KR20030073309A - Fluorinated or/and Chlorinated Itaconic Imide Monomers, their Polymers and Copolymers for Optical Communications - Google Patents

Abstract

PURPOSE: Provided are a homopolymer and a copolymer of itaconic imide monomer containing fluorine and/or chlorine as improved optical communication material. They are used as optical fibers in an automobile, wires in airplane, ship, automobile, medical apparatus, simple measuring instrument, electric instrument, and material for short distance optical transmission. CONSTITUTION: Optical communication material comprises a monomer represented by the formula 1 synthesized by reacting amine containing fluorine and or chlorine with itaconic anhydride, and its homopolymer and copolymer with monomer containing more than two kinds of fluorine and or chlorine. In the formula 1, R is amine containing fluorine and/or chlorine which induces imide reaction.

Description

Fluorinated or / and Chlorinated Itaconic Imide Monomers, their Polymers and Copolymers for Optical Communications

The present invention relates to homopolymers and copolymers prepared using fluorine- and / or chlorine-containing itaconic novel monomers suitable for transmission media for optical communications. Incorporation of fluorine or / and chlorine into the novel itaconic monomer structure results in improved properties that are applicable to optical communications than conventional acrylic polymers.

In general, the polymer as a transmission medium for optical communication should have a high glass transition temperature in order to maintain a stable property in the use environment, and should have a low light absorption rate in the wavelength band in transmitting information to the light. In order to have this function, the molecular structure should have a low hydrogen content, and the method introduced is to replace hydrogen in the monomer structure with atoms having low absorption loss such as fluorine or chlorine. The optical fiber, which is a transmission medium composed of a fluorine or / and chlorine-substituted polymer obtained by the above method, exhibits lower light absorption loss than a polymer composed of hydrogen and carbon bonds when the transmission wavelength of the corresponding region passes. (U.S. Patent No. 6,271,312)

In addition to these properties, the important physical properties required for the optical communication medium include the presence or absence of crystallinity of the polymer. When the wavelength of the corresponding region passes through the optical fiber and the waveguide proceeds, the crystallinity of the polymer becomes a great cause of damaging the optical information of the wavelength. This favors amorphous polymers for ease of use as transmission media for optical communications. Acrylic polymers are generally transparent in the visible range, and the structure of the polymer is amorphous, and is widely used as a transmission medium for optical communication. (US Pat. No. 5,223,593) Acrylic polymers are easy to process and have low light absorption loss in synthetic polymers. However, as a relative disadvantage, glass transition temperature is rather low to use as an optical communication transmission medium, has a high hygroscopicity and a high light absorption loss compared to the conventional glass optical fiber has been studied a lot to improve this. . In order to solve the problems of conventional acrylic polymers as described above, researches on acrylic polymers having excellent transparency and amorphousness have been conducted, but still have high light absorption loss due to transparency, amorphousness, and high hydrogen content in monomer molecules. Indicates. (US Pat. No. 5,760,139) This necessitates the preparation of a new type of acrylic polymer exhibiting excellent mechanical properties suitable for use in optical communication transmission media, and the development of new monomers, Development of new copolymers should be made. In order to improve the problems presented above, in the present patent, a novel monomer was prepared by reacting itaconic anhydride with fluorine or / and chlorine-containing amine. This monomer was copolymerized with a homopolymerized or other fluorine and / or chlorine containing monomer to prepare a new homopolymer and a new copolymer.

The patent proposes novel homopolymers and new copolymers with low light absorption loss and high glass transition temperature that are suitable for application to optical communication media due to the low hydrogen content in the monomers. The purpose of this study is to improve the glass transition temperature, low light absorption loss and other properties of the conventional acrylic optical communication polymer, and this patent has solved the problem of the conventional acrylic optical polymer for optical communication.

