JP3042212B2 - Polymerizable double bond-containing cyclobutenedione derivative, homopolymer or copolymer thereof, and nonlinear optical element using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerizable double bond-containing cyclobutenedione derivative, a homopolymer or a random copolymer thereof, a production method thereof, and a non-linear polymer such as a polymer optical waveguide type wavelength conversion device. It relates to an optical element.

[0002]

2. Description of the Related Art Nonlinear optical elements play an important role in the fields of optical communication and optical detail information processing. Non-linear optical materials used for non-linear optical elements include light mixing that generates sum and difference frequencies of two types of incident light having different frequencies, optical parametrics in which these are irradiated as light having a frequency different from the original frequency, and A Pockels effect or a Kerr effect caused by a change in the refractive index of an optical medium, or conversion of incident light into a second harmonic (SHG) or a third harmonic (THG),
Furthermore, it is a substance that plays a very important role in optical signal processing, such as a memory effect caused by optical bistability. Conventionally, inorganic compounds have been mainly used as such nonlinear optical materials. As an inorganic nonlinear optical material, potassium phosphate titanate (KTP) (KTiOPO)
₄ ) and crystals of inorganic compounds such as lithium niobate (LN) (LiNbO ₃ ) are known, but these did not fully satisfy the requirements. on the other hand,
In recent years, organic nonlinear optical materials have attracted attention as new optical element materials in the field of optoelectronics, and their research has been actively pursued. In particular, compounds having an electron donating group and an electron accepting group in a π electron conjugated system are known to exhibit strong optical nonlinearity at the molecular level due to the interaction between laser light as an electromagnetic wave and π electrons unevenly distributed in the molecule. ing. Compounds that have been studied so far include 2-methyl-4-nitroaniline, m-nitroaniline, N- (4-nitrophenyl) -L-prolinol, 4-dimethylamino-4'-nitrostilbene,
4'-nitrobenzylidene-4-nitroaniline and the like. It is known that a cyclobutenedione structure bonded to a π-electron conjugated system functions as a strong electron-accepting group, and by using such a structure, higher nonlinearity can be obtained as compared with the conventional structure. Is obtained. These materials are used in a single crystal state as in the case of inorganic materials.
In order to exhibit the following nonlinear optical effects, it is essential that they have no central symmetry, but for specific methods to achieve this, it is useful to introduce asymmetric centers and use hydrogen bonds Although there is an indication that this is the case, at present the general method has not been found yet. Further, at present, a device having high efficiency cannot be put into practical use due to the difficulty of crystal growth peculiar to organic substances and the fact that the obtained crystal is fragile and difficult to perform precision processing.

Recently, in order to overcome these drawbacks, an organic compound having a high optical nonlinearity (optical nonlinear dye) is dispersed in a transparent amorphous polymer, and the mixture is used as a mixture. As described above, a method has been developed in which a high electric field is applied while heating, the organic compound is oriented in parallel with the electric field, and then cooled, and the orientation is fixed to obtain a material having no central symmetry. "Dye-dispersed electric field oriented polymer"
These materials, which are commonly referred to as, are characterized in that optical non-linearity and workability caused by a polymer material serving as a base are compatible with each other. By utilizing this processability, an optical waveguide device structure most promising as an optical information processing element can be easily realized. However, even in these electric field oriented polymers, there are limitations in the following points in order to exhibit high optical nonlinearity. That is, first,
The resulting electric-field-oriented polymer is in a thermodynamically non-equilibrium state, so that there is a problem that the alignment of the optical nonlinear dye is relaxed over a long period of use and the optical nonlinearity of the material is reduced. . This orientation relaxation process has a certain correlation with the glass transition temperature of the polymer material serving as the base material (that is, the relaxation rate decreases as the polymer material having a higher glass transition temperature is used). Proceeds quickly at much lower temperatures. Furthermore, in order to achieve high optical nonlinearity, it is necessary to increase the concentration of optical nonlinear dyes in a polymer material, but these dyes have a rigid structure with a developed π-electron conjugated system. Therefore, solubility in a polymer material is generally not high. On the other hand, when the optical nonlinear dye is well compatible with the polymer material serving as the base material, the nonlinear dye itself often acts as a plasticizer for the polymer material, and the glass transition temperature of the compatible material is lowered. There is a great evil of doing so.

[0004] In order to solve these problems, a "side chain type electric field oriented polymer" in which an optical nonlinear dye is directly bonded to a polymer side chain has been proposed. The restrictions on the concentration of the non-linear dye are smaller than those of the dispersion type. Further, it is considered that the relaxation of the orientation of the optical nonlinear dye is generally slower in the side-chain type electric field alignment monomer than in the dispersion type.

[0005]

However, in both the dispersion type and the side chain type, the wavelength range that can be actually used is greatly restricted due to the absorption of light by the optical nonlinear dye itself. At present, there is no satisfactory polymer material when considering the preparation of a polymer. In general,
As a polymer material for waveguides having optical nonlinearity, the magnitude of optical nonlinearity, good processability, heat and environmental stability,
It is required to have a combination of optical transparency, high dielectric breakdown voltage, stability during laser beam irradiation, etc., but it is extremely difficult to select a material that satisfies these characteristics for conventionally known materials. It was difficult. The present invention has been made in view of the above-described problems in the related art. Accordingly, an object of the present invention is to provide a novel polymer compound having excellent optical nonlinearity and a method for producing the same. Another object of the present invention is to provide a novel nonlinear element. Still another object of the present invention is to provide a novel cyclobutenedione derivative used as an intermediate for producing a nonlinear device, and a method for producing the same.

