KR20030073311A - Monomers with Europium Compounds, their Polymers and Copolymers for Optical Amplifier - Google Patents

Abstract

PURPOSE: Provided are an europium complex monomer, its polymer and copolymer for photomultiplier with more improved property than quarts glass optical fiber. Introduction of an imide group and rare earth metal makes enhanced heat resistance and higher glass transition temperature compared with other polymer photomultipliers. CONSTITUTION: Photomultiplier material comprises a novel monomer represented by the formula 1 which is prepared by making complex compound of itaconic imide with europium, its homopolymer and its copolymer with other monomer containing fluorine and or chlorine. In the formula 1, R1 is acids which make complex compounds with europium ion and acids with amino group which react with itaconic acid to make a monomer; and R2, R3, R4 and R5 are 1,3-diketones which form complex with europium ion.

Description

Europium Compounds, Their Polymers and Copolymers for Optical Amplified Materials

The present invention relates to a process for producing a europium-based novel complex monomer, a polymer and a copolymer thereof for an optical amplified material, and a copolymer of two or more kinds of fluorine or / and chlorine-containing monomers. More specifically, a rare earth metal ion complex is introduced into the monomer structure, and the polymerization ratio with the monomer constituting the optical amplification material support is adjusted so that the rare earth complex is regularly dispersed in the polymerization support. The coalescence was prepared.

In general, in optical information communication and exchange, optical signal amplification through optical devices and optical fibers, optical signal modulation, switching, and so on, causes serious loss of optical information. Is needed. Optical amplification is an electro-optical amplification of a semiconductor optical amplifier using a semiconductor and a fully optical amplifier doped with europium ions in an optical fiber, but is still in the development stage, and has a very high manufacturing cost. Since the amplification technique using optical fibers has been actively studied for amplification using rare earth elements, an optical fiber amplifier capable of transmitting up to 300km at 10Gbps has been developed and used. Quartz-based glass fiber amplifiers are mainly used for long-distance transmission where transmission loss is important due to erbium ion doping. Praseodymium ion doping is mainly used for short-range optical transmission because dispersion of optical signals is minimized. Many studies have been conducted because glass fiber amplifiers have high transmittance, excellent thermal stability and environmental resistance. However, the low bending property of the material itself makes it easy to be broken by external impact, and it is difficult to form and form the desired shape. There is a disadvantage in that the price of optical transmission accessories rises because the connection between devices is not easy. In addition, quartz-based glass optical fibers containing praseodymium ions for amplifying signal light having a wavelength of 1.33 um have problems of lattice vibration mitigation in which energy due to oxide is not emitted as light energy but converted to energy of lattice vibration. . Accordingly, a polymer optical fiber amplifier, which is easy to form and process into a desired form, has been introduced to compensate for the disadvantages of expensive glass optical fibers and at the same time, using a non-oxide polymer. The polymer optical amplifiers published so far have been doped with organic dyes in the polymethyl methacrylate-based polymer optical fiber cores, but this is based on the principle of fluorescence based on spontaneous emission process, not induced emission process. Short, it is difficult to use for optical amplifier. In order to improve the problems presented above, the present patent has prepared a copolymer of a europium-based monomer for optical amplification materials, a polymer and a copolymer thereof, and two or more kinds of different fluorine or / and chlorine-containing monomers. Also, by controlling the polymerization ratio between the europium-based monomer and the monomer constituting the optical amplified material support, a new europium-based polymer and copolymer for the optical amplified material in which the rare earth complex is regularly dispersed in the polymerization support were prepared. By introducing an imide group, the heat resistance was increased more than that of a conventional polymer optical amplifier. In this patent, the above method has solved the problem of the existing polymer optical amplifier significantly.

The present invention relates to the production of europium-based monomers, polymers and copolymers thereof for optical amplified materials, and to the production of copolymers of two or more kinds of two or more different fluorine- and / or chlorine-containing monomers. Europium-based polymers and air for optical amplified materials in which the europion metal ion organic complex is introduced into the monomer structure and the europium complex is regularly dispersed in the polymerization support by controlling the polymerization ratio with the monomers forming the optical amplified material support. The copolymer was prepared to obtain improved physical properties from the conventional quartz glass fiber amplifying material. In addition, by introducing an imide group into the europium complex, heat resistance was increased more than that of a conventional polymer optical amplifier. From this, it is an object to provide a novel polymer and copolymer that solves the problems of existing polymer optical amplification material.

In order to achieve the above object, the organic amic acid and the fluorine and / or chlorine-containing amic acid react with itaconic anhydride, which form a complex with europium ions and induce an imidization reaction, and then form a complex with europium ions. Monomers and homopolymers were prepared. Europium complex monomers for achieving the above object is configured to include a structure represented by the following formula (1).

In the above formula, R1 is an amic acid capable of producing a monomer by reacting an amic acid having an acid functional group capable of forming a complex with europium ions and an amine group capable of imidization with an itaconic anhydride, and the substance is 2- Amino-4-fluorobenzoic acid, 2-amino-5-fluorobenzoic acid, 2-amino-6-fluorobenzoic acid, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 2-amino- 4,4,4-trifluorobutyl acid, 3-amino-2- (trifluoromethyl) benzoic acid, 4- (amidomethyl) benzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5 -Methylbenzoic acid, 3-amino-2-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid , 6-amino-2-naphtho acid, 3-amino-2-naphtho acid, 2-aminonitonic acid, 2-amino-2-norborancarboxylic acid, 3-aminophthalic acid, 3-amino -1-propanesulfonic acid, 3-aminopropylforce Acid, 3-aminopyrazine-2-carboxylic acid, 3-amino-4-pyrazolecarboxylic acid, 3-aminosalicylic acid, 2-amino-4thiazole acetic acid, 2-aminotoluene-5-sulfonic acid , 4-aminotoluene-3sulfonic acid, 4-amino-3,5,6-trichloropicolinic acid, 11-aminoundecanoic acid, and the like.

