KR100226442B1 - Fluorinated poly(arylene ether) containing thermally curable ethynyl group, preparation method thereof, and optical devices using the same - Google Patents

Abstract

The present invention relates to a fluorine-substituted polyarylene ether-based polymer having an ethynyl group having the formula (1), a method for producing the same, and a method for manufacturing an optical waveguide type optical device by a conventional method using the same. Since the polymer according to the present invention can exclude light absorption in the optical communication region inherent to the material due to molecular vibration by high fluorine substitution in the main chain structure, it is possible to greatly reduce the light traveling loss, which is the biggest problem of the polymer optical device. In addition, the thermosetting ethynyl group is introduced at the end of the polymer to improve the chemical resistance through thermal crosslinking of the polymer matrix to enable a multilayer thin film process, and an excellent optical waveguide-type photonic with excellent thermal stability that does not thermally decompose and sublimate even at temperatures above 500 ° C. The ruler can be manufactured.

(Formula 1)

Description

Fluorinated poly (arylene ether) containing thermally curable ethynyl group, preparation method, and optical devices using the same}

The present invention relates to a fluorinated poly (arylene ether) having a thermosetting ethynyl group of low light propagation loss (hereinafter abbreviated as FPAE), a manufacturing method thereof, and an optical device using the same. Fluorine-substituted polyarylene ethers having a thermosetting ethynyl group for an optical device according to the present invention are particularly useful for the production of thermoelectric modulators, thermoelectric switches, beam splitters, polarization and wavelength filters, waveguide thermal gratings and the like.

High performance polymer materials used for planar waveguide optical devices and optical interconnections include high thermal and environmental stability, low light propagation loss at 1.3 and 1.55 mm wavelengths, fine refractive index control, availability of various substrates, and stacking. There is a great need for sex, dimensional flexibility, easy alignment with fine optical components, and fundamental low cost technology. In order to solve the most important light loss problem, the infrared absorption wavelength is shifted to the long wavelength by using CH polymer substituted with heavy element deuterium or fluorine, that is, CD or CF bond. Minimizing the absorption of water. In addition, S. Imamura, R. Yoshimara, T. Izawa ( Electronics Letters , 27, 1342, 1991) are planar waveguide optical device materials using conventional PMMA or deuterated MMA and deuterated perfluorinated methacrylates. A copolymer with deuterated perfluoro methacrylate monomers was used in various composition ratios to realize a very low light loss optical device with excellent light loss from 1.3 mm to 0.08 dB / cm using cladding and cores. However, PMMA system is poor in thermal stability as Tg is about 100 ^o C. In addition, T. Matsuura, S. Ando, S. Sasaki, F. Yamamoto ( Electronics Letters , 29 (3) 269, 1993) have been developed by various types of perfluorinated polyimides with excellent heat resistance and processability. In the case of, perfluorinated polyimide, polarization independence is difficult due to large birefringence, and light loss occurs due to relatively large hygroscopicity. On the other hand, L. ELdada, C. Xu, KMTStengel, LWShakletter, JT Yardle, ( J. Lightwave Technol. , 14 (7), 1704, 1996) describe the use of UV-curable fluorinated acrylates. Now announced. This material has a light loss of 1.3 and 1.55 mm, respectively, 0.03 and 0.05 dB / cm, which is almost comparable to that of silica, and its refractive index can be continuously adjusted from 1.3 to 1.6, and its birefringence is about 0.0008. It became. In addition, AAGoodwin, FWMercer and MTMcKenzie ( Macromolecules , 30, 2767, 1997) reported the synthesis and physical properties of fluorine-substituted polyarylene ethers developed as low dielectric materials for semiconductor insulation. This material has potential as an excellent optical device due to its excellent thermal, mechanical properties, low hygroscopicity, etc., but its chemical resistance is so weak that it is impossible to manufacture an optical device using a multilayer thin film.

