KR0163114B1 - Novel polymer having optimum nonlinear optical property - Google Patents

Abstract

The polymer represented by the following general formula (I) can optimize the number of nonlinear optical systems and has excellent nonlinear optical properties such as a stable main chain structure and suitable chromophore absorption wavelength.

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

R ₁ is (l is an integer from 1 to 20), (m is an integer of 1 to 6 or an integer of 8 or 9) (n is an integer from 1 to 3 and Y is H or CH ₃ ) and (p is an integer from 1 to 6 and Y is H or CH ₃ ), and R ₂ is selected from the group consisting of (R is an alkyl group having 1 to 20 carbon atoms).

Description

[Title of the Invention]

A novel polymer having optimized nonlinear optical properties

DETAILED DESCRIPTION OF THE INVENTION [

[Industrial Applications]

The present invention relates to a novel polymer having optimized nonlinear optical properties, and more particularly, to an optical material applicable to optical information processing using a laser, an optical communication device, and development of a new wavelength laser, And to novel polymers having optical properties.

BACKGROUND ART [0002]

Until now, most of the materials used as nonlinear optical materials are inorganic single crystals. These inorganic single crystals have difficulties in obtaining crystals, have an excessive production cost, have slow response times, and have a very high processing temperature .

Therefore, in order to overcome the above problems of these inorganic single crystals used as nonlinear optical materials, researches on the development of nonlinear optical materials using organic crystals or organic polymers have been actively conducted. In particular, the organic polymers are easy to grow, easy to process, and can be processed into thin film materials. In addition to being able to produce materials with large nonlinear optical coefficients by molecular design, they are also easy to mass-produce Has been studied very actively. 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 a much larger amount of information can be transmitted, but also information processing speed is comparatively high in terms of information processing speed.

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 non-linear optical property group can be classified as a functionalized 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, And so on. However, at present, research on the latter type of shared bonding system is actively conducted.

However, various problems have also been pointed out in the case of such covalently bonded organic polymer materials. 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 .

[PROBLEMS TO BE SOLVED BY THE INVENTION]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a nonlinear optical element which can optimize the number of nonlinear optical systems and has excellent nonlinear optical characteristics such as a stable main chain structure, And to provide a novel polymer.

[MEANS FOR SOLVING THE PROBLEMS]

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

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

R ₁ is (l is an integer from 1 to 20), (m is an integer of 1 to 6 or an integer of 8 or 9) (n is an integer from 1 to 3 and Y is H or CH ₃ ) and (p is an integer from 1 to 6 and Y is H or CH ₃ ), and R ₂ is selected from the group consisting of (R is an alkyl group having 1 to 20 carbon atoms).

[Example]

The compound of the following general formula (II) according to the present invention can be easily prepared according to the following reaction route.

Where R ₃ is the same as CI, Br, OH, or OR a (R is an alkyl group having a carbon number of from 1 to 20), R ₁ and R ₂ are R ₁ and R ₂ of formula (I).

Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are only illustrative of preferred embodiments and effects of the present invention, and the present invention is not limited to these embodiments.

[Example 1]

[Synthesis of polymer ^{_{PAPA-6- (NO 2) 2}} ]

Polymers provided by the present invention were named by the method such as PAPA-ℓ- (R _{²⁾ 2} in accordance with characteristics of the groups having a carbon number of R ₁ and R _2. For example, when R ₁ is -O- (CH ₂ ) ₆ -O- and R ₂ is -CN, the polymer may be represented by PAPA-6- (CN) ² .

A 250 ml three-necked round bottom flask was equipped with a stirrer and 1.16 ml (0.006 mol) of SOCL ₂ in an ice bath. 23 g (0.003 mol) of pyridine was added dropwise thereto, followed by stirring for 30 minutes. When the temperature of the solution reached 2-3 ° C, a separate flask was charged with 2,5-di [1- {N- (4-nitrophenyl) - (L) -prourinoxy} hexylen Oxy] terephthalic acid (1.21 g, 0.0015 mol) was dissolved in 10 ml of pyridine and slowly added dropwise. After the ice bath was removed, the mixture was stirred at room temperature for 30 minutes, the temperature of the reactor was raised to 40 ° C or higher, and the reaction mixture was reduced in pressure to remove unreacted materials. Thereto was added 10 ml of pyridine again to dissolve and then 1.21 g (0.0015 mol) of 2,5-di [1- {N- (4-nitrophenyl) - (L) -furinoxy} hexylenoxy] terephthalic acid was dissolved in pyridine And the solution was added dropwise for a second time. The reaction was allowed to react at 100 < 0 > C for 72 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was added to excess methyl alcohol to obtain a solid. The obtained solid was filtered, washed with water and methyl alcohol, and then dried to obtain 1.37 g of a slightly brownish yellow solid (yield: 57.3%). The polymer thus obtained was confirmed by infrared spectroscopy (IR) and nuclear magnetic resonance (NMR).

