JPH06138503A - High polymer nonlinear optical material - Google Patents

Abstract

PURPOSE:To provide the high polymer material excellent in blue light transmittance and the nonlinear optical material consisting thereof. CONSTITUTION:The nonlinear optical material contains the high polymer expressed by the formula. In the formula, X is oxygen, sulfur atom or N-R<5>. Each of R<1> and R<3> is hydrogen atom or methyl group and may be the same or different, R<2> is alkyl group, R<4> and R<5> is alkyl, aryl and heterocyclic group, (m) is integer 2-12. The ratio (p) and (q) is 0-4.

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 Society of Chemistry 1983)
Annual) "" Nonlinear Optical Properties of Organic
and Polymeric Material "ACS SYMPOSIUM SERIES 23
3 Edited by David J. Williams (American Chemical Societ
y, 1983) "," Organic Nonlinear Optical Materials ", supervised by Masao Kato, Hachiro Nakanishi (CMC, 1985)," Nonlinear Optical Properties. "
Of Organic Molecule's and Crystals "Volumes 1 and 2, edited by DS Smura and Jay Jess (Academic Press 198
(7 years) "" Nonlinear Optical Properties of Organic
Molecules and Crystals "vol 1 and 2 DSChemla
and edited by 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 have been made to use single crystals of organic compounds as second-order nonlinear optical materials, and p-nitroaniline derivatives, chalcone derivatives, phenylazole derivatives and the like have been 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.

It is known that compounds having a long π-electron conjugated chain are useful for the expression of a high non-linear susceptibility, and various compounds are described in the above-mentioned literatures. The maximum wavelength becomes longer, and for example, the transmittance of blue light is lowered, which hinders the generation of blue light as the second harmonic. This also occurs in the p-nitroaniline derivative, and the fact that the transmittance of the wavelength has a large influence on the efficiency of the second harmonic generation is due to Alain Azema et al., Proceedings of SPII, Volume 400, New Optical Materials (Alain Aze'ma et al., Proceedings of SPIE, 400)
Vol., New Optical Materials), (1983) p. 186, FIG.

[0006]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a polymer nonlinear optical material having high blue light transmittance.

[0007]

As a result of intensive studies, the present inventor has found that a non-linear optical material containing a polymer represented by the general formula (1) can achieve the object of the present invention. General formula (1)

[0008]

[Chemical 4]

In the formula, X is an oxygen atom, a sulfur atom or N-
Represents R ⁵ . 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. R ⁴ and R ⁵ represent an alkyl group, an aryl group and a heterocyclic group, and m represents an integer of 2 to 12. The ratio of p to q is 0 to 4. Among the polymers represented by the general formula (I), compounds represented by the following general formula (3) are preferable. General formula (3)

[0010]

[Chemical 5]

In the formula, R ²¹ and R ^{23, which} may be the same or different, each represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group. R ²⁴ represents an alkyl group, an aryl group, or a heterocyclic group, and n represents an integer of 2 to 12. r
And the ratio of s is 0 to 4. Also, this polymer
It can be synthesized using a compound represented by the following general formula (2). General formula (2)

[0012]

[Chemical 6]

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an alkyl group, an aryl group and a heterocyclic group. l represents an integer of 2 to 12. Hereinafter, general formula (1), general formula (2), and general formula (3) will be described in detail.

Examples of the alkyl group represented by R ² and R ²² 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). Each of l, m and n is preferably 2 to 6. The ratio of p to q and r to s is preferably 0 to 2. The alkyl group, aryl group and heterocyclic group represented by R ⁴ , R ⁵ , R ¹² and R ²⁴ include, for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (for example, , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl group (eg aralkyl group (eg benzyl group, 2-phenylethyl group), hydroxyalkyl group (eg 2-hydroxyethyl group, 3-hydroxypropyl group)) , A carboxyalkyl group (for example, 2-
Carboxyethyl group, 3-carboxypropyl group, 4-
Carboxybutyl group, carboxymethyl group), alkoxyalkyl group (eg, 2-methoxyethyl group, 2-
(2-methoxyethoxy) ethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
[3-sulfopropoxy] ethyl group, 2-hydroxy-
3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (eg, 3-sulfatopropyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (eg, 2-pyrrolidine-2) -On-
1-yl) ethyl group, tetrahydrofurfuryl group, 2-
Morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group}, aryl group (for example, phenyl group,
2-naphthyl group, etc., substituted aryl group (eg, 4-
Examples thereof include a carboxyphenyl group, a 4-sulfophenyl group, a 3-chlorophenyl group, a 3-methylphenyl group) and a heterocyclic group (for example, a 2-pyridyl group, a 2-thiazolyl group). As the molecular weight of the polymer used in the present invention,
1,000 to 1,000,000 are possible, preferably 3,000 to 500,000, more preferably 5,000.
It is 0 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.