In general, polymer materials for optical devices require low light propagation loss, high thermal stability, low birefringence, and chemical resistance. However, existing polymers for optical devices have a high optical progression loss, low thermal stability and chemical resistance, and thus need to be improved. The present invention eliminates the inherent light absorption of the material and realizes high thermal stability and chemical resistance through thermal curing, thereby making it possible to manufacture an optical device having a low light propagation loss without having the disadvantages of the prior art described above. The main purpose is to provide.

In order to realize the above object, in the present invention, the CH bond of the polymer, which is the root cause of light absorption, is replaced with CF bond to exclude the inherent light absorption of the material, and crosslinks the polymer matrix through thermosetting of the ethynyl group introduced at the polymer terminal. This achieves high thermal stability and chemical resistance. Next, the present invention will be described in more detail.

The fluorine-substituted polyarylene ether polymer derivative having a thermosetting ethynyl group of the following general formula (1) according to the present invention is first subjected to fluorosubstituted polyarylene ether by thermal condensation polymerization of decapulurobiphenyl and aromatic diols having various substituents. After synthesis, the polymer is prepared by reacting an ethynyl substituted phenol derivative.

The present invention will be described in more detail. First, decapulurobibiphenyl and aromatic diols having various substituents are adjusted at various molar ratios, and then thermally polymerized at a high temperature of 100 to 180 ° C. in the presence of K ₂ CO ₃ . Allow decapulurobiphenyl groups to form. Thereafter, the polymer and the ethynyl phenol derivative are synthesized so as to be an ethynyl group at the terminal of the polymer by a fluorine substitution reaction at a high temperature of 100 to 180 ° C. in the presence of K ₂ CO ₃ . The final polymer obtained is dissolved in a suitable solvent and spin-coated on a desired substrate, followed by heat treatment to obtain a final thermoset polymer.

The following examples further illustrate the invention, but do not limit the scope of the invention thereto.

Example 1

Synthesis of Thermosetting Ethinyl Group

(A) Synthesis of 4-iodophenyl acetate:

5 g (22.7 mmol) of 4-iodophenol and 2.12 g (27.3 mmol) of pyridine were completely dissolved in a 100 mL three neck flask. 2.78 g (27.3 mmol) of acetic anhydride was added dropwise to the reaction solution. The reaction temperature was raised to 80 ° C. and stirred for 4 hours. The reaction temperature was then lowered and poured into 150 mL of water. After the reaction mixture was extracted with methylene chloride, the organic layer was dried over anhydrous MgSO ₄ and then the solvent was removed. The resulting product was purified by vacuum distillation. Yield = 97%. Bp = 72 ^o C / 0.1 mmHg. ¹ H-NMR (CDCl ₃ ) δ 2.27 (s, 3H), 6.86 (d, 2H), 7.68 (d, 2H).

(B) Synthesis of 4-phenylethynyl phenol (PEP):

In a 50 mL three neck flask, 4.05 g (15.5 mmol) of 4-iodophenyl acetate and 0.066 g (0.25 mmol) of triphenylphosphine were added, and 7 mL of DMAc was added thereto. 1.89 g (18.5 mmol) of phenylacetylene was added to the reaction vessel, followed by addition of 0.034 g (0.048 mmol) of PdCl ₂ (PPh ₃ ) ₂ and 7 mL of triethylamine. The reaction temperature was raised to 60 ° C., 0.013 g (0.068 mmol) of CuI and 10 mL of triethylamine were added thereto, and the reaction temperature was raised to 80 ° C. and stirred for 24 hours. The temperature was then lowered and the solid produced during the reaction was filtered off to remove triethylamine. The filtrate was precipitated in hydrochloric acid solution, and the resulting solid was filtered, dried and recrystallized from methanol. The resulting product was dissolved in 40 mL THF and 40 mL methanol, and 1.24 g (31 mmol) of sodium hydroxide was added to 20 mL of water in the reaction mixture. The temperature was then raised to 90 ⁰ C and stirred for 12 hours. After again lowering the reaction temperature and poured into 150 mL of hydrochloric acid solution. The reaction mixture was extracted with methylene chloride and the organic layer was dried over anhydrous MgSO ₄ and then the solvent was removed. The resulting product is purified using chromatography (eluent, hexane: ethyl acetate = 3: 1). Yield = 65%. ¹ H-NMR (CDCl ₃ ) δ 5.18 (s, 1H), 6.61 (d, 2H), 7.34 (m, 3H), 7.43 (m, 2H), 7.52 (d, 2H). ¹³ C-NMR (CDCl ₃ ) δ 88.07, 89.21 (etynyl), 115.5, 115.6, 123.5, 127.97, 128.30, 131.4, 133.26, 155.6 (phenyl).