In addition, 1,3-diketone materials corresponding to R2 and R3, R4 and R5, which may form a complex with europium ions, are 1,1,1,3,5,5,5-heptafluoropentane-2. , 4-dione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 3,5-heptanedione, 1,1,1,2 , 2-pentafluoro-6,6-dimethyl-3,5-heptanedione, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione , 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluor-2,4-pentanedione, 3-chloro-2,4-pentanedione , 2,4-pentanedione, 3-ethyl-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2 , 3,3,7,7,8,8,9,9,9, -tetradecafluoro-4,6-nonanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione , 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione, 1-senoyltrifluoroacetone, dibenzoylmethane, decafluorobenzoylmethane, Pentafluorobenzoylmethane, 1-benzoylacetone, 1-pentafluorobenzoylacetone, 1-benzoyl Trifluoroacetone, acetylacetone, dinaphthoylmethane.

As an acrylic monomer to copolymerize with this monomer, fluorine or / and chlorine-containing alcohols capable of inducing nucleophilic reactions are reacted with acrylic acid and methacrylic acid to prepare monomers, and esterified fluorine-containing and chlorine-containing acids. An exchange reaction was performed to prepare monomers based on fluorine or / and chlorine-containing acetates. The copolymers were synthesized by copolymerizing the monomers containing the europium complexes respectively, and the copolymers of two or more kinds of fluorine or / and chlorine-containing monomers were obtained to measure their physical properties.

Homopolymers prepared from the above reactions and copolymers of respective copolymers with other fluorine and / or chlorine-containing monomers can be applied as polymer optical amplification materials, and the polymers and copolymers may be The radical initiator, fluorine and / or chlorine-containing radical initiators at temperatures can be used and dissolved in a solvent or prepared via an extruder. The copolymerization ratio at the time of preparing the copolymer was prepared in a ratio of 0.01% to 99%, and the copolymer may be prepared even by combining two or more types of monomers. The molecular weight of the polymer obtained was 5,000 g / mol to 200,000 g / mol and generally 20,000 g / mol to 100,000 g / mol were obtained.

As the monomer to cause copolymerization with the monomer thus prepared, acrylic and methacrylic monomers can be prepared by introducing fluorine or / and chlorine-containing alcohol into the side chain of the polymer, and fluorine or / and chlorine-containing alcohol is fumaric. The monomer can be prepared by reaction with an acid. Substances such as alcohol, which can cause nucleophilic reactions, can be used as follows. Trifluoroethanol, difluoroethanol, hexafluoroflopanol, heptafluorobutanol, heptafluoropentanol, hexafluoroisopropanol, methyltrifluorobutanol, octafluoropentanol, perfluorodecanol , 2,2-difluoroethanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, 2,2,3,4,4,4-heptafluorobutan-1-ol, hexafluoroa Isopropanol, hexafluoro-2-methylisopropanol, 2-methyl-4,4,4-trifluorobutanol, 1H, 1H, 5H-octafluoro-1-pentanol, perfluororotarybutanol, 1H, 1H, 2H-perfluorodecanol, 1H, 1H-perfluoro-1-heptanol, 1H, 1H-heptafluoro-1-butanol, 2,2,3,3-tetrafluoro-1-propanol , 2,2,2-trifluoroethanol, 1,1,1-trifluoro-2-octanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,2 , 2-pentafluoro-3-propanol, 2-fluoroethanol, 1,1,1,3,3,3-hexafluoro-2-prop Panol, 1H, 1H, 3H-tetrafluoro-1-propanol, 3,3,3-trifluoropropan-1-ol, 1,1,1-trifluoro-2-propanol, 2,2,3 , 3,4,4,4-heptafluoro-1-butanol, 2,2,3,3-tetrafluorocyclobutanol, 2,2,3,4,4,4, -hexafluoro-1- Butanol, hexafluoro-2-methylisopropanol, 4,4,4-trifluorobu-2-en-1-ol, 4,4,4-trifluoro-1-butanol, 2-trifluoro Methyl-2-propanol, 1H, 1H-perfluoropentan-1-ol, 4,4,4-trifluoro-3- (trifluoromethyl) butanol, 4,4,5,5,5-penta Fluoropentanol, 2-methyl-4,4,4-trifluorobutanol, pentafluorophenol, 2,3,5,6-tetrafluorophenol, 2,3,4-trifluorophenol, 2,3,5- Trifluorophenol, 2,3,6-trifluorophenol, 2,4,5-trifluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2.3-difluorophenol , 2.4-difluorophenol, 2.5-difluoro Rophenol, 2.6-difluorophenol, 3.4-difluorophenol, 3.5-difluorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,3-difluoro- 4- (trifluoromethyl) phenol, 3,4-difluoro-5- (trifluoromethyl) phenol, 2,3,4,5,6-pentafluorobenzyl alcohol, 2-fluoro-3 -(Trifluoromethyl) phenol, 2-fluoro-5- (trifluoromethyl) phenol, 2-fluoro-6- (trifluoromethyl) phenol, 3-fluoro-4- (trifluoro) Methyl) phenol, 3-fluoro-5- (trifluoromethyl) phenol, 4-fluoro-2- (trifluoromethyl) phenol, 4-fluoro-3- (trifluoromethyl) phenol, 5 -Fluoro-2- (trifluoromethyl) phenol, 2,3,5,6-tetrafluorobenzyl alcohol, 1H, 1H, 7H-dodecafluoro-1-heptanol, 1,1,1, 3,3,3-hexafluoro-2-propanol, 1,1,1-trichloroethanol, 2,2,2-trichloroethanol, 1,1,1-trichloro 2-methyl 2-propane Ol, 1-chloro-7-heptanol, 2,2-dichloroethanol, 2-chloroethanol, 1,1,1,2,2,3,3-heptachloroflophan, 4,4-dichloro-4- Fluoro-1-butanol, 2,6-dichloro-4-fluorophenol, 2-chloro-4-fluorophenol, 2-chloro-5-fluorophenol, 3-chloro-4-fluorophenol, 4-chloro-3 Fluorophenol or mixtures thereof may also be used.