[0006]

The present inventors have disclosed in Japanese Patent Application Laid-Open
JP-A-71117 discloses a non-linear dye having a large optical non-linearity per molecule and a short absorption edge (cutoff wavelength) by utilizing a cyclobutenedione derivative. By introducing the cyclobutenedione structure of a nonlinear dye into a methacrylate resin with excellent optical transparency, moldability and thermal stability, an excellent polymer material that can be used as a side-chain type electric field alignment polymer is obtained. Successful discovery has led to the completion of the present invention.

A first aspect of the present invention is a compound represented by the following general formula (I):
And a novel polymerizable double bond-containing cyclobutenedione derivative represented by the formula:

Embedded image (Wherein R ₁ represents an alkyl group, and R ₂ and R ₃
Represents a hydrogen atom or an alkyl group, or represents an atomic group necessary for bonding to each other to form a nitrogen-containing 4- to 6-membered heterocyclic ring, and R ₄ represents a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. Represents an alkyl group. )

[0008] A second aspect of the present invention is a compound represented by the above general formula (I)
A method for producing a novel polymerizable double bond-containing cyclobutenedione derivative represented by the following general formula (II):

Embedded image Wherein R ₁ , R ₂ and ₃ have the same meanings as defined above, respectively, and the following general formula (III): CH ₂ ＣＲCR ₄ COX (III) Wherein R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom.) Wherein an unsaturated fatty acid derivative represented by the following formula: is reacted in the presence of an acid binder. .

A third aspect of the present invention is a novel homopolymer or copolymer of a cyclobutenedione derivative containing a polymerizable double bond, characterized by being represented by the following general formula (IV).

Embedded image (Wherein R ₁ represents an alkyl group, and R ₂ and R ₃
Represents a hydrogen atom or an alkyl group, or represents an atomic group necessary for bonding to each other to form a nitrogen-containing 4- to 6-membered heterocyclic ring, and R ₄ represents a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. Represents an alkyl group, R ₅ is a hydrogen atom,
Represents a halogen atom, a lower alkyl group or an alkoxy group, and R ₆ represents a halogen atom, an acyl group, a nitrile group,
Represents an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an optionally substituted aminocarbonyl group or an optionally substituted phenyl group, x is a mole fraction, and is 3 × 10 ^-3 to 1 And n is an average degree of polymerization, and represents a number of 100 to 100,000. )

A fourth aspect of the present invention is a method for producing a homopolymer or a copolymer of the above-mentioned cyclobutenedione derivative containing a polymerizable double bond, wherein the polymerizable double bond is represented by the above general formula (I). A bond-containing cyclobutenedione derivative or a compound represented by the following general formula (V): CH ₂ ＣＲCR ₅ R ₆ (V) (wherein R ₅ represents a hydrogen atom, a halogen atom, a lower alkyl group or an alkoxy group, and R ₆ represents A halogen atom, an acyl group, a nitrile group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an optionally substituted aminocarbonyl group or an optionally substituted phenyl group). Is polymerized in the presence of a radical polymerization initiator.

A fifth aspect of the present invention is a nonlinear optical element comprising a homopolymer or a copolymer of a polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (IV).

Hereinafter, the present invention will be described in detail. In the above polymerizable double bond-containing cyclobutenedione derivative of the present invention, R ₁ in the general formula (I) represents an alkyl group, but preferably represents a lower alkyl group having 1 to 5 carbon atoms. Is a lower alkyl group such as a methyl group, an ethyl group and a propyl group. Also, R ₂ and R
₃ represents a hydrogen atom or an alkyl group,
Or, they represent an atomic group necessary for bonding to each other to form a nitrogen-containing heterocyclic ring. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of an atomic group in which R ₂ and R ₃ are bonded to each other to form a nitrogen-containing 4- to 6-membered heterocyclic ring include: Examples include atomic groups forming an azetidine ring, a pyrrolidine ring, a piperidine ring, and a morpholine ring. R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group or a propyl group.

As specific examples of the polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (I) in the present invention, the following can be exemplified. 1-
[4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene-3,4-dione, 1- [4- {N-methyl-
N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene-3,4-dione, 1- [4- {N-ethyl-N- (2-acryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene-3,4-dione, 1- [4- {N-
Ethyl-N- (2-methacryloyloxyethyl) amino {phenyl] -2-dimethylamino-cyclobutene-
3,4-dione, 1- [4- {N-ethyl-N- (2-
Methacryloyloxyethyl) amino diphenyl] -2
-Diethylamino-cyclobutene-3,4-dione, 1
-[4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-piperidino-cyclobutene-3,4-dione, 1- [4- {N-ethyl-
N- (2-methacryloyloxyethyl) amino} phenyl] -2-morpholino-cyclobutene-3,4-dione, 1- [4- {N-propyl-N- (2-methacryloyloxyethyl) amino} phenyl]- 2-ethylamino-cyclobutene-3,4-dione.

The polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (I) of the present invention is represented by the above formula (III) and the cyclobutenedione derivative represented by the above general formula (II). It can be produced by mixing or dissolving a vinyl compound in a solvent or a solvent in the presence of an acid acceptor. Examples of the solvent used in the reaction include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran, dimethylsulfoxide and the like. As the acid acceptor, triethylamine, pyridine, 1,8-diaza- [5.4.0] -bicycloundecene-7 and the like can be preferably used. As the unsaturated fatty acid derivative represented by the general formula (III), for example, acrylic acid chloride, methacrylic acid chloride, α
-Ethylacrylic acid chloride and the like.

