JP3398185B2 - Polymer nonlinear optical material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymeric material suitable for various elements such as electro-optical elements that utilize nonlinear optical effects, and a method for producing a polymeric nonlinear optical material comprising the same.

[0002]

2. Description of the Related Art In recent years, a material having a non-linear optical material-a non-linearity between a polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, has been attracting attention. Such materials are generally known as nonlinear optical materials and are described in detail in, for example, the following. "Nonlinear Optical Properties of Organic and Polymeric Materials"
C.S. Symposium Series 233 Edited by David Jay Williams (American Chemistry Society 1983)
Annual publication) "" Nonlinear Optical Properties of Organic a
nd Polymeric Material "ACS SYMPOSIUM SERIES 233
Edited by David J. Williams (American Chemical Society,
1983), "Organic Nonlinear Optical Materials" Masao Kato, Hachiro Nakanishi (CMC, 1985), "Nonlinear Optical Properties."
Of Organic Molecule's and Crystals, "Volumes 1 and 2, DS Schmla and Jay Jess, Ed. (Academic Press 198
7 years) "" Nonlinear Optical Properties of Organic
Molecules and Crystals "vol. 1 and 2 DSChem
Edited by la and J. Zyss (Academic Press).

In order to effectively function as a nonlinear optical material, it is necessary to satisfy the requirements according to the order of the nonlinear optical effect to be used. For example, the polarization induced by the electric field needs to be non-centrosymmetric in order to exhibit the second-order nonlinear optical effect. Conventionally, lithium niobate (L
N) and inorganic compounds represented by potassium dihydrogen phosphate (KDP) have been used as second-order nonlinear optical materials.
However, a sufficiently large figure of merit is not always obtained with these inorganic compounds, and π-electron conjugated organic compounds having an electron-donating group and an electron-withdrawing group, which are expected to have a potentially large figure of merit, have attracted attention. . Therefore, active studies were conducted to use single crystals of organic compounds as second-order nonlinear optical materials, and p-nitroaniline derivatives, chalcone derivatives, phenylazole derivatives, etc. were found (for example, "new organic nonlinear optics"). Materials I and II "Takayoshi Kobayashi,
Edited by Shinsuke Umegaki, Hachiro Nakanishi and Shino Nakamura (see CMC, 1991).

However, it is extremely difficult to control the molecules to be arranged in a non-centrosymmetric manner, which is a great obstacle to the development of an excellent second-order nonlinear optical material composed of a single crystal of an organic compound. There is. Therefore, as a method to effectively utilize the excellent performance at the molecular level, a so-called electric field oriented polymer in which the π-electron conjugated organic compound is combined with a polymer and oriented by applying an electric field is used as a second-order nonlinear optical material. Attempts have been made to try. However, this electric field oriented polymer has a drawback that dipoles oriented in one direction by an electric field become disordered with time (so-called orientation relaxation), and its solution is desired (for example, DRUlrich, MolCryst.Lig.Crys
t., 1990, 189, pp. 3-38).

One of the solutions to this orientation relaxation is to use a polymer having a high glass transition temperature (Tg). However, when conducting electric field orientation, the polymer is
It is customary to keep the temperature higher and increase the mobility of the molecules. Therefore, increasing Tg increases the electric field orientation temperature. By the way, it is known that the nonlinear optical constant of a polymer obtained by electric field orientation is inversely proportional to the temperature during electric field orientation. That is, high Tg
The use of a polymer having is contrary to obtaining a large nonlinear optical constant. For these reasons, it is desired to develop a polymer material that can be oriented in an electric field at low temperatures and is free from orientation relaxation.

[0006]

Therefore, the first object of the present invention is to provide a polymer material having no orientation relaxation, and the second object is to be capable of electric field orientation at a low temperature and to provide orientation relaxation. It is to provide a polymer material without A third object is to provide a non-linear optical material composed of the polymer material.

[0007]

Means for Solving the Problems The present inventors have results of extensive studies, by using a high molecular that represented in one general formula (4), a first object of the present invention can be achieved I found that. Furthermore, it was found that by using a high molecular that represented in one general formula (4), a second object of the present invention can be achieved. It was also found that the third object of the present invention can be achieved by using the above-mentioned polymer material.

