KR19980077455A - New nonlinear optical polymer with excellent thermal stability - Google Patents

Abstract

1. Technical field to which the invention described in the claims belongs

The present invention relates to a novel nonlinear optical polymer which is used as an optical material and has excellent thermal stability.

2. Technical Challenges to be Solved by the Invention

It is intended to provide a new nonlinear optical polymer improved in glass transition temperature so as to prevent the degradation of nonlinear optical properties due to disordered order of optical characteristics at low temperatures.

3. The point of the solution of the invention

There is provided a polymer of the following general formula (I).

In the above general formula (I), -A represents to be.

R ₁ is -O- (CH ₂ ) l -O- (wherein l is an integer from 1 to 20), -S- (CH ₂ ) _m -S- (m is an integer of 1 to 6 or 8 or 9 essence, (n is an integer from 1 to 3 and Y is H or CH ₃ ), or (p is an integer from 1 to 6 and Y is H or CH ₃ ).

R ₂ is to be.

Wherein Q is Cl, Br, I, ego;

R is an alkyl group having 1 to 20 carbon atoms.

And Z is a bidentate unit.

4. Important Uses of the Invention

The novel nonlinear optical polymer having excellent thermal stability of the present invention is used as an optical material such as an optical switch, an optoelectronic material, and an optical storage element.

Description

New nonlinear optical polymer with excellent thermal stability

More particularly, the present invention relates to an optical material applicable to optical information processing using a laser, an optical communication device, and development of a new wavelength laser, and has excellent nonlinear optical properties compared with conventional ones, and has a glass transition temperature (Tg ) ≪ / RTI >

All of the nonlinear optical materials currently used are inorganic monocrystals. They are difficult to obtain crystals. Secondly, they are expensive. Thirdly, they have slow response times. Fourth, they have very high processing temperatures.

Therefore, in order to compensate for the disadvantages of these inorganic single crystals, researches on the development of nonlinear optical materials using organic crystals or organic polymers have been actively conducted. Particularly, since the polymer has no difficulty in growing single crystals and is easy to process, it can be processed into a thin film type material, and it is possible to produce a material having a large nonlinear optical coefficient by molecular design, Has been actively studied. These organic polymers (polymers) are very important in that they can produce various optical devices by directly connecting with semiconductor technology due to the maturity of semiconductor technology based on conventional silicon. Among the nonlinear optical effects that organic nonlinear optical polymers can exhibit, the second largest nonlinear optical effect is optical elements or optoelectronic elements that can be fabricated using such second order nonlinear optical effects, By fabricating an optical storage device using a modulator, a switch, a coupler, and modulated wavelength light, it becomes possible to fabricate devices with higher storage capacity than currently used magnetic disks. In addition, when applied to the fields of optical communication and optical computers, not only can a much larger amount of information be transmitted than today, but also the processing speed of information can be improved to an incomparable extent.

Due to the above advantages, there have been many studies on the second-order nonlinear optical materials for organic polymers, and these studies have mainly focused on host-guest systems in which nonlinear optical properties are dispersed in a polymer system, A nonlinear optical property group can be classified as a functional-zed system in which the polymer is bonded to the side chain or main chain of the polymer. In the case of the host-guest system, the non-linear optical properties are generally incompatible with the polymer, and therefore there are limitations in incorporating them into the polymer system, and they may cause crystallization in the polymer system to scatter light, . However, at present, research on covalent bond systems, which is the latter type, has been actively carried out.

However, various problems have also been pointed out in the case of the organic polymer material of the covalent bond system. For example, in the case of a conventional organic polymer material disclosed in EP 243,860, the nonlinear optical coefficient is not optimized because it contains one chromophore per one repeating unit, and the main chain of the polymer is an aliphatic, flexible chain, The nonlinear optical characteristic of the induced nonlinear optical characteristic is relatively easily disturbed even at a low temperature and the absorption wavelength of the TCNQ chromophore used as a nonlinear optical characteristic is too high to investigate the secondary nonlinear optical effect .

In the present invention, it is desired to provide a novel polymer having a nonlinear optical property which is higher than that of the other polymer, among the polymers of the new nonlinear optical material which can overcome these disadvantages.

In order to achieve the above object, the present invention provides a polymer represented by the following general formula (I).

In the above general formula (I) to be.

R ₁ is -O- (CH ₂ ) l -O- (wherein l is an integer from 1 to 20), -S- (CH ₂ ) _m -S- (m is an integer of 1 to 6 or 8 or 9 essence), (n is an integer from 1 to 3 and Y is H or CH ₃ ), or (p is an integer from 1 to 6 and Y is H or CH ₃ ).

R ₂ is to be.

Wherein Q is Cl, Br, I, ego,

R is an alkyl group having 1 to 20 carbon atoms.

