JPH11322690A - New divinyl compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new divinyl compound capable of forming a three- dimensional network structure capable of manifesting high secondary nonlinear optical characteristics and useful as an organic secondary nonlinear optical material by carrying out a photopolymerization while applying an electrical field. SOLUTION: This compound is represented by formula I [R<1> is H or methyl; R<2> is a lower alkyl; (n) is 4-8], e.g. 4-biphenylphenyl 4'-[N-(6- methacryloyloxyhexyl)-N-methylamino]-azobenzene-4-carboxylate. The compound represented by formula I is produced by reacting a compound represented by formula II (e.g. N-methacryloyloxyhexyl-N-methylaniline) with 4-aminobenzoic acid and a nitrite such as sodium nitrite, forming an azo compound represented by formula III e.g. 4'-[N-(6-methacryloyloxyhexyl)-N-methylamino]-azobenzene-4- carboxylic acid}, then converting the resultant compound into an acid halide and subsequently reacting the prepared acid halide with p-vinylphenol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel divinyl compound useful as a new type of organic second-order nonlinear optical material and a method for producing the same.

[0002]

2. Description of the Related Art In the advanced information society in the future,
It is necessary to transmit large-capacity and precise information at high speed, high density and high efficiency. Light is expected to play an important role in this field by complementing electronic technology because it has properties such as parallel progression, spatial processing, large operability, and high density. Recently, an organic nonlinear optical material has been attracting attention as one of the materials necessary for utilizing the above.

[0005] The nonlinear effect of inorganic materials known so far is caused by lattice vibration absorption, whereas the nonlinear effect of organic materials is non-localized π.
This is due to the dipole moment generated when the electron system is distorted by the substituent and basically does not involve lattice vibration, so that a faster response is possible.

By the way, a second-order nonlinear optical material is required to have optical transparency and large nonlinear optical characteristics.
As such a second-order nonlinear optical material, Chained Chromophore has recently been used.
Attention has been paid to e) type organic nonlinear optical materials. This chained chromophore-type organic nonlinear optical material increases the μβ, one of the performance indices of the second-order nonlinear optical material, in proportion to the square of the number of units by linearly combining nonlinear active units. An organic material based on a concept. As one of such chained chromophore-type organic nonlinear optical materials, aromatic esters and aromatic ester oligomers are known. However,
Until now, no practical material has been known as a material having a three-dimensional network structure and exhibiting high second-order nonlinear optical characteristics.

[0005]

SUMMARY OF THE INVENTION According to the present invention, a liquid crystal phase is developed while an electric field is applied in an isotropic phase, and light is irradiated in this state to form a three-dimensional network structure, whereby the orientation of the nonlinear optical characteristic species is adjusted. It is an object of the present invention to provide a practical second-order nonlinear optical material using a divinyl compound capable of forming a liquid crystal having an action of suppressing relaxation and having a high second-order nonlinear optical characteristic.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a compound capable of forming a three-dimensional network structure exhibiting high second-order nonlinear optical characteristics. With the divinyl compound obtained by introducing a vinyl group to the benzene ring at the terminal of acrylic acid or methacrylic acid ester having, it has been found that the object can be achieved,
The present invention has been accomplished based on this finding.

That is, the present invention provides a compound represented by the general formula

Embedded image (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, n is an integer of 4 to 8), and a general formula

Embedded image (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, and n is an integer of 4 to 8), and 4-aminobenzoic acid and nitrite are reacted with an acrylic acid or methacrylic acid ester represented by the formula: Let the general formula

Embedded image (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, and n is an integer of 4 to 8), and then converted to an acid halide, It is intended to provide a method for producing the divinyl compound of the general formula (I) by reacting with p-vinylphenol.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (I), R ¹
Is a hydrogen atom, is an acrylate ester, and R ¹
Is a methacrylic acid ester when is a methyl group, and exhibits a second-order nonlinear optical activity in any case. Next, n in the formula is selected from the range of 4 to 8, but from the viewpoint of second-order nonlinear optical activity, it is preferable that n is as large as possible. R ² includes a lower alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, and a butyl group. Particularly preferred are a methyl group and an ethyl group.