The cyclobutenedione derivative represented by the above general formula (II) is a compound of the formula:
-Dichloro-cyclobutene-3,4-dione) and N-ethyl-N- (2-hydroxyethyl) aniline are condensed to give 1-chloro-2- [4- {N-ethyl-N- (2
-Hydroxyethyl) aminodiphenyl] cyclobutene-3,4-dione can be synthesized, followed by introduction of an amine compound and condensation. Examples of the amine compound include primary amines such as methylamine, ethylamine, n-propylamine and isopropylamine, secondary amines such as dimethylamine and diethylamine, azetidine (triethyleneimine), pyrrolidine, piperidine and morpholine. Cyclic amines such as can be used.

Further, in the homopolymer or random copolymer of the polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (IV), R ₁ , R ₂ ,
R ₃ and R ₄ are as described above. Also,
When R ₅ represents a lower alkyl group, a methyl group,
Examples include an ethyl group and a propyl group. When R ₅ represents an alkoxy group, a methoxy group, an ethoxy group, a propoxy group and the like can be mentioned. Examples of the case where R ₆ represents an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, and the like. Examples of the group include an N-phenyl-N-methyl-aminocarbonyl group and an N, N-dimethylaminocarbonyl group. An acyl group represents an acetyl group, and an acyloxy group represents an acyloxy group. Examples thereof include an acetyloxy group and a butyryloxy group. When R ₆ represents a phenyl group which may be substituted, a phenyl group, o
And a mp-methylphenyl group. The average polymerization degree n of the homopolymer and the copolymer is 100 to 10
Although the range is 10,000, a preferable range is 1000 to 20,000. When the average degree of polymerization is smaller than 100, general properties as a polymer compound are not sufficient,
For example, if the film-forming ability is lost, and if it exceeds 100,000, the processability is deteriorated, and molding by melting, melting, or the like becomes substantially impossible. In the case of a copolymer,
The molar fraction x representing the copolymerization ratio is in the range of 3 × 10 ⁻³ to 1, preferably in the range of 0.08 to 1. If x is smaller than 3 × 10 ⁻³ , desired nonlinear optical characteristics cannot be obtained.

The homopolymer or the random copolymer of the polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (IV) of the present invention is preferably represented by the following general formula. You can give things.

Embedded image (Wherein, R ₇ represents a hydrogen atom or a methyl group, R ₈
Represents a lower alkyl group, and R _{1 to} R ₃ , x and n are as defined above. )

The homopolymer or copolymer of the polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (IV) of the present invention is preferably a polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (I). It can be produced by polymerizing a cyclobutenedione derivative or a vinyl compound represented by the above general formula (V) in a reaction solvent in the presence of a radical polymerization initiator.

Examples of the vinyl compound represented by the general formula (V) which can be used in the present invention include the following. Styrene, o-, m-, p
-Methylstyrene, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, octyl methacrylate, acrylamide, N-phenyl-N- Methylacrylamide, N, N-dimethylacrylamide, methyl vinyl ether, methyl vinyl ketone, acrolein,
Acrylic acid, methacrylic acid, N-vinylpyrrolidone and the like can be mentioned.

As the reaction solvent, other than N, N-dimethylformamide, a solvent having a small chain transfer constant such as dimethylsulfoxide, pyridine and the like can be used. Examples of the radical initiator include azobisisobutyronitrile, benzoyl peroxide and the like, and those well-known as radical polymerization initiators can be used. When the polymerizable double bond-containing cyclobutenedione derivative represented by the general formula (I) and the vinyl compound represented by the general formula (V) are randomly copolymerized, the reactivities of both are almost equal, and Since the reaction proceeds in a homogeneous solution system, the present invention has an advantage that a copolymer having a desired copolymerization ratio can be easily synthesized.

The homopolymer or copolymer of the polymerizable double bond-containing cyclobutenedione derivative represented by the general formula (IV) is extremely useful as a material for a nonlinear optical element. That is, a non-linear optical element having excellent characteristics can be formed by forming these homopolymers or copolymers into a thin film and orienting them in an electric field. More specifically, the polymer or copolymer is dissolved in an appropriate solvent to form a solution, and the solution is applied to a substrate by spin coating, dip coating, or the like to form a polymer thin film. Next, the residue is dried in an oven or the like to completely remove the residual solvent. At that time, the inside of the oven may be kept at a reduced pressure. The thickness of the formed polymer thin film is usually preferably set in the range of 0.3 to 4 μm. As the solvent used for forming the polymer thin film,
Any substance can be used as long as it has a boiling point of 200 ° C. or less that dissolves a homopolymer or a copolymer, but preferably has a boiling point of 60 to 160 ° C. Also,
Examples of the glass substrate include Pyrex glass. In addition, a heat-resistant amorphous plate having a temperature of 300 ° C. or higher, a high insulating property, a low refractive index, and a transparent plate that is not affected by the solvent used. Anything can be used. For example, quartz glass or the like can be used.