This study is based on the high temperature and high glass transition temperature compared to conventional acrylic polymers through optical copolymerization of fluorine and / or chlorine-containing itaconic monomers and homopolymerization and other fluorine and / or chlorine-containing monomers. It is an object of the present invention to provide novel homopolymers and new copolymers with low optical absorption loss and other improved mechanical properties required for optical communication media.

In order to achieve the above object, new monomers are prepared by reacting fluorine or / and chlorine-containing amines capable of inducing imidization with itaconic anhydride, and copolymerizing them with a homopolymer or other fluorine or / and chlorine-containing monomers. It was obtained to measure the physical properties.

Fluorine and / or chlorine-containing itaconic novel monomers according to the present invention for achieving the above object is configured to include a structure represented by the following formula (1).

Formula 1

In the above formula, R is a fluorine or / and chlorine-containing amine that can induce a nucleophilic reaction, the material is 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-trifluoro Lovenzamide, 2,3,5-trifluorobenzamide, 2,3,6-trifluorobenzamide, 2,4,5-trifluorobenzamide, 2,4,6-trifluorobenza Amide, 3,4,5-trifluorobenzamide, 2,3,4-trifluorobenzylamine, 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- (trifluoromethoxy) benzylamine, 4- (trifluoromethoxy) benzylamine, 2- (trifluoro Methyl) benzamide, 3- (trifluoromethyl) benzamide, 4- (trifluoromethyl) benzamide, 2- (trifluoromethyl) benzylamine, 3- (trifluoromethyl) benzylamine, 4 -(Trifluoromethyl) benzylamine, 2- (trifluoromethyl) phenylacetaamide, 3-chloroaniline, 4-chloroaniline, 2-chloro-4-fluoroaniline, 2-chloro-5-fluoro Roaniline, 2-chloro-6-fluoroaniline, 3-chloro-2-fluoroaniline, 3-chloro-4-fluoroaniline, 4-cle Loro-2-fluoroaniline, 5-chloro-2-fluoroaniline, 2-chloro-4-fluorobenzamide, 2-chloro-6-fluorobenzamide, 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-difluoro Aniline, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 3,5-difluoroaniline, 2,3-difluorobenzylamine, 2, 4-difluorobenzylamine, 2,5-difluorobenzylamine, 2,6-difluorobenzylamine, 3,4-diple Oro benzylamine, and the like 3,5-difluoro-benzyl amine, aniline 2-fluoro, 3-fluoro aniline, 4-fluoro-aniline, 2,3,4,5,6-pentafluoro-aniline. In addition, the vinyl acetate monomer copolymerized with the above-mentioned itaconic monomers may be prepared by transesterification of fluorine or / and chlorine-containing acid with vinyl acetate, or by fluorine or / and 2,2-dichlorovinylacetate. The chlorine-containing acid chloride can be prepared by esterification under a tributyl tin methoxide catalyst. Fluorine and / or chlorine-containing acid compounds that may be used include fluoroacetic acid, chloroacetic acid, difluoroacetic acid, dichloroacetic acid, trifluoroacetic acid, trichloroacetic acid, perfluoropropionic acid, perfluorobutylic acid, and Chlorobutyl acid, perfluorovaleric acid, perfluorocarroic acid, perfluoro-normal-heptanoic acid, perfluorocaprylic acid, perfluoroglutaric acid, chloroplatinic acid, trifluorobutyl acid, Perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluororonanoic acid, perfluorodecanoic acid, perfluorododecanoic acid, perfluorocebacic acid, 3H- Decafluorodecanoic acid, 6-fluorohexanoic acid, 4,4,5,5,6,6,6-heptafluorohexanoic acid, 5,5,5-trifluorobaleric acid, 2H, 2H-hepta Fluorovaleric acid, 5H-octafluorovaleric acid, 3H-octafluorovaleric acid, 4-aryl-2,3,5,6-tetrafluoro Benzoic 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 (tri Fluoromethyl) benzoic acid, 2,6-bis (trifluoromethyl) benzoic acid, 3,5-bis (trifluoromethyl) benzoic acid, 2,2-bis (trifluoromethyl) -2-hydrate acetic acid, 2 , 4-bis (trifluoromethyl) phenylacetic acid,, 3,5-bis (trifluoromethyl) phenylacetic acid, 2,2-bis (trifluoromethyl) propionic acid, 4-bromo-2-chloro- 5-fluorobenzoic acid, 3-bromo-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. Each acid can be used to prepare an acid chloride using thionyl chloride.