[0015]

[Chemical 7]

[0016]

[Chemical 8]

The polymer of the present invention can be produced by, for example, a solution polymerization method, a precipitation polymerization method, a suspension polymerization method, a plasma polymerization method, a vapor deposition polymerization method or the like, and a polymerization initiator is used at the initiation of the polymerization. be able to. For the selection of a suitable polymerization initiator for the desired polymerization reaction, see the Chemical Society of Japan, New Experimental Chemistry Course, Vol.
It is possible by referring to (8 years). Further, the π-electron conjugated functional group may be introduced by either a method of introducing at the stage of a monomer or a method of introducing 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 and 4th Edition Experimental Chemistry Course, Vol. 28, edited by The Chemical Society of Japan (Maruzen 1992).

As an example, a method for synthesizing the polymer represented by the general formula (3) of the present invention will be described. The polymer represented by the general formula (3) is obtained by polymerizing the compound represented by the general formula (2) alone or in the coexistence with another acrylate monomer. Specific examples of the compound represented by formula (2) are shown below, but the scope of the present invention is not limited to these.

[0019]

[Chemical 9]

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 (Kn Benagel) containing a benzaldehyde derivative and thiazolidine-2,3-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.

[0022]

EXAMPLES The present invention will be described in detail below based on examples. Example 1 Synthesis of M-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, N. -Add 100 ml of dimethylformamide to a 300 ml three-necked flask equipped with a thermometer and a stirrer at 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, 2H), 4.20
(T, 2H) 7.01 (d, 2H), 7.85 (d, 2H), 9.90 (s, 1
H)

B) 5- [4- (2-hydroxyethoxy) benzylidene] -3-methylthiazolidine-2,4
-Synthesis of dione 4- (2-hydroxyethoxy) benzaldehyde 3.
32 g (0.02 mol), 3-methylthiazolidine-
2.62 g (0.02 mol) of 2,4-dione, 0.8 g (0.02 mol) of ammonium acetate, 1.2 ml of acetic acid and 25 ml of acetonitrile were placed in a 50 ml eggplant flask equipped with a reflux condenser and heated under reflux for 2 hours. did. The reaction mixture was allowed to cool to room temperature and then poured into ice water. The resulting crystals were collected by filtration, washed with water and air dried. The obtained crude crystals were recrystallized from acetonitrile to obtain the desired product. Yield 1.8g (Yield 3
2.3%). Melting point 157.6 ° C

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 2.01 ppm (t, 1H), 3.25 (s, 3H), 4.04
(M, 2H) 4.17 (t, 2H), 7.02 (d, 2H), 7.58 (d, 2
H) 7.88 (s, 1H)

C) Synthesis of M-1 5- [4- (2-hydroxyethoxy) benzylidene]
-3-Methylthiazolidine-2,4-dione 3.7 g
(0.013 mol), 2.4 ml triethylamine and 50 ml dichloromethane 1 equipped with a thermometer and stirrer.
The mixture was placed in a 00 ml three-necked flask, cooled to 0 ° C. and stirred.
1.32 g (0.015 mol) of acryloyl chloride
And a solution of 5 ml of dichloromethane were added dropwise at 5 ° C or lower. After the completion of dropping, the mixture was stirred at 0 ° C for 2 hours. The reaction mixture was washed with water, dried over anhydrous sodium sulfate, and then the target compound was obtained by silica gel column chromatography (eluent chloroform). Yield 2.3 g (yield 53.1%).

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 3.25 ppm (s, 3H), 4.29 (t, 2H), 4.52
(T, 2H) 5.87 ppm (dd, 1H), 6.16 (dd, 1H), 6.45
(Dd, 1H) 7.00 (d, 2H), 7.46 (d, 2H), 7.87 (s, 1
H),

Example 2 Synthesis of compound M-3 a) Synthesis of 4- (6-hydroxyhexyloxy) benzaldehyde 4-hydroxybenzaldehyde 2.44 g (0.02)
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, 1
H)

B) 5- [4- (6-hydroxyhexyloxy) benzylidene] -3-methylthiazolidine-2,
Synthesis of 4-dione 4- (6-hydroxyhexyloxy) benzaldehyde 5.55 g (0.025 mol), 3-methylthiazolidine-2,4-dione 3.28 g (0.025 mol), acetic acid 1.5 ml, 1.0 g of ammonium acetate and 30 ml of acetonitrile were placed in a 100 ml eggplant flask equipped with a reflux condenser and heated under reflux for 4 hours. After allowing to cool to room temperature, the mixture was poured into water, the supernatant was removed by decantation, and acetonitrile was added to the residue. Crystallization started after a while. The crystals were collected by filtration and washed with acetonitrile to obtain the desired product. Yield 4.1 g (yield 49.0%).