Next, the polymer thin film formed as described above is subjected to electric field orientation. FIG. 5 is a schematic configuration diagram of a device for orienting an electric field, and this device is installed in a heating furnace. In the figure, 3 is a grounded plate electrode, 4 is an electric wire for applying a voltage, 5 is a power source, and a substrate 1 on which a polymer thin film 2 is formed is placed on the plate electrode 3. As the flat plate electrode, a flat copper plate is preferably used, but other metals such as silver having high conductivity and good thermal conductivity can be used. In addition, as an electric wire for applying a voltage,
In addition to tungsten, a high heat-resistant metal such as platinum, a high heat-resistant alloy such as a platinum-iridium alloy, or a wire rod formed by plating these with an inert metal such as gold can be used. . The apparatus shown in FIG. 5 may be mounted on an apparatus having a structure in which only the plate electrode is controlled in temperature, instead of being installed in a heating furnace. The polymer thin film formed on the substrate is placed on the grounded copper plate electrode, and the temperature in the heating furnace is maintained at a temperature higher than the glass transition temperature of the homopolymer or copolymer constituting the thin film. Then, an appropriate voltage is applied to the electric wire placed at an appropriate distance from the copper plate electrode, and after maintaining for a certain period of time, heating is stopped and the system is allowed to cool. After the temperature returns to room temperature, when the application of the voltage is stopped, a polymer electric field oriented thin film is obtained. The applied voltage at this time is preferably in the range of 4 KV to 8 KV, and the heating time in the voltage applied state is preferably in the range of 1 minute to 30 minutes.

The polymer electric field oriented thin film prepared as described above has a high nonlinear optical constant (d value) as a nonlinear optical element, and can be used as a wavelength conversion material in a wide wavelength range. A wavelength conversion laser in the blue range, which was extremely difficult with conventional materials, is possible.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments of the present invention. Example 1 1) 150 g (1 mol) of squaric acid dichloride (1,2-dichloro-cyclobutene-3,4-dione) was placed in a 500 ml three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel. Dry methylene chloride 200
ml was added and dissolved under a nitrogen atmosphere. The flask was cooled in an ice-water bath, and a solution obtained by dissolving 150 ml (0.9 mol) of N-ethyl-N- (2-hydroxyethyl) aniline in 30 ml of dry methylene chloride was added to the flask.
It was dropped over time. After the dropwise addition, the reaction solution was kept at 20 ° C., and stirring was continued. As a result, it was confirmed that the product was gradually precipitated. After the stirring was continued for 3 hours, the reaction solution was kept at 0 ° C. and 1-chloro-2- [4- {N-ethyl-N- (2-hydroxyethyl) amino} phenyl] was added.
-Cyclobutene-3,4-dione precipitated. The precipitate was separated by filtration, washed well with a mixed solvent consisting of 1 part of acetone and 1 part of n-hexane, dried under reduced pressure, and dried under reduced pressure to give 1-chloro-2- [4- {N-ethyl-N- ( 95 g (yield 35%) of 2-hydroxyethyl) amino {phenyl] -cyclobutene-3,4-dione were isolated. Infrared absorption spectrum: 3310 cm ^-1 (-OH), 30
04 cm ^-1 (aromatic CH), 2879 cm ^-1 (aliphatic CH), 1780 and 1720 cm ^-1 (carbonyl group) UV-visible absorption spectrum: λmax = 401.0 nm
(CH ₂ Cl ₂ )

2) 28 g of 1-chloro-2- [4- {N-ethyl-N- (2-hydroxyethyl) amino} phenyl] -cyclobutene-3,4-dione synthesized as described above .1 mol) in a 500 ml three-necked flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel.
450 ml of dried acetone was added thereto to make a suspended state. While the flask was cooled in an ice water bath, 50 ml (5 times excess) of an aqueous methylamine solution (40%) was added dropwise.
The reaction system became instantaneously uniform with the dropwise addition, but immediately a yellow precipitate was formed. After allowing the reaction solution to stand at 0 ° C. for 12 hours, the formed precipitate was separated by filtration, washed with water, and dried to give 1-
[4- {N-ethyl-N- (2-hydroxyethyl) amino} phenyl] -2-methylamino-cyclobutene-
15 g (yield 55%) of 3,4-dione was obtained. Melting point: 257 to 260 ° C. Infrared absorption spectrum: 3400 cm ⁻¹ (> NH) Ultraviolet-visible absorption spectrum: λmax = 397.4 nm
(Ε = 4.2 × 10 ⁴ ; CH ₂ Cl ₂ )

3) In a 300 ml three-necked flask equipped with a stirrer, a nitrogen introducing tube and a dropping funnel, 1- [4- {N-ethyl-N- (2-hydroxyethyl) amino] synthesized as described above. [Phenyl] -2-methylamino-cyclobutene-3,4-dione (5.5 g, 0.02 mol), and dried N, N-methylacetamide 50
ml was added to dissolve. Further, 7 ml (excess) of triethylamine was added as a hydrochloric acid acceptor, and 6 ml (excess) of methacrylic acid chloride was added dropwise while cooling the flask in an ice-water bath. As the reaction progressed, it was immediately confirmed that a white precipitate (triethylamine hydrochloride) was formed in the reaction system. After the reaction was continued with stirring for 2 hours, the reaction system was allowed to stand at −20 ° C. for 12 hours to precipitate unreacted raw materials. The precipitate was filtered off, the filtrate was poured into 1 liter of distilled water, and the precipitate formed was filtered and dried to obtain a crude product containing the desired product. Excess methacrylic acid chloride contained in this crude product was removed by recrystallization using toluene as a solvent, and purified 1- [4- {N-ethyl-N
-(2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene-3,4-dione (3 g, yield 42%) was obtained. Melting point: 157-159 ° C. Infrared absorption spectrum (FIG. 1): 1712 cm ⁻¹ (ester carbonyl), 1606 cm ⁻¹ , 980 cm ⁻¹ (C =
C), 1164 cm ⁻¹ (ester C—O—C) UV-visible absorption spectrum: λmax = 401.0 nm
(Ε = 4.3 × 10 ⁴ ; CH ₂ Cl ₂ ), λmax = 4
00.2 nm (ε = 4.5 × 10 ⁴ ; N, N-dimethylacetamide)