In addition, the fluorine or / and chlorine-containing monomer which can be copolymerized with the above-mentioned itaconic monomers include vinyl fluoride, aryl pentafluorobenzene, aryl perfulo-normal-nonanoate, aryl perfluoro Pentanoate, 4-aryl-2,3,5,6-tetrafluorobenzoic acid, aryltrifluoroacetate, 4-buromo-3-chloro-3,4,4-trifluorobutene, 2-part Lomo-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-tree Fluoro1,3-butadiene, 2-bromo-3,3,3-trifluoropropene, 2-chloropentafluoro-1,3-butadiene, 2-chlorostyrene, 4-chlorostyrene, 2, 3-dichloro-1-propene, 1,4-divinylperfluorobutane, 1,6-divinylperfluorobutane, 1H, 1H, 7H-dodecafluoro Methyl acrylate, 1H, 1H, 1H-eicosafluoroundecyl acrylate, 2-fluoroethyl acrylate, 3-fluoropropene, 2-fluorostyrene, 3-fluorostyrene, 4-fluoro Styrene, 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, hexafluoropropene, 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-trifluoro Roethyl acrylate, 3,3,3-trifluoropropene, and the like.

Copolymers of the fluorine or / and itaconic monomers prepared in this patent with homopolymers and other fluorine and / or chlorine containing monomers prepared using the same can be applied as an optical fiber which is a transmission means for optical communication, These copolymers can be obtained by polymerization using a radical initiator for 1 to 96 hours at a temperature of 40 to 90 ° C. Examples of the initiator are azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide and tertiary butyl. Peroxybenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, azodicarbonamide, and the like, and fluorine or / and chlorine-containing radical initiators may also be used, such as N- (4- Chlorobenzoyl) N'-α-cyanocyclohexyl diimide, di- (2-chloroethyl) -2,2'-azo-bis-isobutyrate, 1,1'-bis- (4-chlorophenyl) azo Methane, 1,1'-azo-bis-1-chloro -1-phenylethane, tert-butyl 2-chloro-1,1-dimethylethyl peroxide, 5-chloro-2-theonyl peroxide, perfluoropropionyl peroxide, 2,2,3,3- Tetrafluoropropionyl peroxide and the like.

The copolymerization ratio at the time of copolymer production was prepared in 1%-99% ratio, and the said copolymer can also be manufactured by the combination of two or more types of monomers. The molecular weight of the polymer obtained was 5,000 g / mol to 800,000 g / mol and generally 20,000 g / mol to 200,000 g / mol were obtained.

The novel copolymers produced from this patent show relatively high glass transition temperature and low transmission loss compared to the conventional acrylic polymer for optical communication. Their field of application is very versatile and can be used for optical communication cables and short-range transmission optical media in vehicles, airplanes. The copolymers prepared in this patent can replace the conventional acrylic polymer for optical communication and exhibit properties that exceed those of the conventional acrylic polymer due to the low hydrogen content in the monomer in terms of transmission loss, which is an important property of the optical communication medium. have.

Table 1 shows the absorption loss according to the overtone wavelength of C-D, C-D, C-F, and C-Cl bonds, respectively.

Table 1.

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.

In the general method for preparing fluorine- and / or chlorine-containing itaconic monomers according to the present invention, after adding acetic acid and itaconic anhydride in a flask equipped with a stirrer and a condenser, fluorine or / and chlorine-containing amine mixed with acetic acid Stir and drop. The reaction mixture is stirred and refluxed to obtain a purification method suitable for each reaction.