General formula (4)

[Chemical 3]

[0009]

[0010]

[0011]

[0012]

[0013]

The polymer of the present invention will be described in detail below .

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

The ammonium group represented by Am ² described later is a primary to tertiary ammonium group, for example, ammonium, alkylammonium (eg, methylammonium, ethylammonium, cyclohexylammonium, 1-phenylethylammonium),
Dialkylammonium (eg dimethylammonium, diethylammonium, pyrrolidinium, piperidinium, morpholinium, piperazinemonoammonium, piperazinebisammonium), trialkylammonium (eg trimethylammonium, triethylammonium, triethylenediamineammonium,
Triethylenediamine bis ammonium), the aryl ammonium (e.g., anilinium, N- methyl anilinium, N, N- diethyl anilinium), pyridinium (pyridinium, 2-picolinium, 3-picolinium, 4-picolinium, 4-N, N -Dimethylaminopyridinium), 1,8-diazabicyclo [5,4,0]
-7-Undecenium and guanidinium are mentioned.
Of these, alkyl ammonium secondary and tertiary especially preferred.

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] High-molecular used in the present invention is represented by the general formula (4).

General formula (4)

[Chemical 4]

In the formula, R ¹ and R ³ may be the same or different and each represents a hydrogen atom or a methyl group, and R ² represents an alkyl group. Am ² represents a primary to tertiary ammonium group and a proton, and m represents an integer of 2 to 12. The ratio of p to q is 0 to 4.

Examples of the alkyl group represented by R ² include those having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl). , Isopropyl,
Butyl, sec-butyl, tert-butyl). m is preferably 2 to 6. The ratio of p and q is preferably 0 to 2. The polymer used in the present invention may have a molecular weight of 1,000 to 1,000,000, preferably 3,000 to 500,000, and more preferably 5,000 to 100,000. Specific examples of the polymer used in the present invention are shown below, but the scope of the present invention is not limited to these. Further, the polymer of the present invention may be deuterated.

[0041]

[Chemical 5]

[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

[Chemical 8]

[0045]

[0046]

[0047]

The polymer of the present invention can be produced by a method such as a solution polymerization method, a precipitation polymerization method, a suspension polymerization method, a plasma polymerization method or a vapor deposition polymerization method, and a polymerization initiator is used at the initiation of the polymerization. be able to. Regarding the selection of a suitable polymerization initiator for the desired polymerization reaction, edited by The Chemical Society of Japan, Vol. 19, New Experimental Chemistry, Polymer Chemistry (I) Chapter 2 (Maruzen, 19
It is possible by referring to (1978). Also, π
The electron-conjugated functional group may be introduced by either a method of introducing it at the monomer stage or a method of introducing it after synthesizing a polymer. The polymer of the present invention can be synthesized with reference to the above-mentioned New Experimental Chemistry Course Vol. 19, edited by The Chemical Society of Japan, 4th edition Experimental Chemistry Course Vol. 28, polymer synthesis (Maruzen, 1992).

As an example, a method for synthesizing the polymer represented by the general formula (4) of the present invention will be described. The general formula
The polymer represented by (4) can be obtained by polymerizing the compound represented by the following general formula (5) alone or in the coexistence with another acrylate monomer to form an ammonium salt, if necessary.

General formula (5)

[Chemical 9]

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and L represents an integer of 2 to 12. L is preferably 2 to 6. Specific examples of the compound represented by the general formula (5) are shown below, but the scope of the present invention is not limited to these.

[0052]

[Chemical 10]

These compounds are synthesized by synthesizing a 5-benzylidenethiazolidine-2,4-dione derivative,
It is possible to use either a method of converting to an acrylate ester or a method of synthesizing an acrylate ester of a benzaldehyde derivative and then performing a benzylidene reaction. The benzylidene compound is a Knevena gel (Knenagel) containing a benzaldehyde derivative and thiazolidine-2,4-dione.
can be obtained by reaction. As the solvent, alcohols, ethers, nitriles, amides and the like can be used, and as the catalyst, acid or base can be used. The reaction temperature is -100 ° C to 150 ° C.
It can be carried out in the range of ℃, preferably -78 ℃ ~ 1
20 ° C, more preferably 30 ° C to 100 ° C. The esterification reaction can be carried out by reacting acrylic acid halide with alcohol. Ethers, nitriles, halogenated hydrocarbons and the like can be used as the solvent, and a base can be used as the catalyst. The reaction temperature may be in the range of -100 ° C to 50 ° C, preferably -78 ° C to 30 ° C, more preferably -25 ° C to 15 ° C.