Example 2

Synthesis of Polymer Having Decapulurobiphenyl Group at Terminals in Various Molar Ratios

(A) FPAE 10 (polymerization) polymerization:

In a 100 mL three-necked flask equipped with Dean Stark trap and reflux condenser, 6.074 g (17.997 mmol) of decapulurobibiphenyl and 5.0 g (14.72 mmol) of 4,4 '-(hexafullow) Loisopropylidene) diphenol (6FBPA) was added and completely dissolved in 112 mL of DMAc solvent. 11.2 mL of benzene was added to the reaction mixture, followed by filling the Dean Stock Trap with benzene. 6.10 g of K ₂ CO ₃ was added to the reaction vessel, and the reaction temperature was raised to 120 ° C. and stirred for 4 hours. The temperature was then lowered and the reaction mixture precipitated in 500 mL of NaCl dissolved water. The resulting polymer was filtered and washed successively with water. The obtained polymer was dried in an 80 ° C. vacuum oven. ¹ H-NMR (CDCl ₃ ) δ 7.05 (d, 4H), 7.41 (d, 4H).

(B) FPAE20 polymerization:

The reaction was carried out under the same conditions as in (a) of Example 2 except that 5.492 g (16.27 mmol) of decapulurobiphenyl, 5.0 g (14.72 mmol) of 6FBPA, and 6.10 g of K ₂ CO ₃ were used.

(C) FPAE40 polymerization:

The reaction was carried out under the same conditions as in Example 2 (a) except that 5.0 g (14.97 mmol) of decapulurobiphenyl, 4.786 g (14.234 mmol) of 6FBPA, and 5.90 g of K ₂ CO ₃ were used.

Example 3

Example of introducing the end group with the PEP synthesized in Example 1 to the polymer synthesized in Example 2

(A) Synthesis of FPAE10-PEP:

1 g (0.287 mmol) of FPAE10 and 0.167 g (0.861 mmol) of PEP were added to a 50 mL three necked flask equipped with a Dean Stark trap and a reflux condenser and completely dissolved in 9.8 mL of DMAc solvent. After adding 1.0 mL of benzene to the reaction mixture, benzene was also charged to the Dean stock trap. 0.178 g (1.29 mmol) of K ₂ CO ₃ was added to the reaction vessel, and the reaction temperature was raised to 120 ° C. and stirred for 4 hours. The temperature was then lowered and the reaction mixture precipitated in 200 mL NaCl dissolved water. The resulting polymer was filtered and washed successively with water. The obtained polymer was dried in an 80 ° C. vacuum oven. Yield 95%,

¹ H-NMR (CDCl ₃ ) δ 6.79 (d, 2H), d 6.89 (d, 2H), 7.05 (d, 10H), 7.4 (m, 40H). Pyrolysis temperature of 520 ° C.

(B) Synthesis of FPAE20-PEP:

The reaction was carried out under the same conditions as in (a) of Example 3, except that 2.0 g (0.3 mmol) of FPAE20, 0.36 g (1.8 mmol) of PEP, and 0.376 g of K ₂ CO ₃ were used. Yield 92%. ¹ H-NMR (CDCl ₃ ) δ 6.80 (d, 2H), 6.92 (d, 2H), 7.05 (d, 20H), 7.50 (m, 60H). Pyrolysis temperature 516 ° C.