In addition, fluorine or / and chlorine-containing acids can be produced by the transesterification of new types of monomers. The fluorine or / and chlorine-containing acid compounds can be used as fluoroacetic acid, chloroacetic acid, and difluoro. Furnace acetic acid, dichloro acetic acid, trifluoro acetic acid, trichloro acetic acid, perchloro acetic acid, perfluoro acetic acid, perfluoropropionic acid, perfluoro butyric acid, perchlorobutyl acid, perfluoro valeric acid, perfluorocarboxylic acid Roroic acid, perfluoro-normal-heptanoic acid, perfluorocaprylic acid, perfluoroglutaric acid, chloroplatinic acid, trifluorobutyl acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoro Roheptanoic acid, perfluorooctanoic acid, perfluoroononanic acid, perfluorodecanoic acid, perfluorododecanoic acid, perfluorocebacic acid, 3H-decafluorodecanoic acid, 6-fluorohexanoic acid, 4 , 4,5,5,6,6,6- Tafluorohexanoic acid, 5,5,5-trifluorobaleric acid, 2H, 2H-heptafluorovaleric acid, 5H-octafluorovaleric acid, 3H-octafluorovaleric acid, 4-aryl-2, 3,5,6-tetrafluorobenzoic acid, 2-amino-4-fluorobenzoic acid, 2-amino-5-fluorobenzoic acid, 2-amino-6-fluorobenzoic acid, 4-amino-2,3, 5,6-tetrafluorobenzoic acid, 2-amino-4,4,4-trifluorobutyl acid, 3-amino-2- (trifluoromethyl) benzoic acid, 2,4-bis (trifluoromethyl) Benzoic acid, 2,5-bis (trifluoromethyl) benzoic acid, 2,6-bis (trifluoromethyl) benzoic acid, 3,5-bis (trifluoromethyl) benzoic acid, 2,2-bis (trifluoro Methyl) -2-hydrate acetic acid, 2,4-bis (trifluoromethyl) phenylacetic acid, 3,5-bis (trifluoromethyl) phenylacetic acid, 2,2-bis (trifluoromethyl) propionic acid, 4-Buromo-2-chloro-5-fluorobenzoic acid, 3-Buromo-4-chloropentafluorobutyl acid, 4-chlorobenzoic acid, 2-chlorocinnamic acid, 4-chlorocinnamic acid, 2-chloro-4,5-difluorobenzoic acid, 4-chloro-4,5-difluorobenzoic acid, 2-chloro-4-fluorobenzoic acid, 2- Chloro-5-fluorobenzoic acid, 2-chloro-6-fluorobenzoic acid, 3-chloro-2-fluorobenzoic acid, 3-chloro-4-fluorobenzoic acid, 4-chloro-2-fluorobenzoic acid, 2- Chloro-6-fluorophenylacetic acid, 6-chloronicotinic acid, 2-chlorophenylacetic acid, 3-chlorophenylacetic acid, 4-chlorophenylacetic acid, 2-chloro-3- (trifluoromethyl) benzoic acid, 2-chloro- 5- (trifluoromethyl) benzoic acid and the like. In addition, fluorine or / and chlorine-containing amines may be imidized with itaconic anhydride to form monomers used in the copolymerization reaction. The fluorine or / and chlorine-containing amines used may include 2,2,3,3, 3-pentafluoropropylamine, 2,3,4,5-tetrafluoroaniline, 2,3,4,6-tetrafluoroaniline, 2,3,5,6-tetrafluoroaniline, 4- ( 1,1,2,2, -tetrafluoroethoxy) aniline, 2,2,2-trifluoroacetamide, 2,3,4-trifluoroaniline, 2,3,5-trifluoroaniline , 2,3,6-trifluoroaniline, 2,4,5-trifluoroaniline, 3,4,5-trifluoroaniline, 2,3,4-trifluorobenzamide, 2,3, 5-trifluorobenzamide, 2,3,6-trifluorobenzamide, 2,4,5-trifluorobenzamide, 2,4,6-trifluorobenzamide, 3,4,5- Trifluorobenzamide, 2,3,4-trifluorobenzyla , 2,3,5-trifluorobenzylamine, 2,3,6-trifluorobenzylamine, 2,4,5-trifluorobenzylamine, 2,4,6-trifluorobenzylamine, 3 , 4,5-trifluorobenzylamine, 2,2,2-triethylamine, 2- (trifluoromethoxy) aniline, 3- (trifluoromethoxy) aniline, 4- (trifluoromethoxy) aniline , 2- (trifluoromethoxy) benzamide, 3- (trifluoromethoxy) benzamide, 4- (trifluoromethoxy) benzamide, 2- (trifluoromethoxy) benzylamine, 3- (trifluoro Romethoxy) benzylamine, 4- (trifluoromethoxy) benzylamine, 2- (trifluoromethyl) benzamide, 3- (trifluoromethyl) benzamide, 4- (trifluoromethyl) benzamide, 2- (trifluoromethyl) benzylamine, 3- (trifluoromethyl) benzylamine, 4- (trifluoromethyl) benzylamine, 2- (trifluoromethyl) phenylaceta De, 3-chloroaniline, 4-chloroaniline, 2-chloro-4-fluoroaniline, 2-chloro-5-fluoroaniline, 2-chloro-6-fluoroaniline, 3-chloro-2-fluoro Aniline, 3-chloro-4-fluoroaniline, 4-chloro-2-fluoroaniline, 5-chloro-2-fluoroaniline, 2-chloro-4-fluorobenzamide, 2-chloro-6-fluoro Lovenzamide, 3-chloro-4-fluorobenzamide, 2-chloro-4-fluorobenzylamine, 2-chloro-6-fluorobenzylamine, 3-chloro-4-fluorobenzylamine, 2- Chloro-4-fluoro-5-methoxyaniline, 5-chloro-4-fluoro-2-nitroaniline, 2-chloro-4-methoxyaniline, 2-chloro-5- (trifluoro) benzylamine 4-chloro-3- (trifluoro) benzylamine, 2,6-dichloro-4- (trifluoromethoxy) aniline, 2,6-dichloro-4- (trifluoromethyl) aniline, 2, 3-difluoroaniline, 2,4-difluoroaniline, 2,5-difluoroa Lean, 2,6-difluoroaniline, 3,4-difluoroaniline, 3,5-difluoroaniline, 2,3-difluorobenzylamine, 2,4-difluorobenzylamine, 2 , 5-difluorobenzylamine, 2,6-difluorobenzylamine, 3,4-difluorobenzylamine, 3,5-difluorobenzylamine, 2-fluoroaniline, 3-fluoroaniline , 4-fluoroaniline, 2,3,4,5,6-pentafluoroaniline, and the like.

