzene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an optically active liquid crystalline polyester that can be melt-molded. [Prior Art] Polyesters containing cyclohexylene have been described in recent literature. Here, the cyclohexylene unit is 1.
It is 4-cyclohexane dicarboxylic acid or 1,4-cyclohexane diol, and is a polyester made by combining this with other diols or dicarboxylic acids.

For example, U.S. Pat. No. 4,342,862 discloses that a polyester is prepared by combining a mixture of trans-1,4-cyclohexanedicarboxylic acid and other aromatic dicarboxylic acids with a substituted hydroquinone such as methyl, phenyl or chlorohydroquinone. It is described that it can be obtained by polycondensation. The production of thermotropic liquid crystalline polyesters by polycondensation of only trans-cyclohexanedicarboxylic acid and some of the above-mentioned substituted hydroquinones is described in "Macromolecules" Vol. 19, 18.
24 (19116).

Polyesters of trans-1,4-cyclohexanediol and substituted aromatic dicarboxylic acids or mixtures of cis and trans forms of 1,4-cyclohexanediol and polyesters of aromatic or alicyclic dicarboxylic acids are also described in the above documents. There is. Other thermotropic liquid crystal polymers containing cyclohexane units include "Macromolecules," Vol. 14, p. 1626 (1981).
There are block copolyesters according to “Macro Molecule Hemi (
Macromolecule Chemle)”
There are cobolimers described in Vol. 187, p. 1l45 (1986), which have a rigid structure trans-1.
4-Cyclohexane dibenzoate α. It is obtained by polymerizing ω-alkanedicarboxylic acid. In JP-A No. 64-40,519, a polyester is obtained by polymerizing 4.4°-bicyclohexanediol and alkanedicarboxylic acid. On the other hand, a polymer in which an optically active group is incorporated into the main chain is 2-methylbutyl group in JP-A-64-65,124;
No. 4-79,230 discloses a polymer compound containing optically active 4.4°-biphenylenebisoxybisbropionic acid. [Problem to be solved by the invention] In general, many liquid crystal polymers are known to be aromatic compounds. Recently, polymers containing a cyclohexane ring or a bicyclohexane ring have been discovered, but there are still few that meet physical requirements.

All cyclohexane polyester compounds have no melting point and decompose, making thermoplastic molding difficult. In order to improve this, an optically active alkylene group was introduced to obtain a moldable polyester compound or an infusible liquid crystalline polyester compound that exhibits a cholesteric liquid crystal phase at a melting point of 180°C to 250°C. The polymer of the present invention can be mixed with known polymers to adjust the melting temperature, and since it is a liquid crystal polymer, its mechanical strength can also be increased. The known polymers include, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrenes, polymethyl methacrylate, ABS, polyamides, polycarbonates, polyacrylates, polyesters such as polyethylene terephthalate or polybutylene terephthalate, or polyphenylene oxides. It is. As described above, the compounds of the present invention are useful for improving the heat resistance, chemical resistance, and mechanical strength of known polymers. In addition, a liquid crystal composition for a liquid crystal display device can be prepared by mixing low-molecular liquid crystals. [Means for solving the problem] Many of these are polymeric compounds having the following structure that exhibit a cholesteric liquid crystal phase at 180°C to 250°C. (In the above formula, * indicates an asymmetric carbon, and jZ+m=ax+y snow 1.) It is a cyclohexane optically active polyester represented by the following formula. The cyclohexane optically active polyester of the present invention can be produced according to the conventional melon condensation method. Typical manufacturing methods are as follows. That is, (R)-(◆)-3-methyladipic acid chloride produced from (R)-(+)-3-methyladipic acid and 1-trans- produced from trans-1,4-cyclohexanedicarboxylic acid. 1-,4-Cyclohexanedicarboxylic acid chloride, trans-1,4-cyclohexanediol, and trans,trans-4,4゜-bisclohexanediol in 1,2,4-trichlorobenzene to form the anti-cyclohexane optical activity of the present invention. A polyester reaction was performed to produce the desired optically active cyclohexane polyester. [Effects of the Invention] According to the present invention, it is a moldable cyclohexane optically active polyester compound that exhibits a cholesteric liquid crystal phase at 80°C to 250°C, and is a polymer that can be mixed with known thermoplastic polymers in any proportion.

Therefore, by mixing it with a known polymer in any proportion, it is possible to obtain an optically active liquid crystal polymer, thereby improving the mechanical strength of the molded product. or,
By adding it to a low-molecular liquid crystal composition, it is possible to create a liquid crystal composition for liquid crystal display devices. This will be described in more detail in Examples below. [Examples] The present invention will be explained in more detail below by way of Examples, but the present invention is not limited in any way by these Examples. The raw materials used in the examples were produced as follows. (i) Production of trans-1,4-cyclohexanediol: Olberg et al., Journal of the American Chemical Society, Vol. 68, p. 1097 (1)
trans. by the method described in 944). Cis-mixed 1,4-cyclohexane diol was reacted with acetic anhydride to form acetate, and trans-1,4-cyclohexane diacetate was produced by recrystallization.

