KR20180133012A - Fluorinated azobenzene NLO chromophore - Google Patents

Abstract

The present invention relates to fluorine-substituted azobenzene-based nonlinear optical chromophores, and a fluorine-substituted azobenzene compound according to the present invention exhibits an electro-optic effect in a wavelength band used for optical communication through a poling process, shows a little optical signal loss, and is excellent in thermal stability of an electro-optic effect to be usefully used as a composition for an organic electro-optical device.

Description

Fluorinated azobenzene NLO chromophore Fluorinated azobenzene NLO chromophore

The present invention relates to fluorine-substituted azobenzene nonlinear optical chromophores, and relates to the synthesis of nonlinear optical chromophores with high efficiency, low light loss and excellent electro-optic effect thermal stability at the optical communication wavelength.

In recent years, large-capacity and high-speed data processing and information transmission have been demanded as home Internet and IPTV, ultra-high-definition TV, mobile communication, and Internet have rapidly developed. The optical signal is used for such high-speed and high-capacity information processing. The optical signal has less interference between signals than the electric signal, and a large amount of information can be transmitted at a time by frequency modulation or the like.

When the light travels into the material under the electric field, the polarization is formed in the material by the interaction with the light, which changes the refractive index of the material. This is called electro-optic effect, and the refractive index of the material changes according to the intensity of the electric field, and thus the speed of light can be controlled.

In order to process and transmit an optical signal, a component such as an optical modulator is required. Lithium niobate (LiNbO ₃ ) crystalline material has been mainly used. In the case of electrooptical devices using lithium niobate, many studies have been made to replace them with organic materials due to their high processing cost and high cost. Organic materials are more advantageous than conventional inorganic materials in terms of synthesis and process, as well as the ability to control the change in physical properties depending on requirements, ie, processing temperature, refractive index, optical coefficient, and absorption wavelength. It is progressing.

Organic materials can be classified into monomolecular crystals and polymeric materials depending on their form. Organic monomolecular crystals have been intrigued by many researchers in this field at the beginning of the study due to their very large optical coefficients, but they have limitations due to the stability of the materials, the difficulty of crystal growth and the difficulty of the process. As an effort to overcome this, development of materials through a method of dispersing organic molecules in a polymer medium has been actively conducted. However, even in this case, the thermal stability is deteriorated due to the flowability of monomolecules in the polymer medium, and a phenomenon such as aggregation of organic molecules is an important cause of light loss and shows limited use. Furthermore, there is a problem in that organic nonlinear optical chromophores have a problem in that optical signal loss due to absorption of light used in optical communication wavelength and decrease in electrooptic effect caused by loosening of polled chromophore at high temperature.

Among the characteristics of organic materials used for optical devices, low optical signal loss is to reduce signal loss by minimizing absorption by harmonic vibration at 840 nm, 1310 nm and 1550 nm, which are wavelengths used in optical communication. Absorption due to harmonic vibration in the optical communication wavelength region is mainly caused by C-H bonds. To solve this problem, research has been conducted to replace C-H with C-F. The development of a material having the advantages of processing characteristics of a polymer by polymerizing an organic monomolecule having nonlinearity has been regarded as a very desirable direction.

Accordingly, the present inventors have completed the present invention by synthesizing a fluorine-substituted azobenzene-based compound which can be used as a nonlinear optical chromophore having excellent heat resistance and low optical signal loss.

U.S. Patent No. 5,496,899 U.S. Patent No. 6,229,047

An object of the present invention is to provide a fluorine-substituted azobenzene monomer.

It is another object of the present invention to provide a method for producing the monarch.

It is still another object of the present invention to provide a polymer for a nonlinear optical chromophore.

It is still another object of the present invention to provide a composition for a nonlinear optical chromophore comprising the polymer.

Another object of the present invention is to provide an electro-optical element including the polymer.

In order to achieve the above object,

The present invention provides azobenzene monomers represented by the following general formula (1)

[Chemical Formula 1]

In Formula 1,

X is -NR-, -O-, -S- or -S (= O) ₂ -, wherein R is hydrogen, straight or branched C ₁ -C ₅ unsubstituted or substituted with one or more fluoro Alkyl;

L is straight or branched C ₁ -C ₂₀ alkylene unsubstituted or substituted with one or more fluoro;

Q is a photo-crosslinking functional group containing at least one radically polymerizable double bond in the molecule;

Y is -N =, -C =, -C ( F) =, -C (CN) = or -C (NO ₂₎ =.

Also, as shown in the following Reaction Scheme 1,

(Step 1) of reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (1)):

[Reaction Scheme 1]

In the above Reaction Scheme 1, X, L, Q and Y are as defined above.

Further, the present invention relates to an azobenzene monomer of the above formula (1); And

And a monomer having a vinyl-acrylic group. The present invention also provides a polymer for a nonlinear optical chromophore.