In the production of the compound of the general formula (I), an ω-phenylaminoalkyl ester of acrylic acid or methacrylic acid represented by the general formula (II) is used as a starting material, which is combined with 4-aminobenzoic acid. A first step of diazotizing and coupling with nitrite, a second step of converting the azo compound of the general formula (III) thus obtained into an acid halide, and adding a p to the acid halide thus obtained.
-A third step of reacting vinylphenol.

The ω-phenylaminoalkyl ester of acrylic acid or methacrylic acid of the general formula (II) used as a starting material in the first step is obtained by adding ω-halogenoalkanol to N-lower alkylaniline and dehydrohalogenating agent. And then reacting the product with a halide of acrylic acid or methacrylic acid in the presence of a dehydrohalogenating agent. The N-lower alkylaniline used at this time includes N-methylaniline, N-ethylaniline,
-Propylaniline, N-butylaniline and the like,
As the ω-halogenoalkanol, 4-chlorobutanol, 4-bromobutanol, 4-iodobutanol,
5-chloropentanol, 5-bromopentanol, 5
-Iodopentanol, 6-chlorohexanol, 6-
Bromohexanol, 6-iodohexanol, 7-chloropentanol, 7-bromopentanol, 8-bromohexanol, 8-iodohexanol, and the like.
N-lower alkyl anilines and ω-halogenoalkanols are usually used in stoichiometric proportions. Examples of the dehydrohalogenating agent used in the reaction between N-lower alkylaniline and ω-halogenoalkanol and the reaction between the reaction product and a halide of acrylic acid or methacrylic acid include sodium carbonate, sodium hydrogen carbonate, and carbonic acid. There are inorganic bases such as potassium and potassium hydrogen carbonate, and organic bases such as trimethylamine, triethylamine and pyridine.

Next, as the halide of acrylic acid or methacrylic acid, acryl chloride, acryl bromide, methacryl chloride, methacryl bromide and the like are preferable. These reactions are advantageously performed in an organic solvent such as tetrahydrofuran, tetrahydropyran, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, and acetone.
The diazotization and coupling of the ω-phenylaminoalkyl ester of acrylic acid or methacrylic acid represented by the general formula (II) performed in the first step is a method commonly used in the case of ordinary diazotization and coupling,
That is, a p-aminobenzoic acid hydrochloride is reacted with a nitrite such as sodium nitrite or potassium nitrite in the presence of an excess of hydrochloric acid to form a diazonium salt, and then an acrylic acid represented by the general formula (II) Alternatively, it is performed by coupling an ester of methacrylic acid. This reaction is usually preferably carried out under ice-cooling using water as a solvent.

The thus obtained general formula (II)
Group in the azo compound of I)

Embedded image (Wherein R ² and n have the same meanings as described above) are well known as chromophores that are introduced into the side chain of a polymer compound to form a second-order nonlinear optical material.

Next, in the second step, the carboxyl group bonded to the terminal phenyl group of the azo compound of the general formula (III) obtained in the first step is converted into a halogenocarbonyl group. Can be easily carried out by a method commonly used in the conversion of a compound to its acid halide, for example, a method of reacting with a halogenating agent such as thionyl halide, phosphorus halide or phosphorus oxyhalide. This method comprises dissolving an azo compound of the general formula (III) in an inert organic solvent such as dimethylformamide, dimethylacetamide, diethylsulfoxide and tetrahydrofuran, and adding a polymerization inhibitor such as 2,6-di-ter
The reaction is carried out by adding t-butyl-p-cresol and dripping the halogenating agent into the solution little by little, and after the reaction is completed, distilling off the excess halogenating agent and the solvent.

In the third step, p-vinylphenol is reacted with the acid halide obtained as described above. The p-vinylphenol used at this time is, for example, p-vinylphenol.
It can be produced by dissolving acetoxystyrene in an aqueous alkali solution and neutralizing with carbon dioxide.
In the reaction in the third step, p-vinylphenol is added to the acid halide of the azo compound of the general formula (III) in the presence of a dehydrohalogenating agent and reacted in the same manner as in a normal esterification reaction. This is done by: As the dehydrohalogenating agent at this time, the same one as exemplified in the first step can be used. This reaction is preferably carried out in an inert organic solvent. The inert organic solvent can be arbitrarily selected from those exemplified as the organic solvent in the first step.