This trans isomer was hydrolyzed with barium hydroxide water to produce trans-1,4-cyclohexanediol. Melting point: 140.7-141.6°C. (it) Production of trans,trans-4.4°-bisclohexanediol: Wiles et al., Journal of the American Chemical Society, Vol. 76, p. 1735, (1
Trans and cis mixed 4,4゛-
Bicyclohyxanediol was reacted with benzoyl chloride in dioxane in the presence of pyridine to form dibenzoate. By recrystallization, trans. Trans-4,4'-bicyclohexane dibenzoate was produced. After hydrolysis with an aqueous potassium hydroxide solution, recrystallization is performed. Purpose transformer. Trans-4,4'-bicyclohexanediol melting point 215.5-218.3°C was produced.

(iii) Production of trans-1,4-cyclohexane dicarbonyl chloride: Malachowski et al., Berichte, vol. 71, p. 76l.
(According to the method described in 19381, trans-1,4-cyclohexanedicarboxylic acid was reacted with thionyl chloride using a pyridine catalyst. Thionyl chloride was distilled off, and dried n
- Vacuum distillation after recrystallization with hexane (boiling point 120-130℃)
/7. 5IIlm}Ig) L/ was used for the reaction.
iv) (R) 1(◆)-3-methyladipoyl chloride: A (R)-(+)-3-methyladipic acid was reacted with thionyl chloride using a pyridine catalyst. Thionyl chloride was distilled off and distilled under reduced pressure (boiling point 108~tilt/9).
．． 5mmHg) was used in the reaction. Thermal decomposition is performed at 1/min using TG/DTA200 model manufactured by Seiko Electronics Industries.
Measured at a heating rate of 0℃, ? & Crystal transition temperature, isotropic phase transition temperature was determined using a polarized light microscope @ hot stage (FP manufactured by Mettler).
-82) and was measured at a heating rate of 3°C per minute.

In addition, the intrinsic viscosity is 50 when p-chlorophenol is used as a solvent.
Measured at a concentration of 5 g/i.

Example 1 Production of poly(trans.trans-4.4゛-picyclohexylene-(Rl(◆)-3-methylazibate):
(R) - (+) -3-Methyladiboylc-4.4'-bicyclohexanediol 0.991 in a lQOmu three-bottle flask equipped with a stirrer, condenser, and nitrogen inlet tube.
6g (5mmo1) and! , 2.4-trichlorobenzene (30 mj2) was added, the reaction was carried out for 15 minutes at room temperature under a nitrogen atmosphere, and then the mantle heater was turned on for 2.
3 per reaction mixture in the three-necked flask at 20°C.
I did time distance flow. After cooling this reaction solution to 50°C, methanol 30°C
The precipitate that precipitated was filtered. This precipitate was washed with a small amount of methanol, then boiled with methanol, filtered while hot (three times), and dried. Yield 1.34g
(Yield 83%). This polymer has an intrinsic viscosity of 0.29 and a liquid crystal transition temperature of 259.
~288°C, and the isotropic phase transition temperature was 304~314°C. Table 1 Examples 2 to 5 Trans. Various polyesters were produced in the same manner as in Example 1 using trans-4.4°-bicyclohexanediol and trans-1.4-cyclohexanediol in various proportions.

These results are shown in Table 1 together with the results of Example 1.

note. 1) Patch C: (R)-(+)-3-methyladipoyl chloride 2) BCDO: trans. Trans-4.4
゜-bicyclohexanediol 3) CDO: trans-
1.4-Cyclohexanediol 4) No liquid crystal phase was shown. 5) The temperature was set at a weight loss of 5%. Examples 6 to 1O (R)-(+)-3-methyladipoyl chloride, trans-1,4-cyclohexane dicarbonyl chloride as the acid chloride component, trans. Various polyesters were prepared in the same manner as in Example 1 using trans-4.4°-bicyclohexane diol and trans-1.4-cyclohexane diol in various proportions. These results are shown in Table 2. Note to Table 2. 1) MAC: (R)-(+)-3-methyladipoyl chloride 2) CDCC: }trans.1,4-cyclohexane dicarbonyl chloride 3) BCDO: trans. Trans-4.4°-bicyclohexanediol 4) CDO: trans-1.4-cyclohexanediol 5) The temperature was set at a weight loss of 5%.

Claims (1)

[Claims] (1) A cyclohexane optically active polyester represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the above formula, * indicates an asymmetric carbon and indicates l + m = x + y = 1.)