The present invention also provides a composition for a nonlinear optical chromophore comprising the polymer.

Furthermore, the present invention provides an electro-optical element comprising the polymer.

The fluorine-substituted azobenzene compound according to the present invention exhibits an electro-optic effect at a wavelength band used for optical communication through a poling process, has a low optical signal loss, and is excellent in the thermal stability of an electro- . ≪ / RTI >

1 is a graph showing the absorbance of a fluorine-substituted azobenzene monomer according to the present invention.

Hereinafter, the present invention will be described in detail.

The present invention provides azobenzene monomers represented by the following general formula (1)

[Chemical Formula 1]

In Formula 1,

X is -NR-, -O-, -S-, -S (= O) - or -S (= O) _2- wherein R is hydrogen, unsubstituted or straight- Or branched C ₁ -C ₅ alkyl;

L is straight or branched C ₁ -C ₂₀ alkylene unsubstituted or substituted with one or more fluoro;

Q is a photo-crosslinking functional group containing at least one radically polymerizable double bond in the molecule;

Y is -N =, -C (F) = or -C (CN) =.

Hereinafter, the fluorine-substituted azobenzene monomer according to the present invention will be described in detail.

Preferably, in the fluorine-substituted azobenzene monomer according to the present invention,

X is -NH-, -N (CH ₃ ) -, -N (CH ₂ CH ₃ ) - or -O-;

L is straight or branched C ₂ -C ₁₀ alkylene unsubstituted or substituted with one or more fluoro;

Q is a photo-crosslinkable functional group containing at least one radically polymerizable side-chain vinyl group in the molecule;

Y is -N =, -C (F) = or -C (CN) =.

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등을 예시할 수 있다.Here, the above Q is not particularly limited as long as it is a photo-crosslinkable functional group containing at least one radically polymerizable side-chain vinyl group in the molecule,

,

,

,

,

,

,

,

,

,

,

And the like.

Further, more preferably, the fluorine-substituted azobenzene monomer according to the present invention is characterized in that it is any one selected from the following group:

(1) 6- (methyl (4 - ((perfluorophenyl) diazenyl) phenyl) amino) hexan-1-ol;

(2) 6- (Methyl (4 - ((perfluoropyridin-4-yl) diazenyl) phenyl) amino) hexan-1-ol; And

(3) 2,3,5,6-Tetrafluoro-4 - ((4 - ((6-hydrohexyl) (methyl) amino) phenyl) diazenyl) benzonitrile.

The fluorine-substituted azobenzene monomer according to the present invention exhibits an electro-optic effect at a wavelength band used for optical communication, has a low optical signal loss, and is excellent in the thermal stability of an electro-optic effect, (See Experimental Example 1 below).

Also, as shown in the following Reaction Scheme 1,

(Step 1) of reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (1)):

[Reaction Scheme 1]

In the above Reaction Scheme 1, X, L, Q and Y are as defined above.

Specifically, in Scheme 1, the compound represented by the formula ( ₂ ) is reacted with a reagent capable of producing a diazo compound such as sodium nitrite to diazotize the amino group (-NH ₂ ) of the compound represented by the formula ( ₂ ) , The diazotized compound represented by the formula (2) may be added to the para position of the benzene represented by the formula (3) to produce the azobenzene monomer represented by the formula (1). Can be applied without particular limitation as long as it is a solvent, temperature, and reaction time under which the usual diazotization reaction can occur.

Further, the present invention relates to an azobenzene monomer of the above formula (1); And

And a monomer having a vinyl-acrylic group. The present invention also provides a polymer for a nonlinear optical chromophore.

In the polymer according to the present invention, the monomer having a vinyl acrylic group may include a monomer containing at least one unsaturated double bond which can be polymerized by a radical mechanism and a monomer containing terminal or pendant ethylenically unsaturated bond have. Specifically, the monomer is not particularly limited as long as it is a monomer capable of performing photopolymerization with the photocrosslinking functional group of X of the azobenzene monomer represented by the general formula (1), but monomers having a vinyl acryl group are preferable. Examples thereof include vinyl acrylate, Acrylate, vinyl ethyl acrylate, vinyl ethyl methacrylate, vinyl octyl methacrylate, vinyl hexyl methacrylate, and vinyl butyl methacrylate.

The polymer according to the present invention may be a block copolymer in which the copolymerization sequence of the azobenzene monomer A and the vinyl acrylate group-containing monomer represented by the formula (1) forms a block chain such as AAAAAA-BBBBBB- and a random chain such as ABAABABABBA- And the like. The arrangement of the monomers can be appropriately used in consideration of an increase in the desired refractive index and physical properties.