In the thus obtained divinyl compound of the general formula (I), only peaks attributable to the melting point were observed in the course of temperature rise in the DSC measurement, but an intermediate phase was developed in the course of temperature fall. A peak and a peak indicating a phase transition from the intermediate phase to the crystal were observed. Further, as a result of identification of the intermediate phase by a polarizing microscope, a Schlieren optical structure unique to the N phase was observed, and it was confirmed that this was a monotropic liquid crystal having the N phase. The compound of the present invention
A second-order nonlinear optical material having a three-dimensional network structure is formed by photopolymerization at both terminal vinyl groups.

[0016]

Next, the present invention will be described in more detail with reference to examples.

Reference Example 1 (N-hydroxyhexyl-N-
Production of methyl aniline) 6-chloro- in 300 ml of acetone under argon atmosphere
Dissolve 66.5 ml (0.5 mol) of 1-hexanol and 227 g (1.5 mol) of sodium iodide,
For 6 hours. After the reaction, the solution was filtered to remove salts, and distilled off under reduced pressure to obtain a mixture of 6-chloro-1-hexanol and 6-iodo-1-hexanol. This mixture and 84 g (1 mol) of NaHCO ₃ were dissolved in 300 ml of dimethylformamide under an argon atmosphere. After confirming that the mixture was dissolved, 107.2 ml (1 mol) of N-methylaniline was added, and the mixture was stirred at 70 ° C. for 6 hours. And reacted. After the reaction, the solution was distilled off under reduced pressure to remove the solvent, and extracted with ether. After dehydration overnight with anhydrous magnesium sulfate, vacuum distillation (148 ° C., 1.0 m
mHg) and purified. The product obtained by distillation under reduced pressure was a yellow viscous liquid. 400MHz ¹ H-NM
When the structure was analyzed using R, N-hydroxyhexyl-
It was confirmed to be N-methylaniline. Yield 6
9.7 g. Yield 67.3%. ¹ H-NMR (CDCl ₃ ): 1.29 to 1.62 (m,
_{8H, - (CH 2) 4} -), 2.9 (s, 3H, N- CH
₃ ) 3.28-3.32 (t, J = 7.6 Hz, 2
_{H, - CH 2 -N),} 3.63 (s, 2H, HO- CH 2
−), 6.65-6.70 (m, 3H, aromati)
c), 7.20-7.25 (t, J = 7.8 Hz, 2
H, aromatic)

Reference Example 2 (Production of N-methacryloyloxyhexyl-N-methylaniline) In an argon atmosphere, 60 ml of tetrahydrofuran was added to
-Hydroxyhexyl-N-methylaniline 6.19 g
(0.03 mol) and 2.47 ml of triethylamine
(0.03 mol) and 30 mg of "Irganox 1330" (manufactured by Hoechst) as a polymerization inhibitor, dissolved in an ice bath, and stirred with 10 ml of tetrahydrofuran.
2.47 ml of methacrylic acid chloride dissolved in
3 mol) was slowly added dropwise over time and stirred at 0 ° C. overnight. Next, after removing the solvent, the mixture was extracted with chloroform and dehydrated with magnesium sulfate overnight. The product obtained by extraction was a pale yellow viscous liquid. 400M
Structural analysis by Hz ¹ H-NMR confirmed that it was N-methacryloyloxyhexyl-N-methylaniline. Yield 7.48 g. 90.8% yield. ¹ H-NMR (CDCl ₃ ): 1.36-1.70 (m,
_{8H, - (CH 2) 4} -), 1.9 (s, 3H, CH 2 =
_{C (CH 3) -),} 2.9 (s, 3H, N- CH 3),
3.29-3.32 (t, J = 7.4 Hz, 2H, -C
_{H 2 -N), 4.12-4.16 (t} , J = 6.6H
_{z, 2H, -O- CH 2 -} ), 5.55 and 6.09
(S * ₂ , 2H, CH ₂ =), 6.88 (s, 2H, a
romantic), 7.21-7.25 (t, J = 7.
8Hz, 2H, aromatic)

