JPH06118463A - Nonlinear high polymer material - Google Patents

Abstract

PURPOSE:To obtain strong second higher harmonic by Nd: YAG laser irradiation by incorporating 2 fulylacrylic acid di-substd. anilide deriv. and 2- fulylmethacrylic acid anhydride. CONSTITUTION:The nonlinear high polymer material is composed of the high polymer compd. having light transmissivity and 2-fulylacrylic acid-2, 3- dichloroanilide (FAA) or 2-fulylacrylic acid anhydride(FMA). The production method of the 2-fulylacrylic acid-2, 3-dichloroanilide(FAA) is not limited especially, evry method is usable. And by allowing 2 fulylacrylic acid deriv. selected among 2-fulylacrylic acid, 2-fulylacrylic acid halide and 2 fulylacrylic acid anhydride to react with 2, 3-dichloroaniline, desired FAA is obtained. And the molar ratio of the charge in the reaction is not limited especially, but executing ordinary in the equivalent molar is preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-linear polymer material suitable for use in an optical modulator, an optical switch element and the like utilizing a non-linear optical effect.

[0002]

2. Description of the Related Art Non-linear optical materials have effects such as wavelength conversion and intensity modulation of light when irradiated with light such as laser light, and are indispensable in the fields of optoelectronics such as optical recording, information processing and optical communication. It has attracted attention as an important material and is being actively researched and developed. Conventionally, as a nonlinear optical material,
Inorganic crystals such as potassium dihydrogen phosphate (KDP) and lithium niobate (LN) have been put to practical use as light wavelength conversion elements for laser light, optical shutters, etc., but these inorganic crystals have poor operability and The nonlinear optical effect is also not sufficient. On the other hand, certain organic compounds such as urea and 2-methyl-4-nitroaniline (MNA) are known to have a large nonlinear optical effect. However, the non-linear optical effects of these organic compounds are not yet sufficiently satisfied, and those having a relatively high non-linear optical effect are themselves highly colored and have absorption at long wavelengths, and the wavelength range used is There was the problem of being limited.

Further, although it is known that organic crystals show a large non-linear optical effect, there are drawbacks such that it is difficult to obtain high quality crystals and it is difficult to process the crystals. To compensate for these drawbacks, a method of dispersing a compound exhibiting a large nonlinear optical effect in a polymer is used (for example, JP-A-62-84139 and JP-A-62-2469).
No. 62). However, these non-linear material-dispersed polymer materials have a problem of compatibility between the nitroaniline-based non-linear material and the polymer, and the addition amount of the non-linear material is limited.
As a result, there is a problem that a material having a large nonlinear effect cannot be obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-linear polymer material having a high non-linear optical effect and no absorption in the visible region.

[0005]

Means for Solving the Problems Based on the finding that a π-electron conjugated organic compound has a large nonlinear optical effect, the inventors have synthesized a 2-furylacrylic acid derivative and measured the nonlinear optical effect. As a result, they have found that 2-furyl acrylic acid di-substituted anilide derivatives and 2-furyl methacrylic anhydride have high non-linear optical effects and have already proposed them (Japanese Patent Application Nos. 3-78191 and 3-78192). Furthermore, by dispersing these compounds in an optically transparent polymer, we have succeeded in producing a nonlinear polymer material that can be easily made into a thin film or a fiber and suitable for devices.

That is, the present invention provides (a) a polymer compound having a light-transmitting property, and (b) 2-furylacrylic acid-2.
A non-linear polymer material containing 3-dichloroanilide (hereinafter abbreviated as FAA) or 2-furyl methacrylic anhydride (hereinafter abbreviated as FMA). The method for producing 2-furylacrylic acid-2,3-dichloroanilide (FAA) of the present invention is not particularly limited, and any method may be used. A typical manufacturing method which is generally used preferably is shown below.

The desired FAA can be obtained by reacting a 2-furyl acrylic acid derivative selected from 2-furyl acrylic acid, 2-furyl acrylic acid halide and 2-furyl acrylic acid anhydride with 2,3-dichloroaniline.

The charge molar ratio of the above reaction is not particularly limited, but it is usually preferable to carry out equimolar. Also,
A reaction solvent is preferably used in the above reaction, and examples thereof include benzene, toluene, chloroform, ether, and acetonitrile. The reaction temperature is preferably 0 to 150 ° C, particularly preferably 20 to 100 ° C. Although the reaction time varies depending on the reaction temperature, it may be generally selected from several minutes to several days.