When the polymer material of the present invention is used as a nonlinear optical material, it can be used not only as a second-order nonlinear optical material but also as a third-order and higher-order nonlinear optical material. The use as a nonlinear optical material is
Examples thereof include a wavelength conversion element, an optical deflector, an optical matrix switch, a spatial light modulation element, an optical bistable element, and a phase conjugate element.

[0055]

EXAMPLES The present invention will be described in detail below based on examples. Example 1 Synthesis of compound B-1 a) Synthesis of 4- (2-hydroxyethoxy) benzaldehyde 12.2 g (0.1 mol) of 4-hydroxybenzaldehyde, 16.6 g (0.12 mol) of potassium carbonate and N, 100 ml of N-dimethylformamide was placed in a 300 ml three-necked flask equipped with a thermometer and a stirrer, and the temperature was 60 ° C.
Heated to. Here, 25.0 g of 2-bromoethanol
(0.2 mol) was added dropwise. Internal temperature is 80 ℃ due to reaction heat
Rose to. Thereafter, heating and stirring were continued at 100 ° C. for 2 hours. The reaction mixture was allowed to cool to room temperature, poured into water and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off, and silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/1) was performed to obtain the desired 4- (2-hydroxyethoxy) benzaldehyde as an oil. Obtained. Yield 5.8 g (yield 34.
9%)

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 2.17 ppm (bs, 1H), 4.04 (t, 2
H), 4.20 (t, 2H), 7.01 (d, 2H),
7.85 (d, 2H), 9.90 (s, 1H)

B) Synthesis of 4- (2-acryloyloxyethoxy) benzaldehyde 4- (2-hydroxyethoxy) benzaldehyde 5.
8 g (0.035 mol), 6 ml of triethylamine, a small amount of hydroquinone and 80 ml of acetonitrile were placed in a 200 ml three-necked flask equipped with a thermometer and a stirrer at 0 ° C.
Cooled to. 3.5 g of acryloyl chloride (0.0
39 mol) and 8 ml of acetonitrile at 5 ° C.
Dropped below. After the completion of dropping, the mixture was stirred at 0 ° C for 2 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off, and silica gel column chromatography was performed (eluent ethyl acetate / n-hexane = 1/1) to obtain the desired 4- (2-acryloyloxyethoxy) benzaldehyde as an oil. Got as. Yield 4.1 g (yield 53.2%)

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 4.35ppm (t, 2H), 4.57 (t, 2H),
5.88 (dd, 1H), 6.15 (dd, 1H),
6.46 (dd, 1H), 7.01 (d, 2H), 7.
82 (d, 2H), 9.90 (s, 1H)

C) Synthesis of compound B-1 4- (2-acryloyloxyethoxy) benzaldehyde 3.0 g (0.014 mol), thiazolidine-2,
1.6 g (0.014 mol) of 4-dione, 0.63 g of ammonium acetate, 0.8 ml of acetic acid, a small amount of hydroquinone and 16 ml of acetonitrile, 50 ml equipped with a reflux condenser.
The mixture was placed in an eggplant flask and heated under reflux for 3 hours. The reaction mixture was allowed to cool to room temperature, poured into ice water, and the resulting precipitate was collected by filtration,
Washed with water. After air-drying, silica gel column chromatography (eluent chloroform) was performed to obtain the target compound B-1. Yield 2.3 g (yield 51.5%)

¹ H-nmr was measured in DMSO-d ₆ ,
The following results were obtained. δ 4.35 ppm (m, 2H), 4.48 (m, 2H),
5.98 (dd, 1H), 6.20 (dd, 1H),
6.35 (dd, 1H), 7.13 (d, 2H), 7.
54 (d, 1H), 7.76 (s, 1H), 12.53
(Bs, 1H)

