KR0164100B1 - Thermally stable organic optoelectronic compound for optical device and method of manufacturing same - Google Patents

Abstract

The present invention relates to a thermally stable organic optoelectronic compound for a photonic device and a method for preparing the same, and more particularly, a monomer by reacting a dialkylamino alkylsulfone stilbene and methacryloyl chloride having an OH group attached to a sulfone group end. The present invention relates to a thermally stable organic optoelectronic compound represented by formula (I) prepared by copolymerizing the monomer and methyl methacrylate.

In the general formula (I), the ratio of x to y is 0.1 to 0.7, n is an integer of 2 to 20, and R ₁ and R ₂ are the same or different and have an alkyl group, alkene group or alkyne having 1 to 20 carbon atoms. Group, a phenyl group, a phenyl substituted with an alkyl group, a naphthalene group, or a naphthalene group substituted with an alkyl group.

Description

Thermally stable organic optoelectronic compound for optical device and method of manufacturing same

The present invention relates to a thermally stable organic optoelectronic compound and a method for manufacturing the same, and more particularly to a side chain nonlinear optical polymer material having thermally stable electro-optic properties and very low light transmission loss. It relates to an organic optoelectronic compound used and a method for producing the same.

Optical exchange devices used for information communication have been manufactured mainly using LiNbO ₃ so far. Since the bandwidth of an optical device using LiNbO ₃ is 10 GHz-cm or less, it is expected that the optical device for next-generation information communication will face a limit as LiNbO ₃ . In order to solve the limitations of LiNbO ₃ , the research of the light exchange device using the organic polymer material having electro-optic properties is being actively conducted worldwide.

Organic optoelectronic polymers have particularly good nonlinear optical properties, resulting in very fast switching speeds (2 nanosec. Vs. 50 picosec.) And very high bandwidth (10 GHz vs. 400 CHz) compared to LiNbO ₃ and semiconductor materials. It is easy to connect existing fiber arrays. In addition, organic polymer materials have excellent processability, which means that a variety of optical devices such as linear optical waveguide wiring, phase modulators, Mach-Zender interferometers, beam splitters, and directional couplers are used. It is much easier to integrate X-switch, X-switch, etc., which is very advantageous for optical devices required for next generation.

However, even though the optical device made of the organic polymer material is superior to the LiNbO ₃ optical device currently used, the reason why it is not practical until now is that the electro-optical properties of the polymer material are not thermally stable and the light transmission loss is large.

The organic polymers studied so far are host-guest type polarized by injecting a nonlinear optoelectronic organic material into the polymer medium, and a side chain type polymer which covalently bonds the nonlinear optoelectronic organic material to the polymer medium and the main chain. There is a cross-linked polymer (cross-linked polymer), such as a cross-linked polymer or a cross-linked polymer attached to the polymer, in particular in the case of the cross-linked polymer has been reported to be stable even if the electro-optic properties above 100 ℃. This crosslinked polymer material has solved the thermally stable electro-optic property, but there is a big problem in practical use because the optical transmission loss (10dB / cm) is very high. In addition, the organic polymer material of the host-guest type optical device polarized by injecting a nonlinear optoelectronic organic material has recently been reported to have stable electro-optic properties of a polymer material at 150 ° C. There is a drawback that it cannot be used to manufacture an optical device because it is very small.

In order to solve this problem, instead of doping the nonlinear optical organic material, a side chain nonlinear optical polymer material has been developed in which a nonlinear optical organic material is covalently coupled to the main chain by using a spacer. By this method, the density of non-sunny optical organic materials can be increased to increase the electro-optic coefficient and the thermal stability can be improved. However, the thermal stability has a limit of about 60-70 ℃, causing a problem in the reliability of the device.

Accordingly, it is an object of the present invention to provide an organic optoelectronic compound for photolithography that can solve the above problems.

Another object of the present invention is to provide a method for preparing the compound.

The compound of the present invention for achieving the above object is represented by the following general formula (I).

In the general formula (I), the ratio of x to y is 0.1 to 0.7, n is an integer of 2 to 20, and R ₁ and R ₂ are the same or different and have an alkyl group, alkene group or alkyne having 1 to 20 carbon atoms. Group, a phenyl group, a phenyl substituted with an alkyl group, a naphthalene group, or a naphthalene group substituted with an alkyl group.

