JPH0463805A - High-molecular compound having azomethine group in side chain - Google Patents

Abstract

PURPOSE:To provide a high-molecular compd. useful for an electro-optic device, a piezoelectric device, a laminate device, etc., by preparing the compd. comprising repeating units having an azomethine group in the side chain. CONSTITUTION:The title compd. comprises repeating units of formula I (wherein R<1> is H or methyl; X is 1-20; and D is an electron-donating group) and has a number-average mol.wt. of 1000-1000000. The compd. is prepd. by synthesizing an azomethine compd. of formula II from a starting material comprising p- hydroxybenzaldehyde, converting the azomethine compd. into a compd. of formula III, reacting the compd. (meth)acryloyl chloride to give a polymerizable active monomer of formula IV, and polymerizing the monomer in the presence of a polymn. initiator (e.g. benzoyl peroxide) in an inert solvent (e.g. toluene), thus giving a high-molecular compd. comprising repeating units of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymer compound having an azomethine group in its side chain.

[Prior art and problems to be solved by the invention] The polymer compound of the present invention is a new type of polymer compound that has not been described in any literature, and provides a polymer material useful as various devices in the optoelectronics field. The purpose is to

[Means for Solving the Problems] The polymer compound of the present invention has the following formula (I) -+-(R2-C← C=0 (I)0+-C11
2+TO-o-C1 (=N-o-D (in the formula, R1 represents a hydrogen atom or a methyl group, X represents an integer of 1 to 20, and D represents an electron donating group). and has a number average molecular weight of 1,000 to 1,000,000.

The present invention will be explained in detail below.

The polymer compound of the present invention has a number average molecular weight of 1000 to 1
00,000, preferably 5,000 to 700,000, more preferably 10,000 to 50,000.

In the formula (I), R1 represents a hydrogen atom or a methyl group, preferably a methyl group.

X represents an integer of 1 to 20, preferably 1 to 12, and more preferably 1 to 8.

The electron-donating group represented by D refers to a substituent whose substituent constant O is negative according to Hammett's rule. Among them, those in which 0 is −02 or less are preferable.

Examples of such electron donating groups include amino group, dimethylamino group, diethylamino group, methylamino group,
Among them, dimethylamino group and diethylamino group are preferred, and dimethylamino group is more preferred.

The polymer compound of the present invention can be used, for example, in the following reaction steps 1 to 4.
It can be manufactured through

(Reaction step 1) [In formulas (II) and (+11), D has the same meaning as above 1 The aniline compound represented by formula (II) and a slightly excess p-hydroxybenzaldehyde are mixed with ethanol etc. The azomethine compound represented by the above formula (Ill) is synthesized by reacting with acetic acid as a catalyst in a solvent while distilling off the solvent.

(Reaction step 2) (I■) [In the formulas (IV) and (Vl, X and D are the same as defined above] Azomethine compound (Ill) and tetraroalcohol (I
Compound (V) is synthesized by reacting with V) in the presence of sodium hydride in an inert phase medium.

The inert heating medium is not particularly limited as long as it is inert to the reaction components, but polar solvents such as N,N-dimethylformamide and hexamethylene phosphonylamide are preferred.

The reaction molar ratio is 10 to 20 times, preferably 1.2 to 1.5 times, molar amount of chloroalcohol (IN) to 1 mole of azomethine compound (II).

The amount of sodium hydride used is based on the azomethine compound (I1
) is preferably used in an equimolar amount.

The reaction temperature is 80-200°C, preferably 100-15°C.
It is 0°C.

Reaction time is 2 to 30 hours.

(Reaction step 3) (Vl) 11. =Crt (VU) [In formula (Vl) and (V[I), R', D and x have the same meanings as above] Compound (V) and (meth)acryloyl chloride (Vl)
and are reacted in an inert solvent in the presence of triethylamine to synthesize a polymerizable monomer (vn).

The inert solvent is not particularly limited as long as it is inert to the reaction components, but cyclic ether solvents such as dioxane and tetrahydrofuran are preferred.

The reaction molar ratio is (meth) to 1 mol of compound (V).
The amount of acryloyl chloride (Vl) is 1.0 to 20 times the molar amount, preferably 12 to 15 times the molar amount.