Example 2 Synthesis of compound B-3 a) Synthesis of 4- (6-hydroxyhexyloxy) benzaldehyde 2.44 g (0.02) of 4-hydroxybenzaldehyde
Mole), 2.73 g of 6-chlorohexanol (0.02
Mol), 1.66 g (0.012 mol) of potassium carbonate and 20 ml of N, N-dimethylformamide in a 50 ml three-necked flask equipped with a stirrer and a thermometer.
The mixture was heated and stirred at 0 ° C for 2 hours. The reaction mixture was allowed to cool to room temperature, poured into ice water and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, ethyl acetate was distilled off and the mixture was allowed to stand at room temperature, whereupon the oil gradually crystallized. As indicated by silica gel thin layer chromatography (developing solution ethyl acetate), the crystals were highly pure. Yield 4.4 g (yield 99.0%). The crystals were recrystallized with a mixed solvent of ethyl acetate and n-hexane.
Yield 2.2 g (yield 49.5%), melting point 43.0-4
3.5 ° C.

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.35 to 1.95 ppm (m, 8H), 3.69
(T, 2H), 4.05 (t, 2H), 7.10 (d,
2H), 7.82 (d, 2H), 9.90 (s, 1H)

B) Synthesis of 4- (6-acryloyloxyhexyloxy) benzaldehyde 4- (6-hydroxyhexyloxy) benzaldehyde 8.9 g (0.04 mol), triethylamine 6.8 ml
And 100 ml of acetonitrile were placed in a three-necked flask equipped with a thermometer and a stirrer and cooled to 0 ° C. A solution of 4.0 g (0.044 mol) of acryloyl chloride and 10 ml of acetonitrile was added dropwise thereto at 0 ° C to 5 ° C with stirring. After the dropwise addition was completed, the mixture was stirred at 0 ° C. for 1 hour, poured into ice water, and after a while, precipitated crystals were collected by filtration, washed with water and air-dried to obtain the target compound. Yield 3.94 g (yield 35.7
%) And the melting point was 30 ° C. or lower.

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.25 to 1.95 ppm (m, 8H), 4.05
(T, 2H), 4.18 (t, 2H), 5.81 (d
d, 1H), 6.12 (q, 1H), 6.40 (dd,
1H), 6.98 (d, 2H), 7.82 (d, 2
H), 9.86 (s, 1H)

C) Synthesis of compound B-3 4- (6-acryloyloxyhexyloxy) benzaldehyde 3.9 g (0.014 mol), thiazolidine-
1.65 g (0.014 mol) of 2,4-dione, 0.65 g of ammonium acetate, 0.8 ml of acetic acid, 0.2 g of hydroquinone and 15 ml of acetonitrile were placed in a 50 ml eggplant flask equipped with a reflux condenser and heated under reflux for 1 hour. did.
The reaction mixture was allowed to cool to room temperature, poured into ice water, and the resulting precipitate was collected by filtration, washed with water and air dried. The obtained solid was dissolved in dichloromethane, the insoluble matter was removed, and then acetonitrile was added. The crystals were distilled off under reduced pressure to remove dichloromethane, and the target compound was obtained. Yield 2.8g (yield 53.3%)

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.33 to 2.00 ppm (m, 8H), 4.04
(T, 2H), 4.19 (t, 2H), 5.84 (d
d, 1H), 6.12 (dd, 1H), 6.42 (d
d, 1H), 7.00 (d, 2H), 7.45 (d, 2
H), 8.82 (s, 1H)

Example 3 Synthesis of compound B-4 a) 4- (6-methacryloyloxyhexyloxy)
Synthesis of benzaldehyde In Example 2-b), 4.0 g of acryloyl chloride was replaced with 4.6 g of methacryloyl chloride.
(0.044 mol) was replaced by the same reaction. The reaction mixture was poured into ice water, extracted with ethyl acetate, then washed with aqueous sodium hydrogen carbonate solution, and further washed with water. After drying over anhydrous sodium sulfate, purification by silica gel column chromatography (developed with hexane: ethyl acetate = 1: 1) was performed to obtain the target compound. Yield 9.
9 g (yield 85.3%). Oily.