In addition, fluorine or / and chlorine-containing monomers to copolymerize with the prepared complex monomers include acrylate, methyl methacrylate, styrene, vinyl fluoride, arylpentafluorobenzene, aryl perfulo-normal-nonanoate, Arylperfluoropentanoate, 4-aryl-2,3,5,6-tetrafluorobenzoic acid, aryltrifluoroacetate, 4-buromo-3-chloro-3,4,4-trifluorobutene , 2-Buromo-3,4-dichloro-3,4,4-trifluorobutene, 2-Buromo-3,4,4,5,5,5-hexafluoro3-trifluoromethyl- 1-pentene, 1-buromo, 1- (perfluoro-normal-butyl) ethylene, 4-buromo-3,3,4,4-tetrafluorobutene-1, 3-buromo-1,1 , 2-trifluoro1,3-butadiene, 2-buromo-3,3,3-trifluoropropene, 2-chloropentafluoro-1,3-butadiene, 2-chlorostyrene, 4-chloro Styrene, 2,3-dichloro-1-propene, 1,4-divinyl perfluorobutane, 1,6-divinyl perflu Robutane, 1H, 1H, 7H-dodecafluoroheptylacrylate, 1H, 1H, 1H-eicosafluoroundecyl acrylate, 2-fluoroethyl acrylate, 3-fluoropropene, 2-fluoro Rostyrene, 3-fluorostyrene, 4-fluorostyrene, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, heptafluoro-3,3-bis (trifluoromethyl) -1-hexene , 1H, 1H-heptafluorobutyl acrylate, 1H, 1H, 2H-heptafluoropent-1-ene, 2,2,3,4,4,4-hexafluorobutyl acrylate, hexafluoroprop Pen, 3,4,4,5,5,5 = hexafluoro-3- (trifluoromethyl) -1-pentene, 1H, 1H-pentadecafluorooctyl acrylate, 1,1,3,3 , 3-pentafluoropropene-1,2,3,4,5,6-pentafluorostyrene, 1H, 1H, 2H-perfluoro-1-decene, 1H, 1H, 2H-perfluoro- 1-dodecane, 2,2,2-trifluoroethyl acrylate, 3,3,3-trifluoropropene, acrylate, methacrylate, Tiles and the like alkylene.

The new polymers and copolymers prepared from the synthesized monomers can obtain relatively high glass transition temperature, excellent amplification and improved mechanical properties compared to the conventional polymer optical amplified material.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are merely to illustrate the present invention, and the scope of the present invention is not limited by the present examples.

Example 1

In a 250 ml round bottom flask equipped with a condenser and agitator, 11.2 g of itaconic anhydride, 13.7 g of 4-aminobenzoic acid and 50 ml of dimethylformamide are added. After stirring the mixed solution for about 30 minutes, pour cold water and stir for another 10 minutes. The precipitate obtained is filtered off using a filter apparatus and then dried in a reduced pressure furnace for 24 hours. 10.0 g of dried precipitate, 8 g of acetic anhydride, and 5.6 g of sodium acetate were added to a round bottom flask, followed by stirring at 60 ° C. for 30 minutes. The mixed solution thus obtained is slowly dropped in cold water to form a precipitate, washed with distilled water several times and crystallized from a mixed solution of methanol and water to obtain pure N- (4-carboxyphenyl) itacoimide.

Example 2

20 ml of tetrahydrofuran was placed in a 250 ml round bottom flask equipped with a condenser and a stirrer, 3 g of europium chloride was placed, and 100 ml of benzene and 2-propanol were added at a ratio of 1: 1. The mixed solution was stirred under reflux and refluxed again for 4 hours while dropping 10 g of lithium isopropoxide dissolved in 10 ml tetrahydrofuran. 3 g of dibenzoylmethane dissolved in 10 ml tetrahydrofuran is dropped into the mixed solution and refluxed again for 2.5 hours. Thus, 2 g of N- (4-carboxyphenyl) itacoimide synthesized in Example 1 was dissolved in 10 ml of tetrahydrofuran and dropped to reflux with stirring for 3.5 hours. 1 g of 1,10-phenanthroline was dissolved in 10 ml of tetrahydrofuran, and the mixture was refluxed for 2 hours, and then cooled to room temperature. After removing the tetrahydrofuran in the mixed solution by using a vacuum distillation and dissolving the obtained solid in benzene, by using a filter device to remove the solid in the mixed solution, the solution is taken. The solution thus obtained is precipitated in a cyclohexane solution, and then a monomer is obtained using a filter device. The monomer thus obtained is dried in a vacuum furnace for 24 hours.

Example 3

20 ml of tetrahydrofuran was placed in a 250 ml round bottom flask equipped with a condenser and a stirrer, 3 g of europium chloride was placed, and 100 ml of benzene and 2-propanol were added at a ratio of 1: 1. The mixed solution was stirred under reflux and refluxed again for 4 hours while dropping 10 g of lithium isopropoxide dissolved in 10 ml tetrahydrofuran. 1.4 g of 1,1,1,5,5,5-hexafluoro-2,4-pentadiene dissolved in 10 ml tetrahydrofuran was added to the mixed solution and refluxed again for 2.5 hours. Thus, 2 g of N- (4-carboxyphenyl) itacoimide synthesized in Example 1 was dissolved in 10 ml of tetrahydrofuran and dropped to reflux with stirring for 3.5 hours. 1 g of 1,10-phenanthroline was dissolved in 10 ml of tetrahydrofuran, and the mixture was refluxed for 2 hours, and then cooled to room temperature. After removing the tetrahydrofuran in the mixed solution by using a vacuum distillation and dissolving the obtained solid in benzene, by using a filter device to remove the solid in the mixed solution, the solution is taken. The solution thus obtained is precipitated in a cyclohexane solution, and then a monomer is obtained using a filter device. The monomer thus obtained is dried in a vacuum furnace for 24 hours.

Example 4

Into a 250 ml round bottom flask equipped with a condenser and a stirrer, 18.032 g of pentafluorophenol, 7.884 g of pyridine, and 40 ml of tetrachloromethane were kept at 0 ° C. 10 ml of chlorinated methacrylic acid was dropped into the mixed solution at 0 ° C. for 1 hour, and then stirred at 25 ° C. for 24 hours. The mixed solution was removed using a strainer to remove the precipitate, and then stirred again at 140 ° C. for 8 hours to remove tetrachloromethane in the mixed solution. The solution thus obtained is distilled at 280 DEG C using a low pressure distillation apparatus to obtain a transparent monomer.