Example 2 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene was placed in a 25 ml round bottom flask equipped with a stirrer and a three-way cock. 1 g of -3,4-dione and 1 mg of azobisisobutyronitrile were added, and 1 ml of dried N, N-dimethylacetamide was added and dissolved. Next, oxygen in the reaction system was removed by performing several operations of pressure reduction and nitrogen introduction. Heat the flask in a 70 ° C. oil bath,
The polymerization reaction was allowed to proceed. It was confirmed that the reaction system became viscous as the polymerization proceeded. After reacting for 6 hours, the reaction solution was poured into 200 ml of distilled water, the resulting polymer was separated by filtration, and N, N-dimethylacetamide was used as a good solvent, and methanol was used as a poor solvent as a precipitant. And purified by a reprecipitation method. Thereby, 0.86 g of a polymer having an average degree of polymerization n = about 200 was obtained. The obtained polymer was soluble only in amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone. Intrinsic viscosity [η] = 0.26 (solvent: N, N-dimethylacetamide, measured at 25 ° C.) Infrared absorption spectrum (FIG. 2): 980 cm ⁻¹ (C = C)
Disappears. Ultraviolet-visible absorption spectrum: λmax = 400.6 nm
(Ε = 4.1 × 10 ⁴ ; C (per repeating unit), N,
N-dimethylacetamide) Elemental analysis: C 64.02%, H 6.67%, N
8.29% (calculated: C 65.84%, H 6.14%, N
(8.53%) Analysis by Suggestive Scanning Calorimeter (DSC) (Nitrogen stream, heating rate 10 ° C. · min ⁻¹ ): Melting point 179.4 ° C. Thermal Analysis Result: Analysis by thermogravimetry (TG) (in air) , Heating rate 10
° C · min ^-1 ): decomposition start temperature 269 ° C

Example 3 25 ml round bottom flask equipped with a stirrer and a three-way cock
In addition, 1- [4- {N-ethyl-N- (2-methacryloy)
Ruoxyethyl) aminodiphenyl] -2-methylamido
0.2 g of no-cyclobutene-3,4-dione, methacrylic acid
1.8 g of methyl luate and azobisisobutyronitrile
2 mg and dry N, N-methylacetamide 2
ml was added to dissolve. Next, reduce the oxygen in the reaction system.
Pressure and nitrogen were introduced several times to remove.
The flask was heated in an oil bath at 70 ° C. to allow the polymerization reaction to proceed.
Was. It was confirmed that the reaction system became viscous with the progress of polymerization.
Was. After reacting for 6 hours, 200 ml of distilled water
And the resulting copolymer was filtered off, and the same as in Example 2
Purification by reprecipitation using solvents and poor solvents
Was. Thereby, the mole fraction x = 3.15 × 10^-2And flat
1.8 g of a copolymer having a degree of homopolymerization of n = 3700 was obtained. Get
The copolymer obtained was N, N-dimethylacetamide, N, N
N-dimethylformamide, N-methylpyrrolidone,
Trahydrofuran, dimethyl sulfoxide, pyridine
Aprotic polar solvents such as benzene and toluene
Such as aromatic hydrocarbons, chloroform, methylene chloride
Chlorinated solvents such as acetone, methyl ethyl ketone,
Ketones such as tyl isobutyl ketone, ethyl formate,
Soluble in ester solvents such as methyl acetate and ethyl acetate
Water, diethyl ether, diisopropyl ether
, N-hexane and cyclohexane. Intrinsic viscosity [η] = 1.10 (solvent: benzene, at 25 ° C.
Measurement) Viscosity average molecular weight Mv = 4.6 × 10^Five(Polymethacryl
Formula for calculating molecular weight viscosity of methyl acid [η] = KMv^α(K =
5.5X10^-6, Α = 0.76) (Masetsu Kinoshita)
"Experimental method for polymer synthesis", Doujin Kagaku (1972)) Infrared absorption spectrum (Fig. 3): 980cm^-1(C = C)
UV-visible absorption spectrum: λmax = 400.2 nm
(N, N-dimethylacetamide) Thermal analysis result: Analysis by differential scanning calorimetry (DSC)
Temperature rate 10 ℃ ・ min ^-1): Glass transition point 102 ° C. Analysis by thermogravimetry (TG) (in air, heating rate 10
℃ ・ min^-1): Decomposition onset temperature 272 ° C. content of cyclobutenedione derivative structure: 10.9 weight
%

Example 4 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene was placed in a 25 ml round-bottom flask equipped with a stirrer and a three-way cock. 0.4 g of -3,4-dione, 1.6 g of methyl methacrylate and 2 mg of azobisisobutyronitrile were added, and dried N, N-methylacetamide 2 was added.
ml was added to dissolve. This was reacted in the same manner as in Example 3. Thereby, the mole fraction x = 6.81 × 10
^{In the case of -2} , 0.43 g of a copolymer having an average degree of polymerization of n = 2300 was obtained. The obtained copolymer was composed of N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide,
Aprotic polar solvents such as pyridine, benzene,
Soluble in aromatic hydrocarbons such as toluene, chlorine solvents such as chloroform and methylene chloride, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl formate, methyl acetate and ethyl acetate. And insoluble in water, diethyl ether, diisopropyl ether, n-hexane and cyclohexane. Intrinsic viscosity [η] = 0.79 (solvent: benzene, measured at 25 ° C.) Viscosity average molecular weight Mv = 3.0 × 10 ⁵ (calculated as in Example 3) UV-visible absorption spectrum: λmax = 400. 0 nm
(N, N-dimethylacetamide) Thermal analysis result: Differential scanning calorimeter (DSC) analysis (temperature rise rate 10 ° C. min ^-1 under nitrogen stream): Glass transition point 137 ° C. Analysis by thermogravimetry (TG) (In air, heating rate 10
° C min- ¹ ): Decomposition start temperature 270 ° C Content of cyclobutenedione derivative structure: 19% by weight