The amount of triethylamine used is preferably equimolar to (meth)acryloyl chloride.

The reaction temperature is 0-so'c, preferably 0-40'c.

Reaction time is 2 to 20 hours.

(Reaction Step 4) The polymer compound of the present invention can be obtained by polymerizing the polymerization active monomer (■) in an inert solvent in the presence of a polymerization initiator.

Examples of the polymerization initiator include benzoyl peroxide, azobisisobutyronitrile, and lauroyl peroxide.

The amount of polymerization initiator used is: polymerization active monomer (Vl) 1
The amount is 1,150 to 11,500 times, preferably 1/100 to 1/300 times, and more preferably 1/100 to 1/200 times, based on the mole.

The inert heating medium is not particularly limited as long as it is inert to the polymerization active monomer (VI), but hydrocarbon heating mediums such as toluene, benzene, and hexane are preferred.

Polymerization temperature is 0 to 80°C, preferably 40 to 80°C
It is.

Polymerization time is 2 to 30 hours.

A reprecipitation method can be employed to purify the obtained polymer compound of the present invention.

The polymer compound of the present invention thus obtained has a number average molecular weight of 10 million to 1 million, and the endothermic peak measured by differential scanning calorimeter (DSC) varies somewhat depending on the molecular weight of the polymer, but the number average molecular weight is 80 to 1 million. It can be observed at 140°C (heating rate, 10°C/m1n).

Even if the polymer compound of the present invention is a copolymer with 5 mol% or less of a monomer other than the polymerization active monomer (VII), the polymer compound may be a composite containing 5 mol% or less of another polymer in the present polymer compound. It may be the body.

The polymer material containing the polymer compound of the present invention as a main component can be formed into a film or thin film by a method such as casting or spin cording, and can be used as an electro-optic material for use in optoelectronics fields such as optical information processing and optical communications. It can be suitably used as a material for devices such as devices, second harmonic generation devices, and waveguides.

(Example) Hereinafter, the polymer compound of the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited in any way by this example.

[Example 1] ■ Synthesis of 4-dimethylamino-N-(4-hydroxybenzylidene)aniline p-dimethylaminoaniline (27.2 g, 0.2 mo
i') and p-hydroxybenzaldehyde (26.8g
, 0.22 mof) was dissolved in ethanol II2, and acetic acid 2- was added as a catalyst. Next, ethanol was distilled off while heating this solution at normal pressure. When the amount of distilled ethanol reached about 0.812, heating was stopped, and the reaction mixture was cooled with water ice to precipitate crystals of 4-dimethylamino-N-(4-hydroxybenzylidene)aniline. The crystals were separated in a furnace, thoroughly washed with ethanol, and then dried.

Yield 43.2g (90%), m, p, 264~2
65°C ■ Synthesis of 4-dimethylamino-N-[4-(6-hydroxyhexamethyleneoxy)benzylidene coaniline The obtained 4-dimethylamino-N-(4-hydroxybenzylidene)aniline (I6.8g, 0.07mof)
was dissolved in N,N-dimethylformamide 300-
Cooled to °C. Next, sodium hydride (I, 76 g, 0.0735 mo1) was added to this solution with stirring.

After the evolution of H2 was completed, 1-chlorohexanol (I4.3 g, 0.105 mof) was added to this solution, and 1
Stirred at 20°C for 5-8 hours. After the reaction was completed, the reaction mixture was poured into 1.5°C water.

The precipitated crystals were separated into 4-dimethylamino-N-[
Crude crystals of 4-(6-hydroxyhexamethyleneoxy)benzylidenecoaniline were obtained. The crude crystals were purified by recrystallization with ethanol.

Yield 19.5g (82%), m, p, 86-87
°C ■ Synthesis of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate The obtained 4-
Dimethylamino-N-[4-(6-hydroxyhexamethyleneoxy)benzylidenecoaniline (I2,9g,
0.038 mol) was dissolved in the solvent dioxane 200-.