Example 5

30 g of pentachlorophenol, 7.884 g of pyridine, and 40 ml of tetrachloromethane were added to a 250 ml round bottom flask equipped with a condenser and a stirrer and maintained at 0 ° C. 10 ml of chlorinated methacrylic acid was dropped into the mixed solution at 0 ° C. for 1 hour, and then stirred at 25 ° C. for 24 hours. The mixed solution was removed using a strainer to remove the precipitate, and then stirred again at 140 ° C. for 8 hours to remove tetrachloromethane in the mixed solution. The solution thus obtained is removed using a low pressure distillation apparatus to remove unreacted substances to obtain a solid aggregate, which is then purified using a sublimation apparatus to obtain white crystals.

Example 6

50 g of pentafluorophenol, 8.5 ml of triethylamine, and 200 ml of tetrachloromethane were added to a 250 ml round bottom flask equipped with a condenser and a stirrer and maintained at 0 ° C. 10 ml of acrylic acid chloride was dropped into the mixed solution at 0 ° C. for 1 hour, followed by stirring at 25 ° C. for 24 hours. The mixed solution was removed using a strainer and the tetrachloromethane in the mixed solution was removed by stirring again at 140 ° C. for 8 hours. Water was added to the resulting solution to remove unreacted acrylic acid, followed by dichloromethane. Extraction with methane separates the organic layer. After dichloromethane is removed using this vacuum distillation apparatus to obtain a solid aggregate, the organic layer is purified using a sublimation apparatus to obtain crystals.

Example 7

In a 250 ml round bottom flask equipped with a condenser and a stirrer, 13.3 g of pentachlorophenol, 8.5 ml of triethylamine, and 100 ml of dried benzene were maintained at 25 ° C. 5.0 g of acrylic acid chloride is added to the mixed solution at 25 ° C. for 1 hour with stirring. The temperature of the mixed solution is gradually raised to room temperature while stirring while maintaining 0 ° C for 1 hour. The mixed solution thus obtained is removed using a strainer, and then water is added to remove unreacted acrylic acid. The organic layer is separated using a fractionation extractor, and extracted three times with water. This organic layer is dried over sodium sulfate for 24 hours. The organic layer is then removed using a reduced pressure distillation apparatus to give a brown solid. This solid is recrystallized in ethyl ether solution.

Example 8

Place 42.4 g pentafluorobenzoic acid and 100 g vinyl acetate in a 250 ml round bottom flask equipped with a condenser, a stirrer and a thermometer, and slowly drop 1.71 g of mercury sulfate. The mixed solution is refluxed for 3 hours with stirring. The solution is cooled to 0 ° C. and then diluted with petroleum ether. Sodium acetate is added to remove unreacted acid in the mixed solution, and then extracted using a separatory funnel. After concentration under reduced pressure to remove unreacted vinyl acetate and petroleum ether, the remaining material in the flask is dissolved in ether. After the obtained solution was washed with a sodium carbonate solution, the obtained organic layer was distilled off under reduced pressure to obtain a transparent liquid.

Example 9

Place 42.4 g of trifluoroacetic acid and 100 g of vinyl acetate in a 250 ml round bottom flask equipped with a condenser, agitator, and thermometer, and slowly drop 1.71 g of mercury sulfate. The mixed solution is refluxed for 3 hours with stirring. The solution is cooled to 0 ° C. and then diluted with petroleum ether. Sodium acetate is added to remove unreacted acid in the mixed solution, and then extracted using a separatory funnel. After concentration under reduced pressure to remove unreacted vinyl acetate and petroleum ether, the remaining material in the flask is dissolved in ether. After the obtained solution was washed with a sodium carbonate solution, the obtained organic layer was distilled off under reduced pressure to obtain a monomer.

Example 10)

Place 42.4 g of trichloroacetic acid and 100 g of vinyl acetate in a 250 ml round bottom flask equipped with a condenser, a stirrer and a thermometer, and slowly drop 1.71 g of mercury sulfate. The mixed solution is refluxed for 3 hours with stirring. The solution is cooled to 0 ° C. and then diluted with petroleum ether. Sodium acetate is added to remove unreacted acid in the mixed solution, and then extracted using a separatory funnel. After concentration under reduced pressure to remove unreacted vinyl acetate and petroleum ether, the remaining material in the flask is dissolved in ether. After the obtained solution was washed with a sodium carbonate solution, the obtained organic layer was distilled off under reduced pressure to obtain a transparent monomer.

Example 11

In a flask equipped with a stirrer and a condenser, 500 ml of dichloroethanol (9.55 g, 2-g fumaric acid, 0.075 g 4-methylaminopyridine, 9.922 g 1,3-dimethylaminopropyl-3-ethylcarbodiimide) It is dissolved in methane and reacted at 23 ° C. for 12 hours with stirring. 1000 ml of water is added to the reaction solution, and the mixed solution is extracted three times using 1000 ml of dichloromethane. The resulting solution is combined, dried over sodium sulfide and condensed until the solution is 1000 ml. The above solution is extracted with 900 ml of saturated sodium carbonate solution and dried again with sodium sulfide. The resulting solution was condensed and then precipitated by addition of low temperature dichloromethane at -20 ° C to obtain crystals and then dried in a vacuum furnace.

Example 12)

In a flask equipped with a stirrer and a condenser, 9.55 g of 2,2,2-trifluoroethanol and 2 g of fumaric acid and 0.075 g of 4-methylaminopyridine, 9.922 g of 1,3-dimethylaminopropyl-3-ethylcarbodie The mead is dissolved in 500 ml of dichloromethane and reacted with stirring at 23 ° C. for 12 hours. 1000 ml of water is added to the reaction solution, and the mixed solution thus obtained is extracted three times with 1000 ml of dichloromethane. The resulting solution is combined, dried over sodium sulfide and condensed until the solution is 1000 ml. The above solution is extracted with 900 ml of saturated sodium carbonate solution and dried again with sodium sulfide. The resulting solution is condensed and then precipitated by addition of low temperature dichloromethane at −20 ° C. to obtain a monomer.