Reference Example 3 (Production of p-vinylphenol) p-acetoxystyrene was distilled under reduced pressure,
40 g (0.25 mol) of the fraction obtained at 0.6 mm was added to 9.0
Disperse in 500 ml of aqueous KOH solution and stir at room temperature
Was. After about 2 hours, the solution became homogeneous,
Add neutralized dry ice to the solution and neutralize.
The crude p-vinylphenol is filtered off and dried under reduced pressure overnight.
Was done. Then, recrystallization with n-hexane was performed for 2 days.
Drying under reduced pressure was performed during that time. The product obtained by recrystallization is
It was a white solid. 400MHz¹Structure by H-NMR
Analysis shows that it is p-vinylphenol
confirmed. Yield 2.67 g. Yield 8.9%.¹ H-NMR (CDCl_Three): 4.9 (s, 1H,HO
−), 5.11-5.14 (d, J = 10.8 Hz, 1
H, -CH =CH ₂ ), 5.57-5.62 (d, J =
17.6Hz, 1H, -CH =CH ₂ ), 6.61-
6.68 (m, 1H,-CH= CH_Two), 6.78-
6.80 (d, J = 6.8 Hz, 2H, aromati
c), 7.29-7.31 (d, J = 7.6 Hz, 2
H, aromatic)

Example 4 3.56 g (0.027 mol) of 4-aminobenzoic acid were
After dissolving in 200 ml of 2N hydrochloric acid kept at 40 ° C. and stirring the mixture in a water bath for 30 minutes, 1.95 g (0.027 mol) of sodium nitrite was added little by little and the mixture was stirred. After 30 minutes, the insolubles formed were filtered off. The solution thus prepared was added to the N-methacryloyloxyhexyl-N-methylaniline 7.48 obtained in Reference Example 2.
g (0.027 mol) was added, producing a vermilion clear solution. Next, this is adjusted to pH with aqueous sodium hydroxide solution.
6, and the resulting vermilion suspension was stirred in an ice bath overnight. The reaction mixture was filtered to collect a solid, which was washed with chloroform to remove salts. Then, magnesium sulfate was added thereto, the mixture was left overnight, and dehydrated. Structural analysis of the thus obtained vermilion viscous solid by 400 MHz ¹ H-NMR revealed that 4 ′-[N- (6-methacryloyloxyhexyl) -N-methylamino] -azobenzene-4- It was confirmed to be a carboxylic acid. Yield 9.31 g. Yield 84.4%. ¹ H-NMR (CDCl ₃ ): 1.36-1.72 (m,
_{8H, - (CH 2) 4} -), 1.94 (s, 3H, CH 2
_{= C (CH 3) -)} , 3.07 (s, 3H, N- C
_{H 3), 3.42-3.46 (t,} J = 7.6Hz, 2
_{H, - CH 2 -N),} 4.14-4.17 (t, J =
_{6.6Hz, 2H, -O- CH 2 -} ), 5.56 and _{6.10 (s * 2,2H, CH 2} =), 6.73-6.
75 (d, J = 9.2 Hz, 2H, aromati
c), 7.89-7.91 (d * 2, J = 9.0 Hz,
4H, aromatic), 8.21-8.23 (d,
J = 8.8Hz, 2H, aromatic)

