JPH03126717A - Conjugated organic polymer compound - Google Patents

Abstract

PURPOSE:To obtain a conjugated organic polymer substance suitable for optically functional material, especially liquid crystal polymer substance, having excellent fluorescence emitting properties at long wavelength side, photoconductivity to light rays of long wavelength range, comprising a specific repeating unit and having specific molecular weight. CONSTITUTION:A conjugated organic polymer substance suitable for fluorescence scattering liquid crystal element, luminous liquid crystal element, recording material, polarizing film, high-efficiency electro-optical material, etc., comprising a repeating unit shown by formula IV (alpha and beta are H, cyano, etc.) and having >=1,000, preferably 5,000-30,000 molecular weight, for example, synthesized from a compound shown by formula I [A is group shown by formula II (R1-4 is H, halogen, etc.; (m) is 2-10] and a dicarboxylic acid compound shown by formula III ((n) is 1-23) by ester reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel conjugated organic polymer compound useful as an optical functional material and further as a liquid crystal polymer substance.

<Prior art> In recent years, the conductivity of conjugated organic polymer compounds such as polyacetylene has been dramatically improved by doping with dopants such as AsF5 + I2 (Ph
ys, Rev, Letters, Vol.
39. 1098 (1977)), and by doping a conjugated organic polymer compound such as polyacetylene with an electron-donating or electron-accepting compound, n-type, p-type
(Applied Phys, Let
ters 3318 (197B)), and research on its development has become active.

Furthermore, in conjugated polymers such as polydiacetylene, π electrons exhibit a nonlinear response to the electric field of strong light such as a laser, so their application as nonlinear optical materials is also attracting attention. Further, since conjugated polymers such as polypyrrole and polythiophene change color by doping them with appropriate compounds, attempts have been made to apply them to color switches and the like. [Industrial Materials 31, (NOIO)
69).

As described above, conjugated organic polymer compounds, which have the potential for new applications, are expected to develop even newer functions.

<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide a novel conjugated organic polymer compound useful as an optical functional material and further as a liquid crystal polymer substance.

<Means for Solving the Problems> As a result of intensive studies on organic polymer compounds, the present inventors found that when a specific conjugated system is contained in the repeating unit of the main chain, luminescent properties such as fluorescent light emission are impaired. It has been found that a useful conjugated organic polymer compound can be obtained which exhibits liquid crystal behavior in an appropriate temperature range, and the present invention has been made based on this finding.

That is, the conjugated organic polymer compound of the present invention has a repeating unit represented by the following structural formula (11 or (1)') and has a number average molecular weight of 1,000 or more.

0 111 + (1-MC=C-Ah-0-C(CH2), C←
(11α β 0 ]] 10 C-A (C= C-A C 0 (CHz) - 0+ (1)' α β [In the formula, m is an integer from 2 to 10, and n is an integer from 1 to 23. represent

A- is a group represented by 2, and R1-4 and R5-8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an amino group, an alkyl group having 1 to 5 carbon atoms. Amino group, hydroxy group, alkoxy group having 1 to 5 carbon atoms, cyano group, nitro group or the following formula (aL (b) or [
Represents a group represented by C1. -8 may be the same group or different groups. However, at least one of R1-4 among -A- is the following formula ta+
, (represents a group represented by bl or (C1).

(C) (Formula (al, fb), in fcl, R5-9 and R
I3 arch 6 and RI7 are each independently a hydrogen atom,
Halogen atom, alkyl group having 1 to 5 carbon atoms, amino group,
It represents an alkylamino group having 1 to 5 carbon atoms, a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, an aldehyde group, a carboxyl group, a cyano group, or a nitro group. ) α and β are each independently a hydrogen atom, a cyano group or a nitro group. ] In the above formulas (1) and (1)', m indicates the length of the conjugated system, and is selected to obtain a desired emission spectrum such as fluorescence. Furthermore, for the function of increasing the susceptibility of the nonlinear optical function, it is preferable that m be large, but conversely, it is preferable that m be small in terms of ease of formation. Furthermore, the value of m also influences the liquid crystal formation behavior. In this way, the value of m is selected from the viewpoint of the function to be utilized, the difficulty of the platform, etc., but usually m = '1 to 4 is preferable, more preferably m = 2 to 3, Particularly preferably m='l.

n indicates the length of the spacer in the molecule, which affects the thermal transition behavior, mechanical properties, etc. of the polymer.

For example, it affects the phase transition behavior in liquid crystal formation.

Generally, n=2 to 14 is preferable, n=4 to 12 is more preferable, n=6 to 10 is particularly preferable, and n=3 is most preferable.

In addition, instead of the methylene chain -+-CH2-h-, a part of H is replaced with an alkyl group R (R is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms). It is also possible to use branched alkylene chains substituted with groups, particularly preferably methyl groups.

In the above formulas (1) and (1)', α and β are preferably hydrogen or an amino group, and more preferably α is a cyano group and β is hydrogen, or α is hydrogen and β is a cyano group.

In the above formulas (1) and (1)', -Am is any group. Also, in the repeating unit of the formula,
-A- may all have the same structure or may include those with different structures.