The production method for achieving another object of the present invention is to prepare a monomer by reacting a dialkylamino alkylsulfone stilbene and methacryloyl chloride with an OH group attached to the end of the sulfone group, to prepare a monomer and methyl methacrylate It is made to copolymerize.

Hereinafter, the present invention will be described in more detail.

As described above, the conventional side chain nonlinear optical polymer material is mainly made of stilbene nonlinear optical organic material (DANS; diamino nitro stilbene), which is used for manufacturing optical devices by Heochst-Celanese of USA and Akzo of the Netherlands, as a spacer. It was a side chain nonlinear optical polymer material in which a nonlinear optical organic material was covalently linked to a chain polymethyl methacrylate (PMMA). By this method, the density of the nonlinear optical organic material was increased to increase the electro-optic coefficient and the thermal stability was improved. However, thermal stability has a limit of 60-70 ℃. This is due to the low glass transition temperature (Tg) of the polymer, and the current trend is focused on the development of a side chain nonlinear optical polymer material having a glass transition temperature of 150 ° C or higher.

In the present invention, unlike the DANS system used by Heochst-Celanese in the United States and Akzo in the Netherlands, a non-linear optical organic compound of diaminosulfone- stilbene (DASS) having an alkyl sulfone group as a general formula (I) was developed. A hydroxy group was introduced at the end of the alkylsulfone group as shown in the compound to react with methacryloylcholide to prepare a monomer having electro-optic properties, and methyl methacryl having various composition ratios with the monomer. By copolymerizing the rate (MMA), a side chain nonlinear optical polymer material in which stilbene having an OH group attached to the sulfone group end was covalently bonded to the main chain PMMA was prepared. At this time, the reaction molar ratio of the monomer and MMA is any component of 0.2 to 2.5 times, preferably 1: 1.

In the general formula (I), the ratio of x to y is 0.1 to 0.7, n is an integer of 2 to 20, and R ₁ and R ₂ are the same or different and have an alkyl group, alkene group or alkyne having 1 to 20 carbon atoms. Group, a phenyl group, a phenyl substituted with an alkyl group, a naphthalene group, or a naphthalene group substituted with an alkyl group.

The DASS-based side chain nonlinear optical polymer material of the present invention prepared in this manner was able to increase the electro-optic coefficient by increasing the density of nonlinear optical organic matter, and has a higher Tg value (150 ° C. or higher) than the side chain polymer reported so far. It is possible to improve the thermal stability of the electro-optic effect.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

Of the nonlinear optical polymer material for an optical device represented by the general formula (I) by copolymerization of a monomer of 4 '-[(6-methacryloxyhexyl) sulfone] -4-dimethylaminostilbene and methyl methacrylate (MMA) Synthesis method is the same as in Scheme 1, the reactive components and conditions for each step are as follows.

1-1. 4-methylphenyl-6-acetoxy hexyl sulfide

P-toluene thiol (44.54 g, 0.36 mol) is dissolved in DMF (250 mol) and 74.52 g of K ₂ CO ₃ is added to the flask. 6-chloro-1-hexanol (40.86 g, 0.3 mol) was slowly added dropwise thereto, and the reaction temperature was raised to 70 ° C. and stirred for 24 hours. The reaction mixture was poured into 300 ml of water, extracted with ethyl acetate (EA), dried over MgSO ₄ , the solvent was removed, and the obtained product was placed in a reaction vessel. Reaction for 10 hours. The reaction temperature was lowered, poured into 200 ml water, extracted with ethyl acetate (EA), dried over MgSO ₄ , and purified by vacuum distillation.

Breaking point = 165 ° C./0.1 mmHg. Yield = 81.5%

1-2. 4-methylphenyl-6-acetoxy hexyl sulfone

After dissolving 65 g (0.24 mol) of (1-1) in 300 ml of acetic acid, H ₂ O ₂ (30%, 69.21 g) was poured slowly to reflux for 4 hours. After the reaction temperature was lowered, water and acetic acid were removed, diluted in 400 ml chloroform, washed three times with an aqueous NaOH solution, and dried over MgSO ₄ . The resulting raw material is purified by vacuum distillation.

