JPH02227425A - Conjugated polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, having molecules capable of solely exhibiting a liquid crystal phase as side chain, capable of imparting high electric conductivity by doping and useful as an electronic and optical functional element, separation membrane, etc. CONSTITUTION:The objective polymer obtained by using a polymer (heterocyclic 5-membered ring polymer), prepared by carrying out oxidative polymerization of a substituted aromatic compound (preferably 3-substituted thiophene) and having conjugated double bond as a backbone chain and binding liquid crystal molecules capable of solely exhibiting a liquid crystal phase as substituent groups to side chain with an alkyl chain, ether chain, etc., having a suitable length as a spacer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an atomically conjugated polymer having liquid crystalline molecules as side chains. The husks of the present invention can be used as a cold body, an electronic/optical functional element 1 separation membrane, an optical separation membrane, etc.

[Prior art] Polymers such as polyacetylene, polythiophene, polypyrrole, etc. whose main chain is composed of a conjugated system have a conductivity that changes between an insulator and a metal by doping the conductor. , it can be expected to be used for various purposes. especially,
When side chains are introduced into these, the properties of the polymer change. For example, it has been shown that introducing a long-chain alkyl group into the 3-position of polythiophene causes it to become solubilized and melted (Katsumi Yoshino et al., Fundamentals and Applications of Conductive Polymers (IBC, 193B)'). . In addition, there is an ethanesulfonate group at the 3 position of polythiophene.

In some cases, attempts have been made to introduce a butanesulfonate group, etc.

[Problem to be solved by the invention] Since the properties of the obtained tUt polymer change depending on the properties of the side chain introduced into the tUt conjugated polymer, the type of side chain to be introduced will depend on the functional application. extremely important. However, conventionally, only a small number of molecular species have been introduced into the conjugated polymer.

[Means for Solving the Problems] As a result of repeated studies to improve the functional control of conductive polymers, the present inventors added a substance that exhibits a liquid crystal phase by itself to the side chains of conductive polymers. They discovered that the problem could be solved by introducing this, and completed the present invention. That is, the present inventors bonded a molecule that exhibits a liquid crystal phase by itself to a conjugated molecule in advance, and then polymerized the conjugated molecule using a chemical or electrochemical method to form a conjugated molecule having a liquid crystal molecule in its side chain. We succeeded in creating a#, t+a and arrived at the present invention.

The present invention relates to a tI-containing conjugated polymer having as a side chain a molecule that exhibits a liquid crystal phase by itself.

In the present invention, 1ait and 1ait are polymers whose main chain has a conjugated double bond, and are obtained by oxidative polymerization of various substituted aromatic compounds. Specifically, many aromatic compounds such as substituted virol, substituted thiophene, substituted benzene, and substituted aniline are used as the compound, but 3-substituted thiophene is particularly preferably used.

As the liquid crystal molecules introduced into the side chains as substituents, various types such as nematic and smectic molecules can be used, but ferroelectric liquid crystal molecules are particularly preferably used. Further, for bonding the liquid crystal molecules to the conjugated molecules, an alkyl member, an ester metal fitting, an ether chain, or the like of an appropriate length is preferably used as a spacer.

By introducing this liquid crystal molecule as a side chain, the monomer can be polymerized while controlling its dispersion and orientation in a homogeneous liquid crystal matrix. That is, by polymerizing the molecules while controlling them in the reaction field, it is possible to synthesize a Togami Shibakuima strain with the desired conformation 9 molecular orientation. Furthermore, it has become possible to overcome liquid crystallinity, ferroelectric liquid crystallinity, optical activity, etc., and to impart selectivity to dopant molecules, allowing for separation of molecules.

Sorting 8 selective adsorption becomes possible.

[Example] The present invention will be explained in more detail by showing examples below.

Example 1 l-(1) 4'-(1,1''-thiopheneacetoxycundesyloxy)biphenyl-4-carvone 92-methylbutyl ester 3.0 g of thiophene acetic acid was converted into chloride with an excess equivalent of thionyl chloride. 211-Bromundecanol 5.4
g in toluene for 5 hours to obtain 7.9 g (1) of thiophene acetic acid-11-bromundecanoyl ester.