In the polymer according to the present invention, the ratio of the azobenzene monomer represented by the formula (1) to the monomer having a vinyl acrylic group is not particularly limited as long as the polymer can absorb the desired wavelength before and after the light irradiation, Is from 0.5 to 20 mol%, preferably from 1 to 15 mol%, more preferably from 1 to 10 mol%, of the whole monomers. If the amount of the azobenzene monomer represented by the above formula (1) is less than 0.5 mol%, the amount of light absorption is too low to require too much energy. If the amount of the azobenzene monomer exceeds 20 mol% The efficiency may be deteriorated drastically.

Further, the polymer according to the present invention can be obtained through the usual polymerization reaction of the azobenzene monomer represented by the above formula (1) and the vinyl acrylate monomer, but it is preferable to produce the monomer through a radical polymerization reaction using a radical initiator such as AIBN Do.

The present invention also provides a composition for a nonlinear optical chromophore comprising the polymer.

According to the mode of distributing the fluorine-substituted azobenzene macromolecule compound having a large nonlinear optical effect according to the present invention in a polymer matrix, a guest who mixes a nonlinear optical azobenzene compound (guest) with a polymer matrix (master) A main chain type in which a non-linear optical azobenzene compound is chemically bonded to a side branch of a polymer main chain, and a main chain type in which a non-linear optical azobenzene compound is chemically bonded as a part of a polymer main chain, Any polymer capable of satisfying the shape can be applied without particular limitation.

As described above, the fluorine-substituted azobenzene compound according to the present invention exhibits an electrooptic effect in a wavelength band used for optical communication through a poling process, has a low optical signal loss, and is excellent in the thermal stability of the electrooptic effect, It can be usefully used as a composition for an optical element.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

< Example  1> Preparation of 6- (methyl (4 - ((perfluorophenyl) diazenyl) phenyl) amino) hexan-

In a 250 mL round bottom flask, dissolve 2,3,4,5,6, - pentafluoroaniline (12 mmol, 2.15 g) in acetic acid (25 mL) and propionic acid (5 mL). The temperature of the solution is lowered to 0 ° C, and then nitroxyl sulfuric acid (21.6 mmol, 2.75 g) dissolved in H ₂ SO ₄ (5 mL) is slowly dropped. The solution is stirred for 10 minutes. While maintaining the temperature at 0 ° C, 6- (methyl (phenyl) amino) hexanol (12 mmol, 2.5 g) sufficiently dissolved in methanol (60 mL) is slowly dropped and stirred again for 30 minutes. After the reaction was completed, the reaction mixture was extracted with distilled water and methylene chloride, dried over MgSO ₄ , filtered under reduced pressure, and the solvent was removed. The residue was purified by column chromatography (silica, n-hexane: ethyl acetate = 3: 1) &Lt; / RTI &gt; Yield: 1.1 g (23%);

^{1 H NMR (400 MHz, CDCl} 3) δ 7.83 (t, J = 13.0 Hz, 2H), 6.71 (d, J = 9.0 Hz, 2H), 3.64 (q, J = 6.4 Hz, 2H), 3.41 (dd J = 13.7, 7.1 Hz, 2H), 3.08 (d, J = 4.4 Hz, 3H), 1.70-1.62 (m, 2H), 1.59 2H); uv-vis (CH ₂ Cl ₂ , nm) 440.

< Example  2 > 6- ( Methyl (4 - ((perfluoropyridin-4-yl) diazenyl ) Phenyl) amino) Hexane -1-ol

2,3,5,6-Tetrafluoropyridin-4-amine (12.04 mmol, 2.00 g) is dissolved in a solution of acetic acid (25 mL) and propionic acid (5 mL) in a 250 mL round bottom flask. The temperature of the solution is lowered to 0 ° C, and then nitroxyl sulfuric acid (21.6 mmol, 2.72 g) dissolved in H ₂ SO ₄ (5 mL) is slowly dropped. The solution is stirred for 10 minutes. 6- (Methyl (phenyl) amino) hexanol (12.04 mmol, 1.24 g) which was sufficiently dissolved in methanol (60 mL) was slowly dropped while maintaining the temperature at 0 ° C and stirred for another 30 minutes. After the reaction was completed, the reaction mixture was extracted with distilled water and methylene chloride, dried over MgSO ₄ , filtered under reduced pressure, and the solvent was removed. The product was purified by column chromatography (silica, n-hexane: ethyl acetate = 5: 1) &Lt; / RTI &gt; Yield: 0.78 g (17%);

^{1 H NMR (400 MHz, CDCl} 3) δ 7.86 (d, J = 9.2 Hz, 2H), 6.75 (d, J = 9.3 Hz, 2H), 3.72 - 3.61 (m, 2H), 3.53 - 3.43 (m, 2H), 3.15 (s, 3H), 1.74-1.65 (m, 2H), 1.64-1.56 (m, 4H), 1.43-1.38 (m, 2H). uv-vis (CH ₂ Cl ₂ , nm) 518.