Example 1

In a 250 ml round bottom flask equipped with a stirrer and a condenser, 45 ml of acetic acid was added, 5.08 g of itaconic anhydride, and 2.75 g of pentafluoroaniline solution mixed with 15 ml of acetic acid was stirred for 30 minutes and dropped. The reaction mixture is stirred for 15 hours to reflux and then precipitated in water to obtain a solid material. The obtained solid material is dried in a vacuum furnace and recrystallized with methanol to obtain pure monomer crystals.

Example 2)

In a 250 ml round bottom flask equipped with a stirrer and a condenser, 45 ml of acetic acid was added, 5.08 g of itaconic anhydride, and 3.98 g of pentachloroaniline mixed with 15 ml of acetic acid was dropped for 30 minutes. The reaction mixture is refluxed for 15 hours and then precipitated in water to obtain a solid material. The obtained solid material is dried in a vacuum furnace and recrystallized with methanol to obtain pure monomer crystals.

Example 3

In a flask equipped with a stirrer and a condenser, 500 ml of dichloroethanol, 3.2 g of 2-fluoroethanol, 2 g of fumaric acid, 0.075 g of 4-methylaminopyridine, 9.922 g of 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 4

In a flask equipped with a stirrer and a condenser, 5.02 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-ethylcarbodi Mead is dissolved in 500 ml of dichloromethane and reacted at 23 ° C. for 12 hours with stirring. 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 5

In a flask equipped with a stirrer and a condenser, 6.8 g of pentafluoroethyl alcohol, 2 g of fumaric acid, 0.075 g of 4-methylaminopyridine, 9.922 g of 1,3-dimethylaminopropyl-3-ethylcarbodiimide were added to 500 ml of dichloro 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 6

Place 10.6 g pentafluorobenzoic acid and 35 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 vinylacetate and petroleum ether, the material remaining 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 7

Place 14.72g pentachlorobenzoic acid and 35g vinyl acetate in a 250ml round bottom flask equipped with a condenser, a stirrer and a thermometer, and slowly drop 1.71g 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 vinylacetate and petroleum ether, the material remaining 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 8

5.70 g of trifluoroacetic acid and 35 g of vinyl acetate were placed in a 250 ml round bottom flask equipped with a condenser, a stirrer, and a thermometer, and then slowly dropped 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 streamed under reduced pressure to obtain a monomer.

Example 9

8.16 g of trichloroacetic acid and 35 g of vinyl acetate are placed 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 vinylacetate and petroleum ether, the material remaining 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 10)

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 11

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. 15.65 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 12)

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. 6.62 g of trifluoroacetyl chloride is slowly added to the mixed solution. The reaction product in this mixed solution is obtained by distillation under reduced pressure.

Example 13

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 9.1 g of trichloroacetyl chloride to the mixed solution. The reaction product in this mixed solution is obtained by distillation under reduced pressure.

In addition, a general method for preparing a homopolymer of a fluorine or / and chlorine-containing itaconic monomer according to the present invention and a copolymer with other fluorine or / and chlorine-containing monomers is copolymerization of 1 to 99% of two or more monomers. It is composed of a tetrahydrofuran solution having a range and reacted at a temperature of 40 to 90 ° C. for 1 to 96 hours using the aforementioned initiator or a fluorine or / and chlorine-containing initiator, followed by precipitation in methanol.

Example 14

1 g of the monomer obtained in Example 1 was polymerized at 90 ° C. for 48 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 70,000 / mol)

Example 15)

2 g of the monomer obtained in Example 2 was polymerized at 90 ° C. for 60 hours in an 30 mL solution of toluene using an initiator tert-butyl peroxybenzoate, and the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. = 110,000 / mol)

Example 16

1 g of the monomer obtained in Example 1 and 2 g of the monomer obtained in Example 2 were polymerized at 80 ° C. for 72 hours using an initiator lauryl peroxide in a 30 mL solution of toluene, and then the polymer obtained by precipitating in methanol was subjected to 36 in a vacuum furnace. Dry time (Mw = 60,000 / mol)

Example 17)

Polymer obtained by polymerizing 1.5 g of the monomer obtained in Example 1 and 2 g of the monomer obtained in Example 3 at 100 ° C. for 12 hours using an initiator perfluoropropionyl paroxide in a 30 mL solution of monochlorobenzene. Is dried in a vacuum furnace for 36 hours (Mw = 30,000 / mol).