Breaking point = 190 ° C./0.1 mmHg. Yield = 84%

1-3. 4 '-[(6-acetoxy hexyl) sulfonyl] benzyl bromide

61 g (0.2 mol) of (1-2) was dissolved in 400 ml CCl ₄ , and N-bromo rotsinimide (NBS, 35.6 g, 0.2 mol) and 0.4 g benzoyl peroxide (BPO) were slowly added. give. After stirring for 12 hours under reflux, rotsinide floats on the flask wall. After the reaction mixture is completely cooled down, the rosinimide is filtered off and the filtered solution is washed with water, dried over MgSO ₄ and then the solvent is removed. The obtained product obtained 70% yield of 4 '-[(6-acetoxy hexyl) sulfonyl] benzyl bromide, and the rest (1-2) was obtained. This was used for the next reaction without further purification.

1-4. 4 '-[(6-acetoxy hexyl) sulfonyl] benzyl phosphonate

Add 27 g (0.16 mol) of triethyl phosphite into a 500 ml flask and reflux. In this state, 45 g (0.12 mol) of (1-3) is diluted in 10 ml THF and slowly dropped. At this time, the temperature is maintained at the reflux temperature. After complete dropwise addition, the mixture is kept at reflux for 4 hours, then the temperature is lowered, and volatiles are completely removed by distillation. The viscous liquid obtained was separated and purified by chromatography (eluent, EA / Hex .; 3: 1). Yield = 81%

1-5. 4- (dimethyl amino) -4 '-(6-hydroxy hexyl sulfonyl) stilbene

Into a 250ml flask, add 100ml DME and 3.36g sodium hydride and add 7.5g (50 mmol) of N, N-dimethyl amino benzaldehyde while stirring. After 5 minutes, (1-4) diluted in 40 ml DMF was slowly added dropwise. After complete dropping, the reaction is carried out for 4 hours while maintaining the temperature at 110 ° C. Then heat down completely and slowly pour ice water through the funnel. At this time, yellow powder is formed. This powder is filtered and air dried. The obtained solid is dissolved in 100 ml ethanol, 80 ml water and 20 ml HCl solution, refluxed slightly for about 16 hours, and then poured into cold ammonia water. At this time, a fine yellow powder is produced, which is filtered and completely air dried and then recrystallized with ethanol and pyridine. The melting point was 188 占 폚 and the yield was 57%.

1-6. 4 '-[(6-methacryloxyhexyl) sulfone] -4-dimethyl amino stilbene

3 g (7.8 mmol) of (1-5) above are dissolved in 10 ml THF and 2 g pyridine is added. Methacrylooxy chloride (1.2 g, 11.7 mmol) is slowly added dropwise. After reacting for 48 hours while maintaining the reaction temperature at 50 ℃, 1.2g of methacryloxy chloride was further added, stirred for 12 hours, poured into 100ml water and the obtained solid was filtered. The air dried solid is recrystallized with methylene chloride (MC) and ethanol. Melting point was 143 degreeC and yield was 52%.

1-7. Synthesis of Nonlinear Optical Polymer Material for Optical Devices Represented by General Formula (I) by Copolymerization of 4 ′-[(6-Methylacryloxyhexyl) Sulfone] -4-dimethyl Amino Stilbene and MMA

4 '-[(6-methacryloxyhexyl) sulfone] -4-dimethylamino stilbene (2 g) synthesized in the above (1-6) was dissolved in 20 ml chlorobenzene, and then 0.44 g of methyl methacrylate and 21.6. mg (3 mole% ratio) of azobisisobutylnonnitrile (AIBN) is placed in a reaction vessel, frozen in liquid nitrogen and degassed for one hour. The reaction vessel was polymerized for 48 hours in a 60 ℃ oil bath. The polymer obtained is precipitated in methanol, filtered and dried in vacuo. The weight average molecular weight of the obtained copolymer was 60,000-80,000, and glass transition temperature was 133 degreeC.

Example 2

A method of synthesizing a nonlinear optical polymer material for an optical device represented by the general formula (I) by copolymerization of a monomer of 4 '-[(6-methacryloxypropyl) sulfone] -4-dimethylamino stilbene with MMA is shown in the following scheme. 2, and the reactive components and conditions for each step are as follows.