(C) Synthesis of FPAE40-PEP:

The reaction was carried out under the same conditions as in (a) of Example 3, except that 2.0 g (0.155 mmol) of FPAE40, 0.18 g (0.9276 mmol) of PEP, and 0.192 g of K ₂ CO ₃ were used. Yield 96%. ¹ H-NMR (CDCl ₃ ) δ 6.79 (d, 2H), 6.91 (d, 2H), 7.05 (d, 40H), 7.40 (m, 80H). Pyrolysis temperature 510 ° C.

Example 4

Fabrication of optical device using polymer of the present invention

(A) Optical device fabrication using FPAE10-PEP:

In general, Si may be used as a substrate for manufacturing a polymer device. In this embodiment, a SiO ₂ layer was formed as a lower cladding of the optical waveguide on the prepared Si substrate, or a polymer having a lower refractive index than the core layer polymer was coated. After coating the optical waveguide core material FPAE10-PEP, which is a polymer of the present invention, having low light propagation loss on the lower cladding layer, and thermal curing at 300 ° C. for 1 hour, aligning the optical waveguide mask and forming photolithography for formation of the optical waveguide. Shape of the optical waveguide. Next, the region except for the central portion of the optical waveguide was etched by using reactive ion etching (RIE). Finally, the polymer was coated for the upper cladding to complete the device fabrication. The cross section formation for the input and output of light waves was performed by using a cross section cleaving method or a single side polishing method using a Si cut surface.

(B) Optical device fabrication using FPAE20-PEP:

Except for using FPAE20-PEP as the optical waveguide core material, it was carried out in the same manner as in Example (A).

(C) Optical device fabrication using FPAE40-PEP:

Except for using FPAE40-PEP as the optical waveguide core material, it was carried out in the same manner as in Example (A).

The optical waveguide core polymer of the present invention manufactured by the above-described method has very low optical progression loss of 0.5 dB / cm or less in the optical communication region due to high fluorine substitution. In addition, an optical device having excellent chemical resistance and excellent thermal stability for forming a multilayer thin film essential for device fabrication may be manufactured by a thermosetting process through the introduction of an ethynyl group in the terminal group. That is, as a result of the solubility test, it was dissolved in most organic solvents before thermosetting, but not at all after thermosetting. And thermal stability shows very excellent characteristics that no pyrolysis occurs even above 500 ℃ as a result of TGA temperature record.

Claims (5)

Fluorine-substituted polyarylene ether having an ethynyl group represented by the following general formula (1): (Formula 1)

The method of claim 1, Fluorine substituted polyarylene ether 10-phenylethynyl phenol (FPAE10-PEP), fluorine substituted polyarylene ether 20-phenylethynyl phenol (FPAE20-PEP), or fluorine substituted polyarylene ether 40-phenylethynyl phenol ( Fluorine-substituted polyarylene ether having an ethynyl group, which is FPAE40-PEP). Thermocondensing a decapulurobiphenyl compound and an aromatic diol derivative to produce a polyarylene ether having a pullulophenyl group at the terminal, and replacing the ethynyl phenol derivative at the polymer terminal with the polymer. Method for producing a fluorine-substituted polyarylene ether having an ethynyl group represented by the formula (1) (Formula 1)

Thermally polymerizing a decapulurobenzophenone compound and an aromatic diol derivative to prepare a polyarylene ether having a pullulophenyl group at the terminal; and replacing the ethynyl phenol derivative at the polymer terminal with the polymer. Method for producing a fluorine-substituted polyarylene ether having an ethynyl group represented by the formula (1) (Formula 1)

In the optical waveguide type optical device including a lower cladding layer formed on a silicon substrate, a core layer formed on the lower cladding, and an upper cladding layer formed on the core layer, the core layer is represented by the following formula ( An optical waveguide type optical device characterized by being a fluorine-substituted polyarylene ether having an ethynyl group represented by 1): (Formula 1)