Example 13

In a flask equipped with a stirrer and a condenser, 500 ml of dichloroethyl (9.55 g pentafluoroethyl alcohol, 2 g fumaric acid, 0.075 g 4-methylaminopyridine, 9.922 g 1,3-dimethylaminopropyl-3-ethylcarbodiimide) It is dissolved in methane and reacted with stirring at 23 ° C. for 12 hours. 1000 ml of water is added to the reaction solution, and the mixed solution thus obtained is extracted three times with 1000 ml of dichloromethane. The resulting solution is combined, dried over sodium sulfide and condensed until the solution is 1000 ml. The above solution is extracted with 900 ml of saturated sodium carbonate solution and dried again with sodium sulfide. The resulting solution is condensed and then precipitated by addition of low temperature dichloromethane at −20 ° C. to obtain a monomer.

Example 14

250 ml of diethyl ether was placed in a round bottom flask equipped with a stirrer and a condenser, and 73.75 g of chloral and 39.25 g of acetyl chloride and 39.255 g of metal zinc were placed and refluxed for 24 hours with stirring. Diethyl ether is removed by distillation of the mixed solution, and distilled under reduced pressure to obtain 2,2-dichlorovinylacetate. 7.6 g of 2,2-dichlorovinylacetate thus obtained and 16.05 g of tributyl tin methoxide were mixed and heated with stirring at 70 ° C. for 30 minutes. 11.53 g of pentafluorobenzoyl chloride is slowly added to the mixed solution. The reaction product in this mixed solution is obtained by recrystallization from cold ethanol.

Example 15)

250 ml of diethyl ether was placed in a round bottom flask equipped with a stirrer and a condenser, and 73.75 g of chloral and 39.25 g of acetyl chloride and 39.255 g of metal zinc were placed and refluxed for 24 hours with stirring. Diethyl ether is removed by distillation of the mixed solution, and distilled under reduced pressure to obtain 2,2-dichlorovinylacetate. 7.6 g of 2,2-dichlorovinylacetate thus obtained and 16.05 g of tributyl tin methoxide were mixed and heated with stirring at 70 ° C. for 30 minutes. 11.53 g of pentachlorobenzoyl chloride is slowly added to the mixed solution. The reaction product in this mixed solution is obtained by recrystallization from cold ethanol.

Example 16

250 ml of diethyl ether was placed in a round bottom flask equipped with a stirrer and a condenser, and 73.75 g of chloral and 39.25 g of acetyl chloride and 39.255 g of metal zinc were placed and refluxed for 24 hours with stirring. Diethyl ether is removed by distillation of the mixed solution, and distilled under reduced pressure to obtain 2,2-dichlorovinylacetate. 7.6 g of 2,2-dichlorovinylacetate thus obtained and 16.05 g of tributyl tin methoxide were mixed and heated with stirring at 70 ° C. for 30 minutes. 11.53 g of trifluoroacetyl chloride is slowly added to the mixed solution. The reaction product in this mixed solution is obtained by recrystallization from cold ethanol.

Example 17)

250 ml of diethyl ether was placed in a round bottom flask equipped with a stirrer and a condenser, and 73.75 g of chloral and 39.25 g of acetyl chloride and 39.255 g of metal zinc were placed and refluxed for 24 hours with stirring. Diethyl ether is removed by distillation of the mixed solution, and distilled under reduced pressure to obtain 2,2-dichlorovinylacetate. 7.6 g of 2,2-dichlorovinylacetate thus obtained and 16.05 g of tributyl tin methoxide were mixed and heated with stirring at 70 ° C. for 30 minutes. Slowly add 11.53 g of trichloroacetyl chloride to the mixed solution. The reaction product in this mixed solution is obtained by recrystallization from cold ethanol.

In addition, a general method for preparing a copolymer of europium itacoiimide complex monomer according to the present invention is to add at least two monomers to the tetrahydrofuran solution having a copolymerization range of 1 to 99% to the above-mentioned initiator or fluorine or And reaction with 1 to 96 hours at a temperature of 40 to 90 ° C using a chlorine-containing initiator, followed by precipitation in methanol.

Example 18

1 g of the monomer obtained in Example 2 was polymerized at 80 ° C. for 60 hours using an initiator AIBN in an 80 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 5000 / mol)

Example 19

1 g of the monomer obtained in Example 3 was polymerized in an 80 mL solution of tetrahydrofuran using an initiator AIBN at 60 ° C. for 60 hours and then precipitated in methanol to obtain a polymer. (Mw = 7000 / mol)

Example 20

1 g of the monomer obtained in Example 2 and 10 g of the monomer obtained in Example 3 were polymerized at 90 ° C. for 48 hours using an initiator BPO in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 9000 / mol )

Example 21)

1 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 4 were polymerized at 80 ° C. for 72 hours using an initiator tertiary-butyl peroxide in an 80 mL solution of cyclohexane, and then precipitated in methanol to obtain a copolymer. (Mw = 200,000 / mol)

Example 22)

1 g of the monomer obtained in Example 2 and 5 g of the monomer obtained in Example 5 were polymerized at 50 ° C. for 42 hours using an initiator lauryl peroxide in an 80 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a copolymer. Mw = 50,000 / mol)

Example 23)

0.5 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 6 were polymerized at 75 ° C. for 16 hours using an initiator BPO in an 80 mL solution of 2-butanone, and then precipitated in methanol to obtain a copolymer. = 20,000 / mol)

Example 24)

1 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 7 were polymerized at 100 ° C. for 36 hours using an initiator tertiary-butylhydroperoxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 100,000 / mol)

Example 25)

0.5 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 8 were polymerized at 80 ° C. for 64 hours using an initiator perfluoropropionyl peroxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 50,000 / mol)

Example 26)

0.3 g of the monomer obtained in Example 2 and 5 g of the monomer obtained in Example 9 were polymerized at 60 ° C. for 60 hours using an initiator AIBN in an 80 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a copolymer. 20,000 / mol)

Example 27)

5 g of the monomer obtained in Example 2 and 8 g of the monomer obtained in Example 10 were polymerized at 50 ° C. for 48 hours using an initiator azodicarbonamide in an 80 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a copolymer. Mw = 35,000 / mol)

Example 28)