Next, add triethylamine (5,91-10,
042mol) and methacryloyl chloride (4,10
d, 0.042mol) and stirred at 25°C for 5 hours. The reaction mixture was extracted with ethyl acetate, the organic layer was thoroughly washed with water, and then dried over magnesium sulfate.
Then, ethyl acetate was distilled off to obtain crude crystals of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate. The crude crystals were prepared using hexane/ethyl acetate (
It was purified by recrystallization using a mixed heating medium of I1).

Yield 7.0g (45%), m, p, 85-86℃
■Synthesis of poly [6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate] Obtained 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl methacrylate (2.45 g, 6
．． Ox 10-3 mol') to toluene (0.6 m
f) lauroyl peroxide (I2 mg, 3.
Polymerization was carried out at 70°C for 8 hours in the presence of 10 -'mo of Ox, and then the reaction mixture was poured into methanol to yield the title product. This was purified by dissolving it in chloroform and then reprecipitating it in methanol.

The number average molecular weight of this purified product was 70,000 to 80,000.6 Identification was made by 'H-NMR (400 MHz, CDCβ
3), and it was confirmed that the obtained polymer was the title target product having an azomethine group in the side chain.

The 'H-NMR spectrum is shown in Figure 1, and 'II
-NMR measurement results are shown below.

The powder sample filled in the glass cell was heated with 1.064 mL of NdYAG laser (YAG laser DCR-3 manufactured by Spectra Physics, peak output 110 MW).
- When irradiated with rays, green light emission was observed.

[Example 2] Value (ppm) 9~1° 3~l.

8~4° 6~7° 3~8° 8-3 attribution d C,e Second harmonic generation of the obtained object I evaluated it accordingly.

For the integral ratio (SHG), 1-chloropropanol (99 g, O, 105
Synthesis was carried out in the same manner as in Example 1 except that mof) was used.

The number average molecular weight of the objective purified product obtained was 50,000 to 60,000.

Identification was carried out in the same manner as in Example 1, and it was confirmed that the obtained polymer was the title target product having an azomethine group in the side chain.

The measurement results of H-NM and H are shown below. 6C113 value (ppm) 0, 9 to 1. 1 1 3-1 8 3, 8-41 6, 6-7.8 8, 3-8.4 2, 8-30 Attribution Integral ratio a 2.8 b, d 3.8 c, e 4. 1 f 7.8 g 1. Oh 5. Fluiminomethylphenoxyhexyl p-methoxyaniline (27.1 g, 0.1 g,
Synthesis was carried out in the same manner as in Example 1, except that 22mof) was used.

The number average molecular weight of the objective purified product obtained was 50,000 to 60,000.

Identification was carried out in the same manner as in Example 1, and it was confirmed that the obtained polymer was the title target product having an azomethine group in the side chain.

Identification was carried out in the same manner as in Example 1, and it was confirmed that the obtained polymer was the title target product having an azomethine group in the side chain.

'H-NMR measurement results are shown below.

x, 064P#! When irradiated with light, green luminescence was observed.

[Example 3] Polymethacrylic 6-4-methoxyanilyside 1□-
C'F- ■ Value (ppn+) Attribution Integral ratio 0.
9-1.2 a 2.91.3-1
．． 8 b, c 9.83.8-4.1
c, e 3.86.4-7.6
f 7.883~8.4 g
1.03.6~3.7h
2.8 is a 'H-NMR spectrum diagram of 6-(4-dimethylaminophenyliminomethylphenoxy)hexyl acid 1.

Nd:YAGL was added to the obtained target product in the same manner as in Example 1.
/-za (7) 1. When os4Pmt was irradiated, green light emission was observed.

[Effects of the Invention] According to the present invention, various devices used in optoelectronic fields such as optical information processing and optical communication, such as electro-optic devices, second harmonic generation devices, piezoelectric devices, waveguides, especially film-like Polymeric materials useful as devices, laminates, or aggregate devices can be provided.

[Brief explanation of drawings]

Claims (1)

[Claims] The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or a methyl group, X represents an integer from 1 to 20, and D represents an electron-donating group), and has a number average molecular weight of 1000.
A polymer compound characterized in that the molecular weight is 1 million.