Z is a comonomer selected from the group consisting of benzene derivatives, biphenol isomers, naphthalene isomers and bisphenol isomers as follows.

i] : 1,2-, 1,3-, 1,4- benzene derivatives wherein X ₁ is H, Cl, Br, CH ₃ , _{(CH 2) n -CH 3 (} n is an integer from 1 to 20);

;

ii] : 1,1'-, 2,2'-, 3,3'-, 4,4'-, 1,4'-, 1,3 '-, 1,2' -, 2,3 '-, 2 , 4 ' -, 3,4 '-;

iii] : 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,5-, 2,6, -, 2,7- naphthalene isomers;

iv] : X ₂ is a bisphenol isomer of O, CH ₂ , C (CH ₂ ) ₂ , SO ₂ , S, C = O.

The polymer represented by the general formula (I) according to the present invention has a high solubility in an organic solvent and thus can not only produce a film having excellent optical properties, but also has a thermally excellent property at a glass transition temperature (Tg) Respectively. Therefore, the disturbance phenomenon of nonlinear optical characteristics due to temperature is remarkably reduced.

The polymer according to the present invention having such an advantage can be used for converting the wavelength or energy of a laser, and these polymers are very well dissolved in an organic solvent, so that it is easy to fabricate them as a thin film type material, As an optical modulator, an optical switch, a coupler, and the like.

The polymer of the formula (I) and the compound of the following formula (II) according to the present invention can be prepared by the following polymer and unit synthesis method.

In formula (II), R ₃ is the same as Cl, Br, OH or OR a (R is an alkyl group from C 1 to 20), R ₁ and R ₂ is R _1, R ₂ of formula (I).

[Unit and polymer synthesis method]

In the above formula (II), R is And R 'is , And Ts to be.

Also, DMF is dimethyl formaldehyde, NMP is N-methyl pyrrolidone, and DMSO is dimethyl sulfoxide.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following will describe the present invention in more detail with reference to the preferred embodiments.

However, the following embodiments are provided to facilitate understanding of the present invention, but the present invention is not limited to these embodiments.

[Example 1]

Preparation of 1,4-Dimethylpyridinium p-toluenesulfonate

In a 500 ml three-necked round flask, 15 ml of 4-picoline was dissolved in 100 ml of acetonitrile while stirring, and then an ice bath was added. Then, 23.25 ml of methyl p-toluenesulfonate was dissolved in 70 ml of acetonitrile, slowly added over 30 minutes, the ice bath was removed, and the reaction was allowed to proceed at room temperature for about 1 hour. After completion of the reaction, the obtained white solid was treated with excess acetone and dried in a 60 DEG C vacuum oven to obtain 40.0 g of 1,4-dimethypyridinium p-toluenesulfonate. (Yield: 93%, m.p. 150 [deg.] C)

[Example 2]

Preparation of 4 - [(L) -prourinol] benzaldehyde

23.9 ml of L-prolinol and 38.65 gr of K ₂ CO ₃ were added to 100 ml of 500 ml three-necked flask for about 1 hour at room temperature together with 100 ml of dimethylformaldehyde. After 20 ml of 4-fluorobenzaldehyde was slowly added thereto, the mixture was allowed to react for 24 hours while maintaining the temperature at 100 占 폚. After completion of the reaction, the reaction product was cooled, and then an excess amount of distilled water was added thereto, and the diluted reaction solution was extracted with dichloromethane. The organic layer was concentrated under reduced pressure, and the resulting residue was separated by column chromatography to obtain 20.5 g of a light brown solid. (Yield: 72%, mp 53 ° C)

[Example 3]

Preparation of 1 - [{(L) -furinoxy} benzaldehyde] -4-bromobutane

15 g of 4 - [(L) -purinol] benzaldehyde and 23.19 ml of 1,4-dibromobutane were dissolved in 200 ml of tetrahydrofuran, 2.4 g of NaH was added under nitrogen atmosphere, and the reaction temperature was adjusted to 60 The reaction was allowed to proceed for 24 hours while maintaining the temperature at -65 占 폚. After the reaction was complete, the reaction was filtered to remove excess NaH and the resulting NaOH. The filtrate was concentrated under reduced pressure, and then the residue was separated by column chromatography to obtain 17.4 gr of an orange-colored liquid product having a high viscosity. (70% yield)

[Example 4]

Preparation of diethyl 2,5-di-1 - [{(L) -furinoxy} benzaldehyde] tetramethylene oxide terephthalate

3.4 g of diethyl 2,5-dihydroxyterephthalic acid ester and 5.5 g of K ₂ CO ₃ were dissolved in 100 ml of dimethylformaldehyde in a 250 ml three-necked round flask under nitrogen atmosphere, and the mixture was stirred for about 1 hour. Then, 1- 10.0 g of [{(L) -furinoxy} benzaldehyde] -4-bromobutane was added, and the temperature was maintained at 60 - 65 deg.