Example 18

1 g of the monomer obtained in Example 1 and 1 g of the monomer obtained in Example 4 were polymerized for 96 hours at 75 ° C. using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 90,000 / mol)

Example 19

1.5 g of the monomer obtained in Example 1 and 2 g of the monomer obtained in Example 5 were polymerized at 60 ° C. for 48 hours using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitation in methanol was 36 hours in a vacuum furnace. Dry (Mw = 70,000 / mol)

Example 20

1 g of the monomer obtained in Example 1 and 3 g of the monomer obtained in Example 6 were polymerized at 50 ° C. for 72 hours using an initiator lauryl peroxide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was vacuum-treated. Dry for 36 hours (Mw = 50,000 / mol)

Example 21)

1 g of the monomer obtained in Example 1 and 1.5 g of the monomer obtained in Example 7 were polymerized at 90 ° C. for 28 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 40,000 / mol)

Example 22)

1 g of the monomer obtained in Example 1 and 3 g of the monomer obtained in Example 8 were polymerized at 70 ° C. for 36 hours using an initiator tertiary-butyl peroxide in a 30 mL solution of MEK, and then precipitated in methanol to obtain a polymer obtained in a vacuum furnace. Time to dryness (Mw = 140,000 / mol)

Example 23)

The polymer obtained by polymerizing 1.5 g of the monomer obtained in Example 1 and 2 g of the monomer obtained in Example 9 at 60 ° C. using an initiator AIBN in a 30 mL solution of tetrahydrofuran was precipitated in methanol for 36 hours in a vacuum furnace. Dry (Mw = 80,000 / mol)

Example 24)

2 g of the monomer obtained in Example 1 and 1 g of the monomer obtained in Example 10 were polymerized at 90 ° C. for 48 hours using an initiator azodicarbonamide in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was 36 hours in a vacuum furnace. Dry (Mw = 50,000 / mol)

Example 25)

3 g of the monomer obtained in Example 1 and 2 g of the monomer obtained in Example 11 were polymerized at 50 ° C. for 96 hours using an initiator lauryl peroxide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was subjected to vacuum Dry for 36 hours (Mw = 20,000 / mol).

Example 26)

2 g of the monomer obtained in Example 1 and 1.5 g of the monomer obtained in Example 12 were polymerized at 90 ° C. for 60 hours using an initiator tertiary-butylhydroperoxide in a 30 mL solution of toluene, and then precipitated in methanol. Dry in vacuum furnace for 36 hours (Mw = 120,000 / mol)

Example 27)

1 g of the monomer obtained in Example 1 and 1 g of the monomer obtained in Example 13 were polymerized for 32 hours at 60 ° C. using an initiator AIBN in a 30 mL solution of benzene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 50,000 / mol)

Example 28)

1.5 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 3 were polymerized at 90 ° C. for 48 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 140,000 / mol)

Example 29)

1 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 4 were polymerized at 90 ° C. for 40 hours using an initiator azodicarbonamide in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was 36 hours in a vacuum furnace. Dry (Mw = 30,000 / mol)

Example 30)

1 g of the monomer obtained in Example 2 and 2 g of the monomer obtained in Example 5 were polymerized at 50 ° C. for 72 hours using an initiator lauryl peroxide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was subjected to vacuum Dry for 36 hours (Mw = 70,000 / mol)

Example 31)

3 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 6 were polymerized at 90 ° C. for 24 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 11,000 / mol)

Example 32

2 g of the monomer obtained in Example 2 and 2.5 g of the monomer obtained in Example 7 were polymerized at 90 ° C. for 72 hours using an initiator tertiary-butyl peroxide in a 30 mL solution of toluene, and then the polymer obtained by precipitating in methanol was evacuated. Dry for 36 hours at (Mw = 80,000 / mol).