There are three possible structures in which the elements are connected at the individual, meta, and ortho positions, but a structure in which the elements are connected at the individual positions is preferable from the viewpoint of the degree of conjugation of electrons in the conjugated system and the ability to form liquid crystals.

R1-4 and R5-8 are preferably a hydrogen atom and a carbon number of 1
-3 alkyl group, halogen atom, below (a).

(b) or a group represented by (C1).

0 In the above (al, (bl, (C)), R9-12
, R13-+6RI7 is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a cyano group, a nitro group, an a≧no group, an alkylamino group having 1 to 3 carbon atoms, or an alkoxy group having 91 to 3 carbon atoms. A hydrogen atom, a halogen atom, a methyl group, a cyano group, and a nitro group are more preferred.

Examples of preferred structures for the groups represented by (al, (bl, (C1) above are shown below. 1 2 The partial structures in formulas (1) and (1)' are as follows (I) (X II[) can be mentioned.

(■) 1 " (V) 1)1 3 (VI) p+ [■ ■.

R1 2 in (2) is hydrogen, )\rogen, methyl group, <R3 is hydrogen, cyano group, methyl group), and at least one is a group other than hydrogen.

] (■) (■) (TX) (X) (XI) (m is 2. 3 or 4) 5 (XI[) (XII[) More preferably, the above (I) and (If).

(III), (IV), (V), (Vl)
and particularly preferably (II), (III),
(V), (VI), most preferably (II
), (III).

In addition, in the repeating units represented by formulas +11 and (1)' above, the average content (Ct) of trans bonds in carbon-carbon double bonds is the thermal phase transition behavior of the conjugated organic polymer compound of the present invention. C5 is preferably 60% or more, more preferably 80% or more, since it affects mechanical properties and the like.

The conjugated organic polymer compound of the present invention has a number average molecular weight of 1
,000 or more, preferably 2,000 or more, more preferably 3,000 to ioo, ooo, still more preferably 4,000 to 50,000, particularly preferably 5,000 to 30,000.

Further, the conjugated organic polymer compound of the present invention preferably has a repeating unit represented by the above formula (11) from the viewpoint of fluorescence emission characteristics on the long wavelength side and photoconductivity with respect to light in the long wavelength region. .

The above-mentioned conjugated organic polymer compound (1) of the present invention can be produced, for example, as follows.

First, a polymer compound having a repeating unit represented by the above formula (11) is a diol compound represented by the following formula: % formula % ((m and A are as defined above) and the following formula; % formula % %( ((n has the same meaning as above)) 7 A method of directly synthesizing a dicarboxylic acid compound represented by (2 is an alkyl group, and n has the same meaning as above.) The bottom can also be formed by a transesterification reaction between an ester compound represented by the formula (2) and a diol compound represented by the above formula (al).

On the other hand, a polymer compound having a repeating unit represented by the above formula (1)' can also be produced by a method similar to the above-mentioned method.

That is, a dicarboxylic acid compound represented by the following formula: % formula % () (m and A have the same meanings as above) and a dicarboxylic acid compound represented by the following formula: % formula % () (n has the same meaning as above) The diol compound can be directly reacted with a diol compound by a conventional ester reaction. In addition, the bottom can also be reached by transesterification reaction between an ester compound represented by the following formula: % formula % ((R, m and A have the same meanings as above) and a diol compound represented by the above formula (a). can.

Furthermore, the polymer compounds represented by (1) and (1)' can be synthesized using other known polygon synthesis methods (synthetic polymers ■).

p, 188-191. (edited by Shunsuke Murahashi et al., published by Breakfast Shoten)
It can also bottom out.

For polymerization, a melt polycondensation method can be used in which the monomer and the polymer are heated to a temperature higher than their melting points to carry out a polycondensation reaction in a homogeneous liquid phase system. Furthermore, a solid phase polycondensation method can also be used depending on the case.

Alternatively, for example, the carboxylic acid of the compound represented by the structural formula fb) to d) may be converted into an acid chloride or a chloropormate, this compound is dissolved in an organic solvent, and the structural formula (al
It is also possible to use an interfacial polycondensation method in which a diol compound represented by 1 to fe) is dissolved in water, the two are brought into contact, and a polyester is synthesized at the interface.

Alternatively, a solution polycondensation method in which monomers and polymers are polymerized in a solvent can also be used.

The polycondensed compound is prepared by adding a catalytic amount of iodine to give a concentration of 0 to 1
By reacting at 00° C. for 1 minute to 60 hours, a trans isomerization reaction can be carried out, and the conjugated organic polymer compound of the present invention having a desired C5 can be obtained.

<Function> The conjugated organic polymer compound of the present invention has a long conjugated system in its main chain, and since the length of the substantially effective conjugated system can be controlled, it has a unique energy level. It has luminescent properties such as "fluorescence" that are thought to be due to its structure.

Furthermore, by selecting the structure of the mesogen group (the 0 part that contributes to liquid crystal formation), the length of the methylene chain, etc.
It may also have thermotropic liquid crystal behavior exhibiting an intermediate phase in the region above the transition temperature from a solid phase to an intermediate phase (liquid crystal phase) and below the transition temperature from an intermediate phase to an isotropic fluid.