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.25 to 2.20 ppm (m, 11H), 4.05
(T, 2H), 4.18 (t, 2H), 5.57 (S,
1H), 6.12 (S, 1H), 7.10 (d, 2
H), 7.81 (d, 2H), 9.90 (S, 1H)

B) Synthesis of compound B-4 4- (6-methacryloyloxyhexyloxy) benzaldehyde 9.9 g (0.034 mol), thiazolidine-2,4-dione 4.0 g (0.034 mol), acetic acid 1.56 g of ammonium, 1.9 ml of acetic acid, 0.5 g of hydroquinone and 35 ml of acetonitrile were placed in a 100 ml eggplant flask equipped with a reflux condenser and heated under reflux for 1 hour. The reaction mixture was allowed to cool to room temperature, poured into ice water, and the resulting precipitate was collected by filtration, washed with water and air dried. The solid obtained is 15
After dissolving in 0 ml of dichloromethane to remove insoluble matter,
Acetonitrile was added. The crystals were distilled off under reduced pressure to remove dichloromethane, and the target compound was obtained. Yield 5.8g (Yield 43.9%)

The ¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.35 to 2.10 ppm (m, 11H), 4.04
(T, 2H), 4.17 (t-2H), 5.55 (S,
1H), 6.11 (S, 1H), 7.11 (d, 2
H), 7.47 (d, 2H), 7.83 (S, 1H),
8.06 (S, 1H)

Example 4 Synthesis of Compound A-1 1.1 g of Compound B-1, 0.1 g of azobisisobutyronitrile (AIBN) and 25 ml of THF were placed in a 50 ml eggplant flask equipped with a reflux condenser and placed under a nitrogen stream. The mixture was heated under reflux for 8 hours. AIBN 0.1g was added here, and it heated and refluxed for further 10 hours under nitrogen stream. After allowing to cool to room temperature, insoluble materials were removed and n-hexane was added. The supernatant was removed by decantation, the residue was washed with ethyl acetate and decanted. A resinous target product was obtained. Yield 0.34 g (yield 30.9%).

When ¹ H-nmr was measured in DMSO-d ₆ , a vinyl proton derived from an acrylate group (δ5.
(8-6.5 ppm) disappeared and the signal was broadened. It is clear that the polymerization reaction proceeded and the polymer was polymerized. Molecular weight measured by vapor pressure osmometer is 9,80
It was 0. The Tg measured by DSC was 250 ° C or higher.

Example 5 Synthesis of compound A-5 1.55 g (4.13 mmol) of compound B-3, 0.15 g of azobisisobutyronitrile (AIBN) and 30 ml of 1,2-dimethoxyethane were refluxed in a condenser. The mixture was placed in a 50 ml eggplant flask equipped with and heated under reflux for 20 hours under a nitrogen stream. After allowing to cool to room temperature, n-hexane was added.
The supernatant was removed by decantation, ethyl acetate was added to the residue, and then n-hexane was added. The supernatant was removed again by decantation, and the same operation was performed again. The resinous material was heated and dried at 60 ° C. to obtain the desired product. Yield 1.
05 g (yield 67.7%)

When ¹ H-nmr was measured in CDCl ₃ , it was found that the vinyl protons derived from the acrylate group (δ 5.8-
6.5 ppm) disappeared and the signal was broadened.
It is clear that the polymerization reaction proceeded and the polymer was polymerized.
Molecular weight measured by vapor pressure osmometer is 10,500
Met. The Tg measured by DSC was 227 ° C.

Example 6 Synthesis of Compound A-10 1.55 g (4.13 mmol) of Compound B-3, 0.36 g (4.13 mmol) of methyl acrylate, AI
BN 0.30 g and 1,2-dimethoxyethane 30
ml was placed in a 50 ml eggplant flask equipped with a reflux condenser and heated under reflux for 7 hours under a nitrogen stream. Where AIBN 0.1
0 g was added, and the mixture was heated under reflux for 10 hours under a nitrogen stream. After allowing to cool to room temperature, the same operation as in Example 5 was performed to obtain the target product. Yield 1.22 g (yield 63.9%)

When ¹ H-nmr was measured in DMSO-d ₆ , a vinyl proton derived from an acrylate group (δ5.
(8-6.5 ppm) disappeared and the signal was broadened. It is clear that the polymerization reaction proceeded and the polymer was polymerized. -OCH ₃ (δ 3.49 ppm) and -O-CH _2- (δ
The p / q ratio was determined from the signal intensity derived from 4.00 ppm), and the value was 0.316. The molecular weight measured by a vapor pressure osmometer was 21,000. DS
The Tg measured by C was 300 ° C. or higher.