Example 33)

1 g of the monomer obtained in Example 2 and 2 g of the monomer obtained in Example 8 were polymerized at 80 ° C. for 48 hours using an initiator perfluoropropionyl peroxide in a 30 mL solution of toluene, and then the polymer obtained by precipitating in methanol was evacuated. Dry for 36 hours at (Mw = 60,000 / mol).

Example 34)

3 g of the monomer obtained in Example 2 and 2.5 g of the monomer obtained in Example 9 were polymerized at 60 ° C. for 18 hours using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitation in methanol was 36 hours in a vacuum furnace. Dry (Mw = 30,000 / mol)

Example 35)

1 g of the monomer obtained in Example 2 and 2 g of the monomer obtained in Example 10 were polymerized at 60 ° C. for 36 hours using an initiator lauryl peroxide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was subjected to vacuum Dry for 36 hours (Mw = 50,000 / mol)

Example 36)

After 1.5 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 11 were polymerized at 90 ° C. for 36 hours using an initiator BPO in a 30 mL solution of toluene, the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 90,000 / mol)

Example 37)

1 g of the monomer obtained in Example 2 and 3 g of the monomer obtained in Example 12 were polymerized at 90 ° C. for 48 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 110,000 / mol)

Example 38

2 g of the monomer obtained in Example 2 and 1 g of the monomer obtained in Example 13 were polymerized at 70 ° C. for 36 hours using an initiator tertiary-butylhydroperoxide in a 30 mL solution of MEK, and then the polymer obtained by precipitation in methanol was vacuumed. Dry for 36 hours in a furnace (Mw = 50,000 / mol)

Example 39)

In Example 1, 1 g of monomer and 1.5 g of 2-chlorostyrene 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 40

1.5 g of the monomer obtained in Example 1 and 2 g of vinyltrifluoroacetate were polymerized at 50 ° C. for 96 hours using an initiator azodicarbonamide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. = 60,000 / mol)

Example 41)

2 g of the monomer acrylate and 1 g of vinyl fluoride obtained in Example 1 were polymerized at 50 ° C. for 40 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. 20,000 / mol)

Example 42)

1 g of the monomer acrylate and 1 g of 4-chlorostyrene obtained in Example 1 were polymerized at 90 ° C. for 32 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 70,000 / mol)

Example 43)

2 g of the monomer obtained in Example 1 and 1 g of 2,3-dichloro-1-propene were polymerized for 26 hours at 50 ° C. 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 44

In Example 2, 3 g of monomer and 2 g of 2-chlorostyrene 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. (Mw = 40,000 / mol)

Example 45)

2 g of the monomer obtained in Example 2 and 3 g of vinyltrifluoroacetate were polymerized at 50 ° C. for 96 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. 70,000 / mol)

Example 46

1 g of the monomer acrylate and 1.5 g of vinyl fluoride obtained in Example 2 were polymerized at 80 ° C. for 42 hours using an initiator BPO in a 60 mL solution of MEK, and then precipitated in methanol to obtain a polymer. (Mw = 110,000 / mol)

Example 47)

2 g of the monomer acrylate and 1.5 g of 4-chlorostyrene obtained in Example 2 were polymerized at 60 ° C. for 72 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 40,000 / mol)

Example 48)

1 g of the monomer obtained in Example 2 and 1 g of 2,3-dichloro-1-propene were polymerized at 50 ° C. for 48 hours using an initiator azodicarbonamide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. (Mw = 50,000 / mol)

Example 49)