3.0 g of 4'-hydroxyphenyl-4-benzoic acid,
After pouring 7.9 g of (-)-2-methylbutanol and 0.5 mj of concentrated sulfuric acid for 30 minutes, 100 mj of toluene was added.
A Dean-Stark type flow condenser was attached to the mixture, and the mixture was allowed to flow for 8 hours to complete the ester reaction. Recrystallized from hexane to give 4'-hydroxyphenyl-4-benzoic acid 2-
3.5 g of methyl butyl ester (II) was obtained.

2.9 g of compound (1) and compound (II)2. Og and 0.97 g of potassium carbonate and 150 m of 3-pentanone
The product obtained by flowing in R for 48 hours was recrystallized from hexane to obtain 3.2 g of the desired product (III).

The structure of this object (III) is shown in the NMR spectrum.

Confirmed by infrared spectrum, elemental analysis, etc.

That is, in the infrared spectrum, νC1° is 1735
cm-', consistent with the above structure. The melting point of this substance is 54-58°C, and the specific optical rotation [α]. −+2.5 (chloroform solution).

1-(2) Polymerization/electrochemical method of 2-methylbutyl 4'-(1-beechoffeneacetoxyundecyloxy)biphenyl-4-carboxylic acid The above monomer (+11) 60G+ag and lithium borofluoride (LiBF4) 200B Benzonitrile 2
0 mj to prepare an electrolytic polymerization solution. A Ni plate was attached as a cathode and a Nesaglass was attached as an anode to this solution, and electrolytic polymerization was carried out at a voltage of 7 cm (80 mC/cm 2 ), and a black-purple film with a thickness of about 0.1 μm was formed on the anode. Then, when dedoping was performed, the color changed to yellow. When doped again, it returned to its original color and exhibited reversible doping and dedoping functions similar to ordinary conductive polymers.

The structure of the product was confirmed by 'H-NMR, infrared spectroscopy, and elemental analysis. The carbonyl absorption band in the infrared spectrum became broader due to polymerization, and its center was at 1700 cm-1.

The electrical conductivity of the BF4- doped film immediately after preparation was measured using the four-terminal method, and it was found to be 0. It was IS/ca+.

・Chemical method (III) 2. Og and ferric chloride2.
3 g was stirred in chloroform at room temperature for 24 hours.

Thereafter, it was reprecipitated with methanol to obtain 0.2 g of a polymer.

The obtained product was soluble in polar solvents such as DMSO and DMF. Further, as a result of molecular weight measurement by GPC, the weight average molecular weight Mw of this polymer was 11.400.

It was confirmed that this polymer is a polymer mainly composed of structural units.

1-(3) The above polymer could be mixed into a strongly galvanic liquid crystal.

1-(4) Optical rotation and circular dichroism were confirmed in the above film.

1-(5) When the temperature change in the electrical conductivity of the above film was measured, a birth anomaly was observed around 70°C to 90°C, suggesting the appearance of a liquid crystal phase.

Example 2 In Example 1, 4' instead of compound (III)
Polymerization was carried out in the same manner as in Example 1 using (11''-thiopheneacetoxyundecyloxy)phenylbenzoate-4-carboxylic acid 2-methylbutyl ester. A color change due to reversible doping and dedoping was observed, and the electrical conductivity immediately after preparation was measured using the four-probe method and was found to be 0.257 cm. Abnormalities were observed.

[Effects of the invention] The physical properties of the conjugated polymer of the present invention can be artificially controlled by introducing a specific side chain species, and the conjugated polymer having liquid crystal molecules as a side chain has high properties due to doping. It can impart electrical conductivity and is useful as an 11-element/optical functional element 1 separation film, optical separation film, etc.

Patent applicant Katsu Minoru Yoshino Between Idemitsu Kosan Co., Ltd.

Claims (4)

[Claims] (1) A conjugated polymer having as a side chain a molecule that exhibits a liquid crystal phase by itself. (2) The main chain of the conjugated polymer is a five-membered heterocyclic ring. The conjugated polymer according to claim 1, which is a polymer. body. (3) The conjugated polymer according to claim 2, wherein the five-membered heterocycle is a thiophene ring. (4) The side chain of the conjugated polymer is a ferroelectric liquid crystal The conjugated polymer according to claim 1, which is a molecule. body.