Utilizing such characteristics, the conjugated organic polymer compound of the present invention can be used in a wide range of fields. For example, it can be used for displays that utilize the function of absorbing excitation light and emitting "fluorescence" or "phosphorescence." Furthermore, we have developed a fluorescent light-scattering liquid crystal element that utilizes the liquid crystal function and uses the focal conic structure as a light scattering center to effectively extract fluorescent light to the outside of the liquid crystal element, and a light-emitting liquid crystal that controls the orientation of liquid crystal groups using electric and magnetic fields. It can be applied to elements, etc.

Furthermore, using the polymer of the present invention or a composite material of the polymer of the present invention and a dielectric material such as cyanoethyl cellulose,
It can also be expected to be applied as electroluminescence, which emits light by applying a voltage to it.

Furthermore, the polymer of the present invention can be used as a recording material (thermo recording) by utilizing the thermo-optic effect1.
It can be used as a thermally addressed display material.

The homeotropically oriented transparent polymer film of the present invention is irradiated with laser light to heat it, transition to an isotropic liquid phase, and then rapidly cooled to form a polydomain structure and change the light scattering state. to be retained in memory. In this way, information can be recorded and images can be written. Written information or images can be erased by heating the polymer film to transform it into an isotropic liquid phase again and then slowly cooling it, or by slowly cooling it while applying an electrolytic or magnetic field to create a transparent homeotropic film. This can be done by forming a tissue.

It is also possible to record the information or write the image described above using a heating electrode instead of a laser.

In particular, the polymer of the present invention has a specific conjugated system in its main chain, has an absorption spectrum (color tone) based on this specific conjugated system, and has excellent coordination properties. Therefore, when using the polymer of the present invention,
Information recording and video writing can be performed with high contrast. Furthermore, this property can also be used as a polarizing film.

In addition, the polymer of the present invention has delocalized π electrons in the conjugated system of the main chain, and the conjugated system of the main chain is highly oriented in one direction, so it can be used as a highly efficient electro-optic material. It can also be used for other applications.

Furthermore, it can be used as a photoconductive material.

<Examples> Next, the present invention will be explained in more detail with reference to Examples.

Example 1 50 mj of ethanol in which 5 g of potassium hydroxide and 5 g of terephthalaldehyde were dissolved! 12 g of p-methoxyhensyl cyanide was added dropwise to the solution and reacted at room temperature for 3 hours. The precipitate was filtered, thoroughly washed with water, and then recrystallized with methanol.
Drying under reduced pressure gave 3.

This compound Log was dissolved in 200 mj2 of acetic acid, and 70 mj2 of hydrobromic acid was added dropwise to this mixed solution, followed by reaction at 110°C for 9 hours. The precipitate was filtered and thoroughly washed with water to obtain a compound represented by the following formula.

Add 3 g of this compound and 0.65 g of sodium hydroxide to 2 ml of water.
It was dissolved at 0 mA. Add 20 mj of 0-dichlorobenzene to this aqueous solution! A solution in which 1.94 g of sebacate acid chloride was dissolved in was mixed with 0.01 g of triethylhensyl ammonium chloride, and the mixture was reacted with vigorous stirring at room temperature for 1 hour. The reaction product was poured into 500 mj+ of methanol, and the polymer polycondensate was filtered out, washed with methanol using a Soxhlet extractor, and then dried under reduced pressure.

This polymer was determined by elemental analysis, JR etc. It was confirmed that it is a polymer with repeating units.

The polymer exhibited a mesophase above 250°C, but the transition temperature from the mesophase to the isotropic phase could not be measured because it approached the decomposition temperature.

The fluorescence spectrum of the polymer is shown in FIG.

Thus, the polymer of this example has liquid crystal behavior and exhibits fluorescence behavior with a peak around 470 r+m.

[Brief explanation of the drawing]

FIG. 1 is a fluorescence spectrum diagram of the compound obtained in Example 1.

Claims (1)

[Claims] 1) having a repeating unit represented by the following structural formula (1),
A conjugated organic polymer compound with a number average molecular weight of 1,000 or more. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, m represents an integer from 2 to 10, and n represents an integer from 1 to 23. -A- has formulas ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ It is a group represented by R^1^-^4 and R^5^-
^8 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an amino group, an alkylamino group having 1 to 5 carbon atoms, a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, a cyano group , nitro group or the following formulas (a), (b
) or (c). -A- may be the same group or different groups. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (a) (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) In formulas (a), (b), (c), R^9^-^1^2, R
^1^3^-^1^6 and R^1^7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an amino group, an alkylamino group having 1 to 5 carbon atoms, It represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, an aldehyde group, a carboxyl group, a cyano group, or a nitro group. α and β are each independently a hydrogen atom, a cyano group or a nitro group. 2) A conjugated organic polymer compound having a repeating unit represented by the following structural formula (1)' and having a number average molecular weight of 1,000 or more. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)' [In the formula, m and n, -A-, α and β are
Same as . ]