Example 5 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene was placed in a 25 ml round bottom flask equipped with a stirrer and a three-way cock. 1.0 g of -3,4-dione, 1.0 g of methyl methacrylate and 2 mg of azobisisobutyronitrile, and dried with N, N-methylacetamide 2
ml was added to dissolve. This was reacted in the same manner as in Example 3. Thereby, 1.00 g of a copolymer having a molar fraction x = 0.226 and an average degree of polymerization n = about 600 was obtained. The obtained copolymer was N, N-dimethylacetamide, N,
N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, aprotic polar solvents such as pyridine, benzene, aromatic hydrocarbons such as toluene, chloroform, chlorinated solvents such as methylene chloride, acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl formate,
It was soluble in ester solvents such as methyl acetate and ethyl acetate, and was insoluble in water, diethyl ether, diisopropyl ether, n-hexane and cyclohexane. Intrinsic viscosity [η] = 0.43 (solvent: N, N-dimethylacetamide, measured at 25 ° C.) UV-visible absorption spectrum: λmax = 399.5 nm
(N, N-dimethylacetamide) Thermal analysis result: Analysis by differential scanning calorimeter (DSC) (temperature rising rate 10 ° C. · min ⁻¹ under nitrogen stream): melting point 150.8 ° C. Analysis by thermogravimetry (TG) (In air, heating rate 10
° C min- ¹ ): Decomposition start temperature 270 ° C Content of cyclobutenedione derivative structure: 59% by weight

Example 6 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-cyclobutene was placed in a 25 ml round bottom flask equipped with a stirrer and a three-way cock. 0.2 g of -3,4-dione, 1.8 g of styrene and 2 mg of azobisisobutyronitrile were added, and 2 ml of dried dimethyl sulfoxide was added and dissolved. Next, oxygen in the reaction system was removed by performing several operations of pressure reduction and introduction of nitrogen. The flask was heated in a 90 ° C. oil bath to allow the polymerization reaction to proceed. It was confirmed that the reaction system became viscous as the polymerization proceeded. After reacting for 12 hours, the reaction solution was poured into 400 ml of distilled water, and the produced copolymer was separated by filtration and purified by a reprecipitation method using the same solvent and poor solvent as in Example 2. As a result, 1.5 g of a copolymer having a molar fraction x = 7.3 × 10 ⁻² and an average degree of polymerization n = 350 was obtained. The obtained copolymer is N, N
Aprotic polar solvents such as dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide, pyridine; aromatic hydrocarbons such as benzene and toluene;
Soluble in chlorinated solvents such as chloroform and methylene chloride, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl formate, methyl acetate and ethyl acetate, and water, diethyl ether and diisopropyl. It was insoluble in ether, n-hexane and cyclohexane. Intrinsic viscosity [η] = 0.24 (solvent: benzene, measured at 25 ° C.) Viscosity average molecular weight Mv = 3.9 × 10 ⁴ (molecular weight viscosity conversion equation of styrene [η] = KMv ^α (K = 6.3 × 10 ^-5 ,
α = 0.78) (Masetsu Kinoshita, “Experimental Method for Polymer Synthesis”, Kagaku Doujin (1972)) Infrared absorption spectrum (FIG. 4): 1607, 980 cm ⁻¹
Disappearance of (C = C) absorption, 1500 cm ^-1 (monosubstituted benzene) UV-visible absorption spectrum: λmax = 400.2 nm
(N, N-dimethylacetamide) Thermal analysis result: Differential scanning calorimeter (DSC) analysis (temperature rise rate 10 ° C. min ^-1 under nitrogen stream): Glass transition point 115 ° C. Analysis by thermogravimetry (TG) (In air, heating rate 10
° C · min ^-1 ): Decomposition start temperature 270 ° C Content of cyclobutenedione derivative structure: 13% by weight

Example 7 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-
0.4 g of cyclobutene-3,4-dione, 1.
Using 6 g and 2 mg of azobisisobutyronitrile,
A polymerization reaction was carried out in the same manner as in Example 6, and purification was carried out in the same manner.
1.5 g of a copolymer having a molar fraction x of 0.24 and an average degree of polymerization of n = 350 was obtained. The obtained copolymer was soluble in the same solvents as those exemplified in Example 6, and was insoluble in water, diethyl ether, diisopropyl ether, n-hexane and cyclohexane. Intrinsic viscosity [η] = 0.22 (solvent: benzene, measured at 25 ° C.) Viscosity average molecular weight Mv = 3.5 × 10 ⁴ (calculation method is the same as in Example 6) Infrared absorption spectrum: 1607, 980 cm ⁻¹ (C =
Disappearance of absorption of C) 1500 cm ^-1 (monosubstituted benzene) UV-visible absorption spectrum: λmax = 400.2 nm
(N, N-dimethylacetamide) Thermal analysis result: Analysis by differential scanning calorimeter (DSC) (temperature rising rate: 10 ° C. · min ⁻¹ under nitrogen stream): Glass transition point: 105 ° C. Analysis by thermogravimetry (TG) (In air, heating rate 10
° C min- ¹ ): Decomposition start temperature 270 ° C Content of cyclobutenedione derivative structure: 27% by weight