2-1. 4-[(3-chloropropyl) sulfonyl] toluene

1-bromo-3-chloropropane (31g, 0.2mol) diluted in 60ml toluene with p-toluene sulfinic acid sodium salt (17.8g, 0.1mol) and 1g tetrabutyl ammonium bromide (TBAB) in 60ml water ) Is added. The reaction mixture was stirred at 80 ° C. for 24 hours, then the temperature was lowered and the organic layer was extracted with toluene. The extracted solution was dried over MgSO ₄ , toluene was removed, and the product was purified by recrystallization from toluene and hexane. The melting point was 97 ° C. and the yield was 89%.

2-2. 4-[(3-acetoxy propyl) sulfonyl] toluene

After dissolving 35 g of sodium acetate and 3 g of TBAB in 70 mL water, add 20 g (0.09 mol) of (2-1) dissolved in 70 mL toluene, react for 20 hours at 80 ° C., and then pour the reaction mixture into 200 mL of water. . The organic layer was extracted with EA, dried over MgSO ₄ , and the product was purified by vacuum distillation. Breaking point = 155 ° C / 0.1mmHg, yield = 82%

2-3. 4-[(3-acetoxy propyl) sulfonyl] benzyl bromide

Using 50 g (0.195 mol) of (2-2), NBS (35.6 g, 0.2 mol) and 0.4 g of BPO, the reaction product was obtained in the same manner as in (1-3). Yield = 69%

2-4. 4-[(3-acetoxy propyl) sulfonyl] benzyl phosphate

25 g (0.15 mol) of triethyl phosphite and 33 g (0.1 mol) of (2-3) were obtained by the same method as in (1-4). Yield = 81%

2-5. 4- (diethylamino) -4 '-(3-hydroxy propyl sulfonyl) stilbene

The product was obtained by the same method as (1-5) using 1.2g sodium hydride, 3.72g N, N-diethylamino benzaldehyde, and 10.2g of said (2-4). Yield = 65%

2-6. 4 '-[(3-methacryloxypropyl) sulfone] -4-diethylamino stilbene

2.5 g (6.7 mmol) of (2-5) and pyridine and methacryloyl chloride (1.4 g, 13.4 mmol) were obtained in the same manner as in (1-6). Yield = 72%

2-7. Synthesis of 4 '-[(6-methacryloxyhexyl) sulfone] -4-dimethylamino stilbene with non-linear optical polymer material for an optical device represented by general formula (I) by copolymerization with MMA

4 '-[(3-methacryloxypropyl) sulfone] -4-diethylamino stilbene (2 g) synthesized in the above (2-6) was dissolved in 20 mL chlorobenzene, followed by 0.45 g of methyl methacrylate and 22.3. Azobisisobutyronitrile (AIBN) in mg (3 mole% ratio) is placed in a reaction vessel, frozen in liquid nitrogen, and degassed for one hour. The reaction vessel was polymerized for 48 hours in a 60 ℃ oil bath. The polymer obtained is precipitated in methanol, filtered and dried in vacuo. The weight average molecular weight of the obtained copolymer was 60,000-80,000, and glass transition temperature (Tg) was 155 degreeC.

As can be seen from the above examples, the DASS-based side chain nonlinear optical polymer material prepared according to the present invention was able to increase the electro-optic coefficient by increasing the density of nonlinear optical organic matter, and was higher than the side chain polymer reported so far. By having a Tg value (above 150 ° C.), the thermal stability of the electro-optic effect could be improved. Optical devices manufactured using this material are expected to have very good reliability.

Claims (3)

The thermally stable organic optoelectronic compound represented by the following general formula (I). In the general formula (I), the ratio of x to y is 0.1 to 0.7, n is an integer of 2 to 20, and R ₁ and R ₂ are the same or different and have an alkyl group, alkene group or alkyne having 1 to 20 carbon atoms. Group, a phenyl group, a phenyl substituted with an alkyl group, a naphthalene group, or a naphthalene group substituted with an alkyl group. Formula (I), wherein the monomer is prepared by reacting dialkylamino alkylsulfone stilbene and methacryloylchlorolide in which an OH group is attached to a sulfone group end, and copolymerizing the monomer and methyl methacrylate. Method for producing a thermally stable organic optoelectronic compound represented by the. The method according to claim 2, wherein the molar ratio of the monomer and methyl methacrylate is 0.2 to 2.5 times.