IR (cm < ^-1 >); 2950 (CH Str), 1830 (Anhydride C = O Str),

1512 (N-O Str.), 1308 (C-O Str.).

NMR (CDc13, ppm) 6.5 ( d, 8H, Aromatic NO 2 -ortho),

7.6 (s, 4H, Aromatic Terephtalic),

8.0 (d, 8H, Aromatic NO ₂ -meta)

[Example 2]

Synthesis _{(PAPA-6- (NO 2)} 2) of the polymer;

The procedure of Example 1 was repeated except that N-methylpyrrolidone (NMP) was used in place of pyridine in Example 1 to obtain 1.05 g of a polymer at a yield of 43.9%.

[Example 3]

[Synthesis of polymer (p-4-NO ₂ -AM)

A 250 ml three-necked round bottom flask was equipped with a stirrer and about 5 ml of SOCL ₂ was added in an ice bath. To the mixture was added a solution of 2,5- [1- {N- (4-nitrophenyl) - ) -Furinoxy} butylenoxy] terephthalic acid (0.5 g, 6.7 × 10 ^-4 mol) was added thereto. The mixture was stirred for about 30 minutes and then refluxed for 2 hours. After the completion of the reaction, the same procedures as in Example 1 were carried out to obtain 0.85 g (yield: 85.9%) of a polymer having the same IR and NMR.

[Example 4]

Manufacture of Thin Film

10% by weight of the polymer prepared in the above example was dissolved in an organic solvent and the impurities were removed by filtration. The film was formed into a thin film using a spin coater, and then dried completely in a vacuum dryer to prepare a thin film.

[effect]

The polymer represented by the general formula (I) according to an embodiment of the present invention can produce a film having high optical properties because of high solubility in an organic solvent even though the concentration of the chromophore is very high. The polymer according to the present invention is characterized by a very high nonlinear optical coefficient. This can be easily understood from the fact that the second-order nonlinear optical system number d ₃₃ (d (2) = 2d) is directly proportional to the concentration of the generation stage. The nonlinear optical coefficient d ₃₃ of the polymer according to the present invention exhibits a value of about 10 ^-6 esu, which is the largest nonlinear optical coefficient of nonlinear optical polymers known so far. The reason why the polymer according to the present invention has such a large nonlinear optical coefficient is that the polymer according to the present invention has a high concentration of molecules or chromophores and has a main chain structure that is stronger than PMMA (Poly (MehtylMethacrylal)} [{poly (Methyl methacrylate)}], and the like, and the unit used as a chromophore has a very large second-order nonlinear optical coefficient. The polymers according to the present invention having the advantages described above 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. A modulator, a switch, a coupler, and the like.

The thin film produced according to the embodiment of the present invention was poled using a corona poling apparatus and evaluated for nonlinear optical properties. The maximum absorption wavelength in the UV-visible light absorption spectrum of the polymer was determined by measuring the fundamental wave (1064 nm) and the second-order harmonic wave (532 nm) of the Nd-Yag laser used for measuring the second- Did not overlap.

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 number of nonlinear optical systems of the polymers according to the present invention thus evaluated is about 500 to 1200 pm / V, which is the highest value of the nonlinear optical system known to date.

Claims (1)

A polymer represented by the following general formula (I). In the general formula (I), A represents to be. R ₁ is (l is an integer from 1 to 20), (m is an integer of 1 to 6 or an integer of 8 or 9) (n is an integer from 1 to 3 and Y is H or CH ₃ ) and (p is an integer from 1 to 6 and Y is H or CH ₃ ), and R ₂ is selected from the group consisting of (R is an alkyl group having 1 to 20 carbon atoms).