Example 7 Synthesis of Compound A-14 Compound B-4 2.9 g (7.45 mmol), AIB
N (0.29 g) and 1,2-dimethoxyethane (30 ml) were placed in a 50 ml eggplant flask equipped with a reflux condenser and heated under reflux for 24 hours under a nitrogen stream. After allowing to cool to room temperature, the same operation as in Example 5 was performed to obtain the target product. Yield 1.
34 g (yield 46.2%)

When ¹ H-nmr was measured in DMSO-d ₆ , the vinyl proton (δ
5.5 to 6.2 ppm) disappeared and the signal was broadened. It is clear that the polymerization reaction proceeded and the polymer was polymerized. The number average molecular weight measured by GPC is 459.
It was 0. Tg measured by DSC is 184.5 ° C
Met.

Example 8 Synthesis of compound A-18 2.1 g (5.3 mmol) of compound B-4, 0.46 g (5.3 mmol) of methyl acrylate, AIBN
0.20 g and 20 ml of 1,2-dimethoxyethane were placed in a 50 ml eggplant flask equipped with a reflux condenser and heated under reflux for 24 hours under a nitrogen stream. After allowing to cool to room temperature, the same operation as in Example 5 was performed to obtain the target product. Yield 1.85
g (yield 72.3%)

The number average molecular weight measured by GPC is 59.
It was 60. Tg measured by DSC is 201.0
It was ℃.

Example 9 Synthesis of Compound A-19 Compound B-4 2.9 g (7.45 mmol), ethyl methacrylate 0.85 g (7.45 mmol), AI
0.29 g of BN and 30 ml of 1,2-dimethoxyethane
Was placed in a 50 ml round-bottomed flask equipped with a reflux condenser, and the same operation as in Example 8 was carried out to obtain the desired product. Yield 1.14
g (yield 30.7%)

The number average molecular weight measured by GPC is 95.
It was 30. The Tg measured by DSC was 215 ° C.

Example 10 Synthesis of Compound A-20 Compound B-3 2.0 g (5.3 mmol), ethyl methacrylate 0.61 g (5.3 mmol), AIBN
0.20 g and 20 ml of 1,2-dimethoxyethane were placed in a 50 ml eggplant-type flask equipped with a reflux condenser and Example 8 was used.
The same operation as above was performed to obtain the desired product. Yield 0.98g
(Yield 37.5%)

The number average molecular weight measured by GPC is 59.
It was 00. The Tg measured by DSC was 189 ° C.

Example 11 Synthesis of Compound A-21 Compound B-3 0.9 g (2.4 mmol), Compound B
-4 1.0 g (2.6 mmol), AIBN 0.20
20 ml of g, 1,2-dimethoxyethane was placed in a 50 ml eggplant flask equipped with a reflux condenser, and the same operation as in Example 8 was performed to obtain the desired product. Yield 0.91 g (48% yield)

The number average molecular weight measured by GPC is 43.
It was 00. The Tg measured by DSC was 188 ° C.

Example 12 Synthesis of Compound A-2 0.1 g of Compound A-1 and 20 ml of dichloromethane were placed in a 50 ml eggplant flask equipped with a stirrer, and 1 ml of triethylamine was added with stirring. After 5 minutes, the solution in which the insoluble matter was removed after almost completely dissolved was poured into a petri dish and left overnight in the fume hood. A resinous material was obtained but was not completely solidified. This is probably because Tg is lowered to room temperature or lower. When ¹ H-nmr was measured in CDCl ₃ , a signal derived from triethylamine was observed (δ
1.35 ppm t, 3.25 q).

Example 13 Synthesis of Compound A-6 Using 0.1 g of Compound A-5, the same operation as in Example 12 was carried out, and the same result was obtained.

Example 14 Synthesis of Compound A-7 Using 0.1 g of Compound A-5, the same procedure as in Example 12 was performed except that morpholine was used instead of triethylamine. A solidified polymer film was obtained after evaporation of the solvent and excess morpholine. This was taken, and ¹ H-nmr and Tg were measured. When ¹ H-nmr was measured in CDCl ₃ , a morpholine signal was observed (δ3.0.
0 ppm t, 3.69 ppm t). The Tg was 24 ° C.