3 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 11 were polymerized at 70 ° C. for 72 hours using an initiator tertiary butyl peroxy benzoate in an 80 mL solution of 2-butanone, and then precipitated in methanol to obtain a copolymer. (Mw = 90,000 / mol)

Example 29)

5 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 12 were polymerized at 65 ° C. for 24 hours using an initiator azodicarbonamide in an 80 mL solution of cyclohexane, and then precipitated in methanol to obtain a copolymer. = 450,000 / mol)

Example 30)

1 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 13 were polymerized at 100 ° C. for 16 hours using an initiator tertiary-butylhydroperoxide in an 80 mL solution of monochlorobenzene, and then precipitated in methanol. (Mw = 28,000 / mol)

Example 31)

1 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 14 were polymerized at 90 ° C. for 72 hours using an initiator 5-chloro-2-theonyl peroxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 20,000 / mol)

Example 32

1 g of the monomer obtained in Example 2 and 0.5 g of the monomer obtained in Example 15 were polymerized at 90 ° C. for 45 hours using an initiator BPO in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 15,000 / mol)

Example 33)

0.1 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 16 were polymerized at 80 ° C. for 56 hours using an initiator tertiary-butyl peroxide in an 80 mL solution of 2-butanone, and then precipitated in methanol to obtain a copolymer. (Mw = 50,000 / mol)

Example 34)

1 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 4 were polymerized at 80 ° C. for 28 hours using an initiator perfluoropropionyl peroxide in an 80 mL solution of 2-butanone, and then precipitated in methanol. (Mw = 500,000 / mol)

Example 35)

1 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 5 were polymerized at 90 ° C. for 96 hours using an initiator BPO in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 350,000 / mol )

Example 36)

1 g of the monomer obtained in Example 3 and 0.5 g of the monomer obtained in Example 5 were polymerized at 65 ° C. for 60 hours using an initiator lauryl peroxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. = 30,000 / mol)

Example 37)

1 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 7 were polymerized for 48 hours at 60 ° C. using an initiator AIBN in an 80 mL solution of dimethylformamide, and then precipitated in methanol to obtain a copolymer. 40,000 / mol)

Example 38

1 g of the monomer obtained in Example 3 and 2 g of the monomer obtained in Example 8 were polymerized at 75 ° C. for 24 hours using an initiator 5-chloro-2-theonyl peroxide in an 80 mL solution of cyclohexane, and then precipitated in methanol to obtain air. Obtain coalescence (Mw = 100,000 / mol)

Example 39)

2 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 9 were polymerized at 65 ° C. for 10 hours using initiator AIBN in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 50,000 / mol )

Example 40

1.5 g of the monomer obtained in Example 3 and 2 g of the monomer obtained in Example 10 were polymerized at 50 ° C. for 72 hours using an initiator azodicarbonamide in an 80 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a copolymer. (Mw = 40,000 / mol)

Example 41)

2.5 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 11 were polymerized at 80 ° C. for 48 hours using an initiator tertiary-butylperoxybenzoate in a 2-butanone 80 mL solution, and then precipitated in methanol. Obtain a copolymer (Mw = 60,000 / mol)

Example 42)

1.5 g of the monomer obtained in Example 3 and 2 g of the monomer obtained in Example 12 were polymerized at 95 ° C. for 36 hours using an initiator perfluoropropionyl peroxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 70,000 / mol)

Example 43)

1 g of the monomer obtained in Example 3 and 1.5 g of the monomer obtained in Example 13 were polymerized at 90 ° C. for 12 hours using an initiator BPO in an 80 mL solution of dimethylformamide, and then precipitated in methanol to obtain a copolymer. = 110,000 / mol)

Example 44

2 g of the monomer obtained in Example 3 and 2.5 g of the monomer obtained in Example 14 were polymerized at 55 ° C. for 48 hours using an initiator laruryl peroxide in an 80 mL solution of cyclohexane, and then precipitated in methanol to obtain a copolymer. Mw = 70,000 / mol)

Example 45)

1 g of the monomer obtained in Example 3 and 1.4 g of the monomer obtained in Example 15 were polymerized at 80 ° C. for 60 hours using an initiator AIBN in an 80 mL solution of benzene, and then precipitated in methanol to obtain a copolymer. (Mw = 40,000 / mol)

Example 46

2 g of the monomer obtained in Example 3 and 1 g of the monomer obtained in Example 16 were polymerized at 90 ° C. for 96 hours using an initiator tertiary-butylhydroperoxide in an 80 mL solution of toluene, and then precipitated in methanol to obtain a copolymer. (Mw = 140,000 / mol)

Example 47)

In Example 2, a polymer of 1.5 g of monomer and 2 g of 2-chlorostyrene was polymerized for 42 hours at 50 ° C. using an initiator azodicarbonamide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 50,000 / mol)

Example 48)

1.0 g of the monomer obtained in Example 2 and 2 g of vinyltrifluoroacetate were polymerized at 110 ° C. for 7 hours using an initiator 5-chloro-2-theonyl peroxide in a 60 mL solution of monochlorobenzene, and then precipitated in methanol. Obtain a polymer. (Mw = 20,000 / mol)

Example 49)

1 g of the monomer acrylate and 2 g of vinyl fluoride obtained in Example 2 were polymerized at 85 ° C. for 36 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 80,000 / mol)

Example 50)

1.5 g of the monomer acrylate and 1.5 g of 4-chlorostyrene obtained in Example 2 were polymerized at 60 ° C. for 24 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. 100,000 / mol)

Example 51)

2.5 g of the monomer obtained in Example 2 and 2 g of 2,3-dichloro-1-propene were polymerized at 70 ° C. for 52 hours using an initiator tertiary-butyl peroxide in a 60 mL solution of 2-butanone. Precipitation to give the polymer (Mw = 90,000 / mol).