In the above production method, when 2-furyl acrylic acid halide is used as a raw material, hydrogen halide is produced as a by-product. Therefore, usually, double amount of 2,3-dichloroaniline is used, or hydrogen halide is trapped. It is preferable to use agents. The scavenger is not particularly limited, and known ones can be used. Examples of generally used scavengers include triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like. When 2-furyl acrylic acid is used as a raw material in the above production method, water is by-produced.
Usually, it is preferable to use a dehydrating agent. The dehydrating agent is not particularly limited and known ones can be used. Examples of dehydration methods that are generally suitably used include a method using carbodiimides represented by dicyclohexylcarbodiimide, a method by azeotropic distillation, a method using a dehydrating agent such as molecular sieves, anhydrous sodium sulfate, and anhydrous magnesium sulfate. .

The obtained product is usually purified by recrystallization using a solvent such as benzene, acetone or chloroform.

The method for producing 2-furylmethacrylic acid anhydride (FMA) of the present invention is not particularly limited, and any method may be used. A typical manufacturing method which is generally used preferably is shown below.

The desired FMA can be obtained by heating and stirring 2-furylmethacrylic acid in the presence of a dehydrating agent. As the dehydrating agent, an acid anhydride such as acetic anhydride,
Acid chlorides such as acetyl chloride, and chlorides such as thionyl chloride, oxalyl chloride, carbonate ester, phosphoryl chloride and the like are preferably used.

The above reaction usually does not use a reaction solvent, but a reaction solvent may be used. Examples of the solvent in that case include benzene, toluene, chloroform, ether, acetonitrile and the like. Reaction temperature is 0-1
50 ° C., especially 20-100 ° C. is preferred. Although the reaction time varies depending on the reaction temperature, it may be generally selected from several minutes to several days.

When a dehydrating agent which produces hydrogen chloride as a by-product is used in the above reaction, it is usually preferable to use a hydrogen chloride scavenger. The scavenger is not particularly limited, and known ones can be used. Examples of the scavenger that is generally suitably used include triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like. The product obtained is usually benzene, acetone,
Alternatively, it is purified by recrystallization using a solvent such as chloroform. As the light-transmitting polymer of the present invention, various polymers can be used without particular limitation as long as they are transparent polymers. Preferred examples include polymers soluble in organic solvents such as polyethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polystyrene, polyvinyl chloride, polyacrylamide, polycarbonate, polyoxyethylene, and polysiloxane. .

The non-linear polymer material of the present invention, that is, a polymer material composed of a polymer compound having a light-transmitting property and a 2-furylacrylic acid compound (FAA or FMA) is in the form of a thin film or fiber, and has an electric field, a magnetic field, Excellent non-linear optical performance can be obtained by orientation treatment such as stretching. Further, it is desirable that the polymer material is heated to a temperature equal to or higher than the melting point and cooled to a temperature equal to or lower than the melting point while applying an electric field or magnetic field.

In the present invention, the compounding ratio of the polymer compound and the 2-furylacrylic acid compound (FAA or FMA) is 100 parts by weight for the former and 1 to 80 for the latter.
It is desirable to use 3 parts by weight, preferably 3 to 50 parts by weight. When the compounding amount of the 2-furylacrylic acid compound is small, the non-linear effect tends to be small, and when it is too large, the physical properties of the polymer tend to deteriorate.

In the non-linear polymer material of the present invention, a 2-furyl acrylic acid compound (FAA or F) is added to the polymer compound.
MA) is dispersed and contained therein, and the manufacturing method thereof is not limited at all. For example, 2-furylacrylic acid-2,3-dichloroanilide (FAA) may be added to an acetone solution of PMMA, and the resulting homogeneous solution may be spin-coated or cast on a glass substrate and then dried. At this time, heating is also suitable. Further, good non-linear optical performance can be obtained by heating the film to a temperature equal to or higher than the melting point, applying an electric field, and cooling to a temperature equal to or lower than the melting point with the electric field applied. As a method of applying the electric field, electrodes may be provided on both surfaces of the film, or corona discharge or the like may be used.

[0018]

Industrial Applicability The polymer material provided by the present invention generates a strong second harmonic (green light of 532 nm) by irradiation with, for example, an Nd: YAG laser (1064 nm). Further, since the non-linear polymer material provided by the present invention is a material which is almost transparent and stable in the visible region, it is useful as an optical wavelength conversion element, an optical switching element and the like.

[0019]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these examples.