Example 15 Synthesis of Compound A-11 Using 0.1 g of Compound A-11, the same operation as in Example 12 was carried out, and similar results were obtained.

Example 16 Synthesis of compound A-12 The same operation as in example 14 was carried out using 0.1 g of compound A-10. Similar results were obtained for ¹ H-nmr. The Tg was 35 ° C.

Example 17 Synthesis of compound A-15 The same operation as in example 14 was carried out using 0.1 g of compound A-14. Similar results were obtained for ¹ H-nmr. The Tg was 41 ° C.

Example 18 Synthesis of Compound A-22 The same operation as in Example 12 was carried out using 0.1 g of Compound A-18. Similar results were obtained for ¹ H-nmr. The Tg was 30 ° C.

Example 19 Desorption of amine by heat of high-molecular amine salt DSC measurement was carried out using compound A-7 and compound A-12. In the case of compound A-7, at 157.6 ° C, compound A
In −12, a sharp endothermic peak appeared at 175.5 ° C. It suggests that Amin detachment has occurred.

Example 20 Preparation of electric field oriented polymer film and generation of second harmonic (S
HG) 0.2 g of the experimental compound A-1 and 2.5 ml of chloroform were placed in a test tube and 0.5 ml of triethylamine was added. After applying ultrasonic waves for 5 minutes, the total amount of the solution from which the insoluble matter was removed was dropped on the ITO-coated glass substrate and spin-coated at 4000 rpm. Further, the same experiment was carried out in which a sample in which triethylamine was replaced with morpholine and piperidine, and further compound A-1 was replaced with compound A-10. The thickness of each of the obtained thin films was about 5 μm. 30 these films
After holding at 24 ° C. for 24 hours, electric field orientation was performed by the corona poling method.

The corona poling conditions were as follows: Voltage applied to corona wire: -10 kV Temperature; (Condition A) After holding at 50 ° C for 1.5 hours, 1 ° C
The temperature was raised to 150 ° C. in 1 minute, held at 150 ° C. for 30 minutes, and then cooled to 40 ° C. in 1 hour. (Condition B) 50 ° C
For 3 hours and 40 minutes, then at 40 ℃ for 1 hour (40 ℃
(Including the time to cool down). Immediately after the electric field orientation, SHG was measured by the apparatus shown in FIG. The results are shown in Table 1.

[0097]

[Table 1]

Example 21 Samples 1 to 8 of Example 20 were held at 30 ° C. for 3 months, and then SHG measurement was carried out. The results are shown in Table 2.

[0099]

[Table 2]

[0100]

As described above, the polymer material of the present invention is useful as an organic nonlinear optical material. Especially Example 2
As shown in FIG. 1, it is apparent that by using the method for producing a nonlinear optical material of the present invention, a material having excellent stability over time can be obtained.

[Brief description of drawings]

FIG. 1 shows an apparatus for measuring SHG intensity.

[Explanation of symbols]

1 sample 2 fundamental wave cut filter 3 spectroscope 4 Photomultiplier tube 5 amplifiers 6 (11) Wavelength 1.064μm 7 (12) Wavelength 0.532μm

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 20/38 C08F 220/12-220/18 G02F 1/361 C07D 277/02 CA (STN) REGISTRY (STN )

Claims (5)

(57) [Claims] 1. A polymer represented by the following general formula (4). General formula (4) In the formula, R ¹ and R ³ may be the same or different and each represents a hydrogen atom or a methyl group, and R ² represents an alkyl group.
Am ² represents a primary to tertiary ammonium group and a proton, and m represents an integer of 2 to 12. The ratio of p to q is 0 to 4. 2. The ratio of p to q is 0.
The described macromolecule. 3. A nonlinear optical material comprising a polymer thin film containing the polymer according to claim 1 or 2. 4. The non-linear structure according to claim 4, wherein the polymer thin film prepared from the polymer according to claim 1 or 2 is once oriented in an electric field and then further heated to 40 ° C. or higher under application of an electric field. How to make optical materials. 5. A compound represented by the following general formula (5). General formula (5) In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and L is 2
Represents an integer of 1 to 12.