Example 8 1- [4- {N-ethyl-N- (2-methacryloyloxyethyl) amino} phenyl] -2-methylamino-
Example 6 was prepared using 1 g of cyclobutene-3,4-dione, 1 g of styrene and 2 mg of azobisisobutyronitrile.
A polymerization reaction was carried out in the same manner as described above, and purification was carried out in the same manner. A copolymer having a molar fraction x = 0.24 and an average degree of polymerization n = 300 was obtained.
6 g were obtained. The obtained copolymer was soluble in the same solvents as those exemplified in Example 6, and was insoluble in water, diethyl ether, diisopropyl ether, n-hexane and cyclohexane. Intrinsic viscosity [η] = 0.20 (solvent: benzene, measured at 25 ° C.) Viscosity average molecular weight Mv = 3.1 × 10 ⁵ (calculation method is the same as in Example 6) UV-visible absorption spectrum: λmax = 400. 0 nm
(N, N-dimethylacetamide) Thermal analysis result: Analysis by differential scanning calorimeter (DSC) (temperature rising rate 10 ° C. min ^-1 under nitrogen stream): Glass transition point 130 ° C. Analysis by thermogravimetry (TG) (In air, heating rate 10
° C min- ¹ ): Decomposition start temperature 265 ° C Content of cyclobutenedione derivative structure: 59% by weight

Example 9 The copolymer synthesized in Example 3 (cyclobutenedione copolymer structure content: 10.9% by weight) was dissolved in methyl isobutyl ketone, and washed well in advance to form a 1 mm thick plate. A polymer thin film was formed on a Pyrex glass substrate by spin coating. It was then placed in an oven and heated to 80 ° C. for 24 hours to remove any residual solvent. The formed polymer thin film was subjected to electric field orientation by a device installed in a heating furnace as shown in FIG. The polymer thin film formed on the flat Pyrex glass substrate is placed on a grounded copper plate electrode, and the temperature in the heating furnace is set at a temperature not lower than the glass transition temperature of the copolymer constituting the thin film. While maintaining the temperature at 120 ° C., a voltage of 5 KV was applied to a tungsten electric wire installed at an interval of 1 cm from the copper plate electrode. After keeping the applied voltage constant for 5 minutes, the heating was stopped and the system was allowed to cool. After the temperature reached room temperature, the application of the voltage was stopped to obtain a polymer electric field oriented thin film. When the nonlinear optical constant of the produced polymer electric field oriented thin film was measured by a manufacturer fringe method, the measured nonlinear optical constant d ₃₃ was 8 pm · V ⁻¹ . At the time of measurement, quartz was used as a reference substance, and the above numerical values were calculated by comparing d ₁₁ = 0.4 pm · V ⁻¹ .

FIG. 6 shows the results of examining the change over time in the d value of the polymer electric field oriented thin film. As is apparent from the figure, in the polymer electric field oriented thin film of the present invention, about 10
The d value after ² hours was 3.6 pm · V ⁻¹ , and no further decrease in the d value was observed, indicating that the material was excellent as an organic nonlinear optical material. From the measurement of the transmittance, it was found that the absorption edge (cutoff wavelength) of the polymer electric field alignment thin film was 460 nm. Therefore,
The polymer electric field oriented thin film can be used as a wavelength conversion material in a wide wavelength range, and a wavelength conversion laser in a blue region, which was extremely difficult with a conventional material, was possible. Similarly, with respect to the homopolymer of Example 2 and the copolymers of Examples 4 and 5, polymer thin films were formed and subjected to electric field orientation in the same manner as described above, and the same results as in the above case were obtained. .

Example 10 The copolymer synthesized in Example 6 was dissolved in methyl isobutyl ketone, a polymer thin film was formed in the same manner as in Example 9, and the electric field was changed in the same manner except that the applied voltage was 5 KV. Orientation was performed to obtain a polymer electric field oriented thin film. For manufacturing polymeric field oriented thin film was measured for a nonlinear optical constant by manufacturers fringe method, nonlinear optical constant d ₃₃ measured was 4.3pm · V ^-1. At the time of measurement, quartz was used as a reference substance, and d ₁₁ = 0.4 p
The above numerical values were calculated in comparison with m · V ⁻¹ .

FIG. 7 shows the results of examining the change over time in the d value of the polymer electric field oriented thin film. As is clear from the figure, the polymer electric field oriented thin film of the present invention did not show any decrease in d value, indicating that it was excellent as an organic nonlinear optical material. Furthermore, from the transmittance measurement,
The absorption edge (cutoff wavelength) of this polymer electric field alignment thin film was found to be 460 nm. Therefore, the polymer electric field oriented thin film can be used as a wavelength conversion material in a wide wavelength range, and can be used as a wavelength conversion laser in a blue region, which was extremely difficult with conventional materials. Similarly, with respect to the copolymers described in Examples 7 and 8, polymer thin films were prepared and subjected to electric field orientation in the same manner as described above. As a result, the same results as in the above case were obtained.

Comparative Example 1 A polymer electric field oriented thin film was prepared using a material in which a cyclobutenedione derivative was dispersed in polymethyl methacrylate. That is, 1- (R)-(1
-Hydroxymethyl) propylamino-2- [4- (N
1 g of -methyl-N- (2-methoxyethyl) aminodiphenyl] -cyclobutene-3,4-dione and 9 g of polymethyl methacrylate ([η] = 0.5) were dissolved in methyl isobutyl ketone. In the same manner as described above, a polymer electric field oriented thin film was prepared.