After 48 hours, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography to obtain 8.8 g of an orange solid product. (Yield: 85%, m.p. 78 [deg.] C)

[Example 5]

Preparation of 2,5-di-1 - [{(L) -furinoxy} benzaldehyde] tetramethylene oxide terephthalic acid

5.0 g of diethyl 2,5-di-1 [{(L) -furinoxy} benzaldehyde] tetramethylene oxide terephthalate was dissolved in dichloromethane in 200 ml of refined ethanol while refluxing it in a 500-ml three-neck round flask. 1.09 gr of potassium hydroxide was dissolved in 30 ml of ethanol and refluxed for 6 hours. After completion of the reaction, the ethanol was concentrated under reduced pressure to obtain a light brown viscous product. The product was diluted with an excess of distilled water and acid-treated with 2.7 ml of 2N-hydrochloric acid. The mixture was extracted with dichloromethane, and the organic layer was concentrated under reduced pressure. The orange solid product was recrystallized from ethanol to obtain 4.3 g of an orange solid (yield: 93%, m.p. 58 ° C)

[Example 6]

(E) -N-methyl-4- [2- [4 - {(L) -furinoxy} phenyl] -ethynyl] pyridinium p- toluenesulfonate] -tetramethyl Preparation of Rhenoxyterephthalic Acid

In a 250 ml three-necked round flask, 4.7 g of 1,4-dimethylpyridinium p-toluenesulfonate was dissolved in 100 ml of methanol. Then 2,5-di-1 - [{(L) -purinoxy} benzaldehyde] tetramethyleneoxy 4.0 gr of terephthalic acid was added. To this was added 1.7 ml of piperidine. The reaction was carried out for 72 hours while maintaining the temperature at 50 캜 in a nitrogen atmosphere. The reaction solution was concentrated under reduced pressure and then precipitated in ethyl acetate five times to remove unreacted 1,4-dimethylpyridinium p-toluenesulfonate and pyrrolidine. At this time, the red solid obtained by filtration was dried in a 60 deg. C vacuum dryer to obtain 4.9 gr of a light crimson solid. (Yield: 77%, m.p. 102 [deg.] C)

[Example 7]

Synthesis of polymer

To a 250 ml three-neck round flask was added a solution of 2,5-di-1 - [(E) -N-methyl-4- [2- [4 - {(L) Sulfonate] -tetramethylene oxide terephthalic acid, and about 10 ml of thionyl chloride was added in an ice bath. The ice bath was removed, the temperature was raised to room temperature, and the reaction was performed for about 30 minutes. The remaining thionyl chloride was blown with nitrogen blown. To this, 20 ml of dimethyl sulfoxide was added to dissolve the reaction product, and 215 mg of p-phenylenediamine was added thereto. After the addition, reaction was carried out at room temperature for about 1 hour, and the reaction solution was poured into ethyl acetate to obtain a precipitate. The residue was redissolved in ethyl acetate, filtered, and dried to obtain 2.0 g of a reddish-brown colored polymer.

[Example 8]

Manufacture of Thin Film

10% by weight of the polymer prepared in Examples 1 to 7 was dissolved in an organic solvent and the impurities were removed by filtration. The film was then formed into a thin film using a spin coater, and then completely dried in a vacuum dryer. The film was poled using a corona poling device and then nonlinear optical properties were evaluated.

In the nonlinear optical property evaluation, quartz was used as a reference material and the absolute value of the nonlinear coefficient of the polymer was evaluated as the intensity of the nonlinear optical property relative to the reference material. The nonlinear optical coefficient of the polymer according to the present invention thus evaluated showed a high value of about 10-100 pm / V.

The thermal properties of the polymer (p-6-NO ₂ ) prepared by the method of Korean Patent Application No. 95-13864 are compared with the polymer prepared by the process of the present invention. In the case of glass transition temperature (Tg) The glass transition temperature of the polymer was 139 ° C, which was 80 ° C higher than the glass transition temperature of p-6-NO ₂ .

The polymer prepared according to the present invention exhibits excellent non-linear optical properties, which have an excellent thermal property because the glass transition temperature (Tg) thereof is as high as about 140 ° C. as compared with conventional polymers, and the phenomenon of nonlinear optical property due to temperature is remarkably improved .

Claims (2)

A novel non-circular optical polymer having excellent thermal stability represented by the following general formula (I). In the above general formula (I) to be. R ₁ is -O- (CH ₂ ) l -O- (wherein l is an integer from 1 to 20), -S- (CH ₂ ) _m -S- (m is an integer of 1 to 6 or 8 or 9 essence), (n is an integer from 1 to 3 and Y is H or CH ₃ ); (p is an integer from 1 to 6 and Y is H or CH ₃ ). R ₂ is to be. Wherein Q is Cl, Br, I, ego, R is an alkyl group having 1 to 20 carbon atoms. And Z is a bidentate unit. The novel non-linear optical polymer according to claim 1, wherein Z in the above-mentioned unsaturated bond is selected from the group consisting of benzene derivatives, non-phenolic isomers, naphthalene isomers and bisphenol isomers. i] : 1,2, 1,3, as benzene derivatives of 1,4, where X is H, Cl, Br, CH _3, , (CH ₂ ) _n -CH ₃ (n is an integer from 1 to 20), Lt; / RTI > ii] : 1,1'-, 2,2'-, 3,3'-, 4,4'-, 1,4'-, 1,3 '-, 1,2' -, 2,3 '-, 2 , 4 '-, 3,4' -, iii] : Naphthalene isomers of 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,5-, 2,6-, 2,7-, iv] : X is O, Of the bisphenol isomer.