¹ H-nmr was measured in DMSO-d ₆ and the following results were obtained. δ 1.25 to 1.55 ppm (m, 6H), 1.75 (m, 2H),
3.11 (s, 3H) 3.42 (t, 1H), 4.05 (t, 2H), 4.37 (t, 1
H) 7.10 (d, 2H), 7.40 (d, 2H), 7.88 (s, 1
H)

C) Synthesis of M-3 5- [4- (6-hydroxyhexyloxy) benzylidene] -3-methylthiazolidine-2,4-dione 3.3
5 g (0.01 mol), 1.8 ml of triethylamine and 25 ml of cyclochloromethane were placed in a 50 ml three-necked flask equipped with a thermometer and a stirrer and cooled to 0 ° C. to this,
A solution of 1.0 g (0.011 mol) of acryloyl chloride and 5 ml of dichloromethane was added dropwise with stirring at 0-5 ° C. The mixture was subsequently stirred at 0 ° C for 30 minutes, poured into ice water, and extracted with dichloromethane. After drying over magnesium sulfate, dichloromethane was evaporated under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent ethyl acetate) to obtain the desired product. Yield 1.10 g (Yield 2
8.3%).

¹ H-nmr was measured in CDCl ₃ and the following results were obtained. δ 1.35 to 1.95 ppm (m, 8H), 3.25 (s, 3H),
4.03 (t-2H), 4.17 (t-2H), 5.84 (dd, 1
H), 6.15 (dd, 1H), 6.41 (dd, 1H), 6.98
(D, 2H), 7.45 (d, 2H), 7.87 (s, 1H)

Example 3 Synthesis of Compound P-1 2.3 g of Compound M-1, 0.1 g of azobisisobutyronitrile (AIBN) and 50 ml of THF were placed in a 100 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 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 0.35 g (yield 15.2%).

When ¹ H-nmr was measured in CDCl ₃ , a vinyl proton derived from an acrylate group (δ 5.8) was obtained.
.About.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 7,3
It was 00. The Tg measured by DSC was 115 ° C.

Example 4 Synthesis of compound P-3 1.10 g (2.83 mmol) of compound M-3, 0.10 g of azobisisobutyronitrile (AIBN) and 20 ml of 1,2-dimethoxyethane are 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, and ethyl acetate was added to the residue. 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 0.83 g (yield 75.5
%).

When ¹ H-nmr was measured in CDCl ₃ , a vinyl proton derived from an acrylate group (δ 5.8) was obtained.
.About.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 9.5
It was 00. The Tg measured by DSC was 156 ° C.

Example 5 Preparation of electric field oriented polymer film and generation of second harmonic (S
HG) Experiment 0.2 g of compound P-1 and 2.5 ml of chloroform were put into a test tube. After applying ultrasonic waves for 5 minutes, the total amount of the solution from which the insoluble matter was removed was dropped onto the ITO-coated glass substrate,
It was spin coated at 4000 rpm. An experiment in which the sample, and further the compound P-1 was replaced with the compound P-3, was conducted in the same manner.
Further, an experiment using the compound R-1 was also conducted as a comparative example.

[0039]

[Chemical 10]

The thickness of each of the obtained thin films was about 5 μm. After holding these films at 80 ° 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: 170 ° C After holding for 1.5 hours, 1 to 40 ° C
Cooled in time. Immediately after the electric field orientation, SHG was measured by the apparatus shown in FIG. The results are shown in Table 1. The compound of the present invention has SHG activity and is excellent in blue light transmittance.

[0042]

[Table 1]

[0043]

The polymer material of the present invention is useful as a nonlinear optical material.

[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 amplifier 6 (11) wavelength 1.064 μm 7 (12) wavelength 0.532 μm

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08F 220/36 MMQ 7242-4J 220/38 MMU 7242-4J

Claims (3)

[Claims] 1. A nonlinear optical material comprising a polymer represented by the following general formula (1). General formula (1) In the formula, X represents an oxygen atom, a sulfur atom or NR ⁵ . 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. R
⁴ and R ⁵ represent an alkyl group, an aryl group and a heterocyclic group, and m represents an integer of 2 to 12. The ratio of p to q is 0 to 4. 2. A compound represented by the following general formula (2).
General formula (2) In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an alkyl group, an aryl group and a heterocyclic group. l represents an integer of 2 to 12. 3. A polymer represented by the following general formula (3).
General formula (3) In the formula, R ²¹ and R ²³ may be the same or different and each represents a hydrogen atom or a methyl group, and R ²² represents an alkyl group.
R ²⁴ represents an alkyl group, an aryl group or a heterocyclic group, and n represents an integer of 2 to 12. The ratio of r to s is 0 to 4.