Embedded image (Wherein * represents an asymmetric carbon atom.) Shows the nonlinear optical constant d ₃₃ of the polymer electric field oriented thin film in FIGS. As is clear from the figure, 2.5 pm
A V ^-1, the post 10 ^{for 2} hours was 0.3 pm · V ^-1.

Comparative Example 2 A polymer electric field oriented thin film was prepared using a material in which p-nitroaniline was dispersed in polymethyl methacrylate. That is, 1 g of p-nitroaniline and 9 g of polymethyl methacrylate ([η] = 0.5) were dissolved in methyl isobutyl ketone, and a polymer electric field oriented thin film was produced in the same manner as in Example 9. The polymer electric field oriented thin film of the nonlinear optical constant d ₃₃ is in immediately after preparation was 1.5 pm · V ^-1.

Comparative Example 3 A polymer electric field oriented thin film was prepared using a material in which 2-methyl-p-nitroaniline was dispersed in polymethyl methacrylate. That is, 2-methyl-4-nitroaniline 1
g and 9 g of polymethyl methacrylate ([η] = 0.5) were dissolved in methyl isobutyl ketone, and a polymer electric field oriented thin film was prepared in the same manner as in Example 9. The nonlinear optical constant d ₃₃ of this polymer electric field oriented thin film is 0.9 pm immediately after fabrication.
^-It was V- ¹ .

[0041]

The polymerizable double bond-containing cyclobutenedione derivative of the present invention is a novel compound and is used for preparing a material for a nonlinear optical element. The homopolymer and copolymer of the polymerizable double bond-containing cyclobutenedione derivative of the present invention are novel substances and are useful as materials for nonlinear optical elements exhibiting excellent nonlinear optical characteristics. Also,
The nonlinear optical element of the present invention exhibits excellent nonlinear optical characteristics, and is extremely excellent, for example, as an optical wavelength conversion element, an optical shutter, a high-speed optical switching element, an optical logic gate, an optical transistor, and the like.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a cyclobutenedione compound of Example 1.

FIG. 2 is an infrared absorption spectrum of the homopolymer of Example 2.

FIG. 3 is an infrared absorption spectrum of the copolymer of Example 3.

FIG. 4 is an infrared absorption spectrum of the copolymer of Example 6.

FIG. 5 is a schematic configuration diagram of an apparatus for performing electric field alignment.

FIG. 6 is a graph showing the change over time of the nonlinear optical constants of the electric field oriented thin films of Example 9 and Comparative Example 1.

FIG. 7 is a graph showing the change over time of the nonlinear optical constants of the electric field oriented thin films of Example 10 and Comparative Example 1.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Base, 2 ... Polymer thin film, 3 ... Plate electrode, 4 ... Electric wire for voltage application, 5 ... Power supply.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-71117 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 225/22 C07C 213/06 C08F 220 / 12 C08F 220/36 G02F 1/35 504 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A polymerizable double bond-containing cyclobutenedione derivative represented by the following general formula (I). Embedded image (Wherein R ₁ represents an alkyl group, and R ₂ and R ₃
Represents a hydrogen atom or an alkyl group, or represents an atomic group necessary for bonding to each other to form a nitrogen-containing 4- to 6-membered heterocyclic ring, and R ₄ represents a hydrogen atom or a carbon atom having 1 to 3 carbon atoms. Represents an alkyl group. ) 2. The following general formula (II): (Wherein R ₁ represents an alkyl group, and R ₂ and R ₃
Represents a hydrogen atom or an alkyl group, respectively, or an atomic group necessary for bonding to each other to form a nitrogen-containing 4- to 6-membered heterocyclic ring. ) And the following general formula (III) CH ₂ CR ₄ COX (III) (wherein R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a halogen atom. The method for producing a cyclobutenedione derivative containing a polymerizable double bond according to claim 1, wherein the unsaturated fatty acid derivative represented by the formula (1) is reacted in the presence of an acid binder. 3. A homopolymer or a copolymer of a polymerizable double bond-containing cyclobutenedione derivative represented by the following general formula (IV). Embedded image (Wherein R ₁ represents an alkyl group; R ₂ and R
₃ represents a hydrogen atom or an alkyl group,
Or an atomic group necessary for forming a nitrogen-containing 4- to 6-membered heterocyclic ring by bonding to each other, R ₄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₅ represents a hydrogen atom, a halogen atom, An atom, a lower alkyl group or an alkoxy group, R ₆ represents a halogen atom, an acyl group, a nitrile group, an alkoxy group, an acyloxy group, a carboxyl group,
Represents an alkoxycarbonyl group, an aminocarbonyl group which may be substituted or a phenyl group which may be substituted, x is a mole fraction, and represents a number of 3 × 10 ^-3 to 1; It is a degree and represents a number from 100 to 100,000. ) 4. A polymerizable double bond-containing cyclobutenedione derivative represented by the above general formula (I) or a compound represented by the following general formula (V): CH ₂ ＣＲCR ₅ R ₆ (V) (where R ₅ is hydrogen Represents an atom, a halogen atom, a lower alkyl group or an alkoxy group, and R ₆ represents a halogen atom, an acyl group, a nitrile group, an alkoxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an optionally substituted aminocarbonyl group or A polymerizable double bond-containing cyclobutenedione derivative according to claim 3, wherein the vinyl compound represented by the formula (1) is polymerized with a vinyl compound represented by the formula: A method for producing a homopolymer or a copolymer. 5. A nonlinear optical element comprising a homopolymer or copolymer of a polymerizable double bond-containing cyclobutenedione derivative represented by the general formula (IV).