0.5 g of the monomer obtained in Example 1 and 1 g of methyl methacrylate were polymerized at 60 ° C. for 60 hours using an initiator AIBN in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 80,000 / mol)

Example 50)

0.5 g of the monomer obtained in Example 2 and 1 g of methyl methacrylate were polymerized at 50 ° 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 = 70,000 / mol )

Example 51)

0.5 g of the monomer obtained in Example 1 and 1 g of styrene were polymerized at 60 ° C. for 36 hours using an initiator 5-chloro-2-theonyl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 40,000 / mol)

Example 52)

0.5 g of the monomer obtained in Example 2 and 1 g of styrene were polymerized at 90 ° C. for 24 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer.

Example 53)

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 50 ° 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 = 30,000 / mol)

Example 54)

0.5 g of the monomer obtained in Example 1, 1 g of the monomer obtained in Example 5, and 2.5 g of the monomer obtained in Example 7 were polymerized at 50 ° C. for 72 hours using an initiator AIBN in a 60 mL solution of benzene, and then precipitated in methanol. (Mw = 60,000 / mol)

Example 55)

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 48 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. To obtain a polymer (Mw = 70,000 / mol).

Example 56)

0.5 g of the monomer obtained in Example 2, 1 g of the monomer obtained in Example 6 and 2.5 g of the monomer obtained in Example 8 were polymerized at 50 ° C. for 30 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, Precipitate in methanol to give polymer (Mw = 50,000 / mol)

The fluorine- and / or chlorine-containing itaconic novel homopolymers and novel copolymers produced by the present invention have improved both high glass transition temperature and low absorption loss compared with conventional acrylic polymers for optical communication. From such physical properties, economic effects are expected by replacing acrylic polymers currently used in optical fibers in automobiles, airplanes and ships, automobiles, medical devices, simple measuring instruments, electronic device wiring, and short-range optical transmission media.

Claims (3)

Monomers prepared by reacting fluorine or / and chlorine-containing amines, etc., capable of inducing imidization reactions having a structure represented by the following formula 1 with itaconic anhydride: Formula 1 In which R is a fluorine or / and chlorine-containing amine capable of inducing an imidization reaction, such as 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-trifluoroacetace 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-trifluoro Lovenzamide, 3,4,5-trifluorobenzamide, 2,3,4-trifluorobenzylamine, 2,3,5-trifluoro Nitrile, 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) benza Amide, 3- (trifluoromethoxy) benzamide, 4- (trifluoromethoxy) benzamide, 2- (trifluoromethoxy) benzylamine, 3- (trifluoromethoxy) benzylamine, 4- (tri Fluoromethoxy) benzylamine, 2- (trifluoromethyl) benzamide, 3- (trifluoromethyl) benzamide, 4- (trifluoromethyl) benzamide, 2- (trifluoromethyl) benzylamine , 3- (trifluoromethyl) benzylamine, 4- (trifluoromethyl) benzylamine, 2- (trifluoromethyl) phenylacetaamide, 3-chloroaniline, 4-cle Roroaniline, 2-chloro-4-fluoroaniline, 2-chloro-5-fluoroaniline, 2-chloro-6-fluoroaniline, 3-chloro-2-fluoroaniline, 3-chloro-4-fluoro Roaniline, 4-chloro-2-fluoroaniline, 5-chloro-2-fluoroaniline, 2-chloro-4-fluorobenzamide, 2-chloro-6-fluorobenzamide, 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- (tri Fluoro) benzylamine, 2,6-dichloro-4- (trifluoromethoxy) aniline, 2,6-dichloro-4- (trifluoromethyl) aniline, 2,3-difluoroaniline, 2, 4-difluoroaniline, 2,5-difluoroaniline, 2,6-difluoroaniyl , 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 Copolymer of the monomer of claim 1 with at least two kinds of fluorine and / or chlorine-containing monomers mentioned above. The homopolymer and copolymer, characterized in that used as the transmission medium for optical communication according to claim 2