Example 52)

In Example 3, 1 g of monomer and 1.5 g of 2-chlorostyrene were polymerized at 85 ° C. for 96 hours using an initiator lauryl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 40,000 / mol )

Example 53)

2 g of the monomer obtained in Example 3 and 2.5 g of vinyltrifluoroacetate were polymerized at 90 DEG C for 24 hours using an initiator perfluoropropionyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. Mw = 80,000 / mol)

Example 54)

1 g of the monomer acrylate and 2 g of vinyl fluoride obtained in Example 3 were polymerized at 60 ° C. for 60 hours using an initiator BPO in a 60 mL solution of 2-butanone, and then precipitated in methanol to obtain a polymer. (Mw = 60,000 / mol)

Example 55)

1 g of the monomer acrylate and 2 g of 4-chlorostyrene obtained in Example 3 were polymerized at 60 ° C. for 36 hours using an initiator AIBN in a 60 mL solution of cyclohexane, followed by precipitation in methanol to obtain a polymer. (Mw = 70,000 / mol )

Example 56)

2 g of the monomer obtained in Example 3 and 1.5 g of 2,3-dichloro-1-propene were polymerized at 50 ° C. for 72 hours using an initiator azodicarbonamide in a 60 mL solution of benzene, and then precipitated in methanol to obtain a polymer. (Mw = 110,000 / mol)

Example 57)

0.5 g of the monomer obtained in Example 1 and 1 g of methyl methacrylate were polymerized at 80 ° C. for 48 hours using an initiator tertiary-butylperoxybenzoate in a 60 mL solution of toluene, followed by precipitation in methanol to obtain a polymer. Mw = 50,000 / mol)

Example 58)

0.5 g of the monomer obtained in Example 2 and 1 g of methyl methacrylate were polymerized at 60 ° C. for 36 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 30,000 / mol )

Example 59)

0.5 g of the monomer obtained in Example 2 and 1 g of styrene were polymerized at 90 ° C. for 18 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 50,000 / mol)

Example 60

0.5 g of the monomer obtained in Example 2 and 1 g of styrene were polymerized at 75 ° C. for 24 hours using an initiator 5-chloro-2-theonyl peroxide in a 60 mL solution of 2-butanone, followed by precipitation in methanol to obtain a polymer. (Mw = 40,000 / mol)

Example 61

0.5 g of the monomer obtained in Example 1 and 1 g of the monomer obtained in Example 5 and 2.5 g of the monomer obtained in Example 6 were polymerized at 60 ° C. for 48 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. To obtain a polymer (Mw = 90,000 / mol).

Example 62)

0.5 g of the monomer obtained in Example 1 and 1 g of the monomer obtained in Example 5 and 2.5 g of the monomer obtained in Example 7 were polymerized at 80 ° C. for 45 hours using an initiator lauryl peroxide in a 60 mL solution of toluene, followed by methanol. Precipitation to give the polymer (Mw = 20,000 / mol).

Example 63)

0.5 g of the monomer obtained in Example 2, 1 g of the monomer obtained in Example 5 and 2.5 g of the monomer obtained in Example 8 were polymerized at 60 ° C. for 60 hours using an initiator AIBN in a 60 mL solution of cyclohexane, and then precipitated in methanol. Obtain a polymer (Mw = 120,000 / mol).

Example 64

0.5 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 6 and 2.5 g of the monomer obtained in Example 8 were polymerized at 90 ° C. for 96 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol. (Mw = 80,000 / mol)

The present invention is to prepare a copolymer of europium-based monomers and polymers for optical amplification materials and copolymers thereof and other fluorine or / and chlorine-containing monomers to obtain improved properties than conventional quartz-based glass optical fiber amplification material, europium complexes By introducing an imide group, the heat resistance was increased more than that of a conventional polymer optical amplifier. In addition, by introducing a rare earth metal ion organic complex into the monomer structure and controlling the polymerization ratio with the monomer forming the optical amplified material support, europium-based polymers and copolymers for optical amplified materials in which the rare earth complex is regularly dispersed in the polymerization support are prepared. Compared with the conventional polymer optical amplification material, the glass transition temperature, excellent amplification and improved mechanical properties were obtained.

The prepared novel polymers and copolymers are expected to have a large economic ripple effect by exhibiting properties to replace the polymer optical amplified materials currently used.

Claims (3)

A novel monomer having a structure represented by the following formula 1, prepared by complexing the above-mentioned itaconic imide with europium. In the above formula, R1 is an amic acid capable of producing a monomer by reacting an amic acid having an acid functional group capable of forming a complex with europium ions and an amine group capable of imidization with an itaconic anhydride, and the substance is 2- Amino-4-fluorobenzoic acid, 2-amino-5-fluorobenzoic acid, 2-amino-6-fluorobenzoic acid, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 2-amino- 4,4,4-trifluorobutyl acid, 3-amino-2- (trifluoromethyl) benzoic acid, 4- (amidomethyl) benzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-5 -Methylbenzoic acid, 3-amino-2-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 2-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid , 6-amino-2-naphtho acid, 3-amino-2-naphtho acid, 2-aminonitonic acid, 2-amino-2-norborancarboxylic acid, 3-aminophthalic acid, 3-amino -1-propanesulfonic acid, 3-aminopropylforce Acid, 3-aminopyrazine-2-carboxylic acid, 3-amino-4-pyrazolecarboxylic acid, 3-aminosalicylic acid, 2-amino-4thiazole acetic acid, 2-aminotoluene-5-sulfonic acid , 4-aminotoluene-3sulfonic acid, 4-amino-3,5,6-trichloropicolinic acid, 11-aminoundecanoic acid, and the like. In addition, 1,3-diketone materials corresponding to R2 and R3, R4 and R5, which may form a complex with europium ions, are 1,1,1,3,5,5,5-heptafluoropentane-2. , 4-dione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 3,5-heptanedione, 1,1,1,2 , 2-pentafluoro-6,6-dimethyl-3,5-heptanedione, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione , 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 1,1,1-trifluor-2,4-pentanedione, 3-chloro-2,4-pentanedione , 2,4-pentanedione, 3-ethyl-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,2,2 , 3,3,7,7,8,8,9,9,9, -tetradecafluoro-4,6-nonanedione, 4,4,4-trifluoro-1-phenyl-1,3-butanedione , 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione, 1-senoyltrifluoroacetone, dibenzoylmethane, decafluorobenzoylmethane, Pentafluorobenzoylmethane, 1-benzoylacetone, 1-pentafluorobenzoylacetone, 1-benzoyl Trifluoroacetone, acetylacetone, dinaphthoylmethane and the like. Copolymers of the monomers according to claim 1 with fluorine and / or chlorine-containing monomers of at least the other fluorine species mentioned above. It is used as the polymer for optical amplification material of Claim 2, The homopolymer and copolymer characterized by the above-mentioned.