Production Example 1 2-furylacrylic acid (3.3 g) and benzene (30 ml) were placed in a round-bottomed flask, oxalyl chloride (4 ml) was added dropwise with stirring at room temperature, and the mixture was stirred at room temperature for 1 hour. Benzene and unreacted oxalyl chloride were removed from the reaction solution under reduced pressure. After adding acetonitrile to the flask, while stirring at room temperature, a solution of 2,3-dichloroaniline (8.0 g) in acetonitrile was added,
Stir for 3 hours. Then, after removing acetonitrile under reduced pressure, chloroform was added. The chloroform solution was washed with water and then dried over anhydrous sodium sulfate. Chloroform was removed and the obtained solid was recrystallized from ethanol to obtain colorless crystals of 2-furylacrylic acid-2,3-dichloroanilide (FAA) (3.8 g). The yield was 56%.

The results of instrumental analysis of the product are shown below.

Mp. : 152 ° C absorption spectrum (in ethanol): λcutoff; 3
55 nm IR (cm ^-1 ): 3292 (NH), 1662 (C =
O), 1620 (CH = CH) ¹ H-NMR (CDCl ₃ ): δ = 6.35-8.60p
pm Mass: m / e = 283,281 (M +), 121 Elemental analysis _{(C 13 H 9 Cl 2 NO} 2 = 282.12) measurement (%) C, 55.22; H , 3.04; N,
4.77 Calculated value (%) 55.35 3.22
4.97 Production Example 2 2-furylmethacrylic acid (30.0
g), pyridine (23.5 g) and benzene (500 m
1) and put thionyl chloride (17.5
g) was gradually added dropwise. After completion of dropping, the mixture was stirred at room temperature for a while and then heated and stirred at 50 ° C. for 2 hours. The reaction solution was washed with water, washed with a dilute aqueous alkali solution and a dilute aqueous hydrochloric acid solution, and the produced solid was filtered. The benzene layer was separated from the filtrate and dried over anhydrous sodium sulfate. A mixture of a solid obtained by removing benzene and a filtered solid was recrystallized with a mixed solvent of benzene / hexane to give colorless fine powder crystals of 2-furylmethacrylic acid anhydride (FMA) (17.
4 g) was obtained. The yield was 62%.

The results of instrumental analysis of the product are shown below.

Mp. : 135 ° C absorption spectrum (in ethanol): λcutoff; 3
57 nm IR (cm ^-1 ): 1750 (C = O), 1622 (CH
═CH) ¹ H-NMR (in CDCl ₃ , based on tetramethylsilane): δ = 2.29 ppm (s, 6H), 6.50-7.70
ppm (m, 8H) Mass: m / e = 286 (M ⁺ ), 135 Elemental analysis value (C ₁₆ H ₁₄ O ₅ = 286.27) Measurement value (%) C, 67.28; H, 5.08 Calculated value (%) 67.13 4.93 Example 1 1 g of PMMA was dissolved in 10 ml of acetone, and FAA0.
After adding 05 g to form a uniform solution, a transparent thin film was formed by spin coating (1500 rpm, 10 seconds) on a glass substrate. The obtained thin film was heated to 125 ° C. and subjected to corona poling (5 kv, 0.4 mA) for 15 minutes. The thickness of the film was 4.3 μm, and Nd-YA
Upon irradiation with G laser (1064 nm), generation of optical second harmonic (532 nm) was observed.

Example 2 1 g of PMMA was dissolved in 10 ml of acetone, and FMA0.
After adding 05 g to form a uniform solution, a transparent thin film was formed by spin coating (1000 rpm, 10 seconds) on a glass substrate. The obtained thin film is heated to 125 ° C. and corona poling for 15 minutes (4.8 kv, 0.5 mA)
I went. The film thickness was 4.8 μm, and Nd-
When irradiated with a YAG laser (1064 nm), generation of an optical second harmonic (532 nm) was observed.

Example 3 1 g of polyvinyl chloride was dissolved in 10 ml of THF, and FAA was added.
After adding 0.5 g to make a uniform solution, it was cast on a glass substrate and dried at room temperature to prepare a cast film. The obtained thin film was heated to 120 ° C. and subjected to corona poling (4.8 kv, 0.5 mA) for 10 minutes. On the film, an Nd-YAG laser (1064n
When irradiated with m), generation of optical second harmonic (532 nm) was observed.

Example 4 1 g of polystyrene was dissolved in 10 ml of THF to prepare FMA.
After 0.2 g was put into a uniform solution, the solution was cast on a glass substrate and dried at room temperature to prepare a cast film. The obtained thin film was heated to 125 ° C. and subjected to corona poling (4.8 kv, 0.5 mA) for 15 minutes. On the film, an Nd-YAG laser (1064n
When irradiated with m), generation of optical second harmonic (532 nm) was observed.

Claims (1)

[Claims] 1. A polymer compound having (a) a light-transmitting property,
And (b) 2-furyl acrylic acid-2,3-dichloroanilide or 2-furyl methacrylic anhydride, which is a non-linear polymer material.