4.65 g (0.01 mol) of the above 4 '-[N- (6-methacryloyloxyhexyl) -N-methylamino] -azobenzene-4-carboxylic acid and a polymerization inhibitor (2,6 (Di-tert-butyl-p-cresol) (30 mg) was added with 5 drops of dimethylformamide, and 41.6 ml (0.57 mol) of thionyl chloride was added dropwise with stirring at room temperature. The mixture was allowed to stand for 30 minutes after dropping, and then the excess thionyl chloride was removed under reduced pressure to obtain the above-mentioned carboxylic acid chloride as a viscous solid. This acid chloride was dissolved in acetone (300 ml) under an argon atmosphere, and triethylamine (3 ml) was added.
1.13 g (0.094 mol) of p-vinylphenol obtained in the above and 10 ml of tetrahydrofuran containing 8.9 ml (0.094 mol) of triethylamine are slowly added dropwise over a period of time. The mixture was stirred and reacted. Then, extracted with chloroform, 400 MHz
Structural analysis by ¹ H-NMR revealed that many impurities were contained and analysis was impossible. Next, this product was subjected to column chromatography using a developing solvent of chloroform / ethyl acetate (9/1), and further recrystallized using (acetone / n-hexane). The product thus obtained was a vermilion solid. 400MHz ¹ H
-Structural analysis by NMR and EI-MASS,
4 '-[N- (6-methacryloyloxyhexyl)-
[N-methylamino] -azobenzene-4-carboxylic acid was confirmed to be 4-vinylphenyl ester.
Yield 1.81 g. Yield 37.7%. ¹ H-NMR (CDCl ₃ ): 1.36-1.73 (m,
_{8H, - (CH 2) 4} -), 1.95 (s, 3H, CH 2
_{= C (CH 3) -)} , 3.09 (s, 3H, N- C
_{H 3), 3.43-3.47 (t,} J = 7.4Hz, 2
_{H, - CH 2 -N),} 4.14-4.17 (t, J =
_{6.6Hz, 2H, -O- CH 2 -} ), 5.27 and 5.74 (d * 2,2H, -CH = CH 2), 5.56
And 6.10 (s * 2,2H, - CH 2 = C (M
e)), 6.71-6.78 (m, 3H, aromat)
ic and _{-CH = CH 2), 7.20-7.22 (} d,
J = 8.8 Hz, 2H, aromatic), 7.47
−7.49 (d, J = 8.8 Hz, 2H, aromat
ic), 7.92-7.94 (m, 4H, aromat)
ic), 8.29-8.31 (d, J = 8.8 Hz, 2
H, aromatic)

Elemental analysis value As C ₃₂ H ₃₅ O ₄ N ₃

[Table 1]

Next, the above-mentioned 4-vinylphenyl ester of 4 '-[N- (6-methacryloyloxyhexyl) -N-methylamino] -azobenzene-4-carboxylic acid was annealed at 100.degree. 0 to 1 per minute
The temperature was raised to 00 ° C and then lowered to 90 to 0 ° C at 5 ° C / min. As a result, an endothermic peak at 78.1 ° C. during the temperature rise process, an exothermic peak indicating a transition from the isotropic phase to the intermediate phase at 56.2 ° C. during the temperature decrease process, and an exothermic peak at 29.9 ° C. from the intermediate phase to crystals An exothermic peak indicating the transition was observed. From this, monotropic transition (K29.9, M56.2I)
It turns out that it is. When the temperature was raised to 200 ° C. at a rate of 10 ° C./min in an argon atmosphere in order to measure the onset temperature of the thermal polymerization, a gentle exothermic peak of the thermal polymerization was observed at 140 ° C. or higher. Further, when observed with a polarizing microscope, no liquid crystal phase was observed during the heating process.
When the temperature was lowered from 7 ° C. at a rate of 0.1 ° C./min, 64.7.
At 0 ° C, the optical texture began to appear and at 60.9 ° C, it became completely optical. A schlieren structure unique to the N phase was observed in this optical structure. Further, it was recognized that the phase transition from the liquid crystal phase to the crystal started at 41.1 ° C. and ended at 36.8 ° C. Further, a film (10000) dispersed in polymethyl methacrylate at a concentration of 10% by weight and subjected to electric field orientation by corona poling (5 kV / cm).
The d ₃₃ value calculated by measuring the second harmonic generation (SHG) for Å) was 100 × 10 ⁻⁹ esu.

[0024]

According to the present invention, a novel divinyl compound capable of forming a second-order nonlinear optical material having a three-dimensional network structure by photopolymerization while applying an electric field is obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroo Matsuda 1-408, Azuma 1-chome, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Hiroshi Miyachi 2641 Yamazaki, Noda-shi, Chiba Pref. Faculty of Engineering Science, Tokyo University of Science (72) Inventor Kato Masao Noda, Chiba Pref. 2641 Yamazaki, Tokyo University of Science

Claims (2)

[Claims] 1. A compound of the general formula (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, and n is an integer of 4 to 8). 2. A compound of the general formula (Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a lower alkyl group, and n is an integer of 4 to 8), and 4-aminobenzoic acid and nitrite are reacted with an acrylic acid or methacrylic acid ester represented by the formula: Let the general formula (Wherein R ¹ , R ² and n have the same meanings as described above), which is then converted to an acid halide and then reacted with p-vinylphenol. The general formula (Wherein R ¹ , R ² and n have the same meaning as described above).