< Example  3> 2,3,5,6- Tetrafluoro -4 - ((4 - ((6- Hydrohexyl ) ( methyl ) Amino) phenyl) diazenyl) benzonitrile

2,3,5,6-tetrafluoro-4-cyanoaniline (11.9 mmol, 2.00 g) was dissolved in a solution of acetic acid (25 mL) and pyrophinonic acid (5 mL) in a 250 mL round bottom flask. The temperature of the solution is lowered to 0 ° C, and then nitroxyl sulfuric acid (21.6 mmol, 2.72 g) dissolved in H ₂ SO ₄ (5 mL) is slowly dropped. The solution is stirred for 10 minutes. 6- (methyl (phenyl) amino) hexanol (12.04mmol, 1.24g), which is sufficiently dissolved in methanol (60mL), is slowly dropped while maintaining the temperature at 0 ° C and stirred for another 30 minutes. After the reaction was completed, the reaction mixture was extracted with distilled water and methylene chloride, dried over MgSO ₄ , filtered under reduced pressure, and the solvent was removed. The product was purified by column chromatography (silica, n-hexane: ethyl acetate = 5: 1) &Lt; / RTI &gt; Yield: 0.82 g (18%), 1 H NMR (400 MHz, CDCl ₃ )? 7.88 (d, J = 9.2 Hz, 2H), 6.45 (d, J = 9.3 Hz, 2H), 3.71-3.60 ), 3.53-3.40 (m, 2H), 3.15 (s, 3H), 1.74-1.65 (m, 2H), 1.64-1.56 (m, 4H), 1.43-1.38 (m, 2H). uv-vis (CH ₂ Cl ₂ , nm) 522.

< Experimental Example  1> Absorbance of the azobenzene compound according to the present invention

In order to examine the absorbance of the azobenzene monomer according to the present invention, the compounds of Example 1 and Example 2 were respectively dissolved in a dichloromethane solvent and placed in a cell for UV-Vis absorption spectrum measurement. The absorbance at wavelengths from 300 nm to 700 nm And the results are shown in Fig.

1 is a graph showing the absorbance of the compounds of Example 1 and Example 2 according to wavelengths.

As can be seen from FIG. 1, the absorbance at a wavelength of 473 nm was high in Example 1, and the absorbance at a wavelength of 493 nm in Example 2 was high. Therefore, the compound according to the present invention exhibits excellent absorbance at a long wavelength, and thus can be usefully used as an electro-optical element.

Claims (9)

An azobenzene monomer represented by the following formula (1):
[Chemical Formula 1]

(In the formula 1,
X is -NR-, -O-, -S-, -S (= O) - or -S (= O) _2- wherein R is hydrogen, unsubstituted or straight- Or branched C ₁ -C ₅ alkyl;
L is straight or branched C ₁ -C ₂₀ alkylene unsubstituted or substituted with one or more fluoro;
Q is a photo-crosslinking functional group containing at least one radically polymerizable double bond in the molecule;
Y is -N =, -C (F) = or -C (CN) =.
The method according to claim 1,
X is -NH-, -N (CH ₃ ) -, -N (CH ₂ CH ₃ ) - or -O-;
L is straight or branched C ₂ -C ₁₀ alkylene unsubstituted or substituted with one or more fluoro;
Q is a photo-crosslinkable functional group containing at least one radically polymerizable side-chain vinyl group in the molecule;
Y is -N =, -C (F) = or -C (CN) =.
The method according to claim 1,
Q is

,

,

,

,

,

,

,

,

,

or

&Lt; / RTI &gt;
The method according to claim 1,
Wherein the azobenzene monomer is any one selected from the group consisting of azobenzene monomers:
(1) 6- (methyl (4 - ((perfluorophenyl) diazenyl) phenyl) amino) hexan-1-ol;
(2) 6- (Methyl (4 - ((perfluoropyridin-4-yl) diazenyl) phenyl) amino) hexan-1-ol; And
(3) 2,3,5,6-Tetrafluoro-4 - ((4 - ((6-hydrohexyl) (methyl) amino) phenyl) diazenyl) benzonitrile.
As shown in Scheme 1 below,
A process for producing an azobenzene monomer according to claim 1, comprising: (1) reacting a compound represented by the formula (2) with a compound represented by the formula (3) to prepare a compound represented by the formula (1)
[Reaction Scheme 1]

(Wherein X, L, Q and Y are as defined in claim 1).
An azobenzene monomer of claim 1; And
And a monomer having a vinyl acryl group.
A composition for a nonlinear optical chromophore comprising the polymer of claim 6.
An electro-optical device comprising the polymer of claim 6.
9. The method of claim 8,
Wherein the electro-optical element exhibits absorption of a wavelength of 450 to 520 nm.

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