KR20030073312A - Fluorinated or/and Chlorinated Fumaric Monomers, their Polymers and Copolymers for Optical Communuications - Google Patents

Abstract

The present invention relates to the preparation of fluorine or / and chlorine-containing fumaric monomers suitable for transmission media for optical communication, and to the preparation of copolymers thereof with homopolymers and fluorine and / or chlorine-containing monomers. Fluorine or / and chlorine-containing fumaric monomers according to the present invention is configured to include a structure represented by the following formula (1).

Formula 1

Through the present invention, fluorine or / and chlorine may be introduced into the fumaric monomer structure to obtain polymers and copolymers having improved physical properties applicable to optical communication than conventional acrylic polymers.

Description

Fluorinated or / and Chlorinated Fumaric Monomers, their Polymers and Copolymers for Optical Communuications}

The present invention relates to homopolymers and copolymers prepared using fluorine or / and chlorine-containing fumaric novel monomers suitable for transmission media for optical communications. Incorporation of fluorine or / and chlorine into the novel fumaric monomer structure yields 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. (US Pat. No. 6,271,312) In addition to these properties, important physical properties required as optical communication media include the presence or absence of crystallinity of polymers. When the waveguide passes through the optical fiber and the waveguide proceeds, the crystallinity of the polymerizer is 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 solve the problems presented above, the present patent prepares novel monomers by reacting fumaric acid with fluorine or / and chlorine-containing aliphatic alcohols. 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 present patent proposes a method for producing novel homopolymers and copolymers having low light absorption loss and high glass transition temperature suitable for application to optical communication media due to the low hydrogen content in the monomers. The purpose of these studies 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 fluorine and / or chlorine-containing fumaric monomers for optical communication and the copolymerization of two or more kinds of fluorine and / or chlorine-containing monomers such as homopolymerization and heterogeneous monomers. It is an object of the present invention to provide novel homopolymers and new copolymers having improved transition temperatures, low light absorption loss and other mechanical properties required for optical communication media.

In order to achieve the above object, a novel monomer is prepared by reacting a fluorine or / and chlorine-containing aliphatic alcohol or the like that can induce a nucleophilic reaction with fumaric acid, which is monopolymerized or two or more kinds of different fluorine or / and chlorine-containing compounds. The copolymer with the monomer was obtained and its physical properties were measured.

The fluorine or / and chlorine-containing fumaric 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 formula, R is a fluorine or / and chlorine-containing aliphatic alcohol and the like to induce a nucleophilic reaction, the substance is as follows. 2,2, -trifluoroethanol, 2-fluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1H, 1H-pentafluoropropanol-1, 1H, 1H , 3H-tetrafluoro-1-propanol, 3,3,3-trifluoropropan-1-ol, 1, 1, 1-trifluoro-2-propanol, 1-chloro-3-fluoroisopropanol, 2,2,3,4,4,4-hexafluoro-1-butanol, hexafluoro-2-methylisopropanol, 4,4,4-trifluorobut-2-ten-1-ol, 4, 4,4-trifluoro-1-butanol, 2-trifluoromethyl-2-propanol, 4,4,5,5,5-pentafluoro-1-pentanol, 2-methyl-4,4, 4-trifluorobutanol, 1H, 1H, 2H, 2H-perfluorohexan-1-ol, 1H, 1H-pentadecafluoro-1-octanol, 1H, 1H, 2H, 2H-perfluorooctane -1-ol, 1H, 1H-perfluoro-1-nonanol, 1H, 1H, 9H-hexadecafluorononanol, 3- (perfluoro-N-hexyl) pro-2-ene-1- Ol, 1H, 1H, 2H, 3H-perfluoro-2-nonen-1-ol, 1H, 1H, 2H, 2H-perfluoro-7-methyloctan-1-ol, 1H, 1H- Fluoro-1-decanol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, 1H, 1H-perfluoroundecan-1-ol, 1H, 1H, 2H, 2H-perfluoro -9-methyldecan-1-ol, 3- (perfluorooctyl) propanol, 1H, 1H-perfluoro-1-dodecanol, 1H, 1H, 2H, 2H-perfluorododecanol, 1H, 1H -Perfluoro-1- tetradecanol, 1H, 1H- perflurouro-1-octadecanol, or mixtures thereof.

In addition, the vinyl acetate monomer copolymerized with the above-mentioned fumaric monomers may be prepared by transesterification of fluorine or / and chlorine-containing acid, or by fluorine and / or chlorine-containing acid chloride with 2,2-dichlorovinylacetate. Can be prepared by esterification under a tributyltinmethoxide 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- (trifluoromeryl) benzoic acid, 2-chloro-5- (trifluoromethyl) benzoic acid, and the like. Each acid can be used to prepare an acid chloride using thionyl chloride, and to prepare a vinyl acetate monomer.

In addition, the fluorine or / and chlorine-containing monomers that can be copolymerized with the above-mentioned fumaric monomers include vinyl fluoride, arylpentafluorobenzene, aryl perfulo-normal-nonanoate, aryl perfluoropenta Noate, 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-trifluoro Rho 1,3-butadiene, 2-buromo-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-dodecafluorohep Acrylate, 1H, 1H, 1H-eicosafluoroundecyl acrylate, 2-fluoroethyl acrylate, 3-fluoropropene, 2-fluorostyrene, 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, 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 Ethyl acrylate, 3,3,3-trifluoropropene, methyl acrylate, styrene, acrylonitrile, acrylate, etc. There is this.

Copolymers of the fluorine or / and fumaric monomers prepared in this patent with a homopolymer and two or more kinds of fluorine or / and chlorine-containing monomers prepared by using the same, it is not applicable to the 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 150 ° C. Examples of the initiators include azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, Tert-butyl peroxybenzoate, tert-buryl peroxide, tert-butyl hydroperoxide, azodicarbonamide, and the like; 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-chloro Phenyl) azomethane, 1,1'- Crude-bis-1-chloro-1-phenylethane, tert-butyl 2-chloro-1,1-dimethylethylperoxide, 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 polymer obtained had a molecular weight of 5,000 g / mol to 800,000 g / mol and generally 20,000 g / mol to 250,000 g / mol.

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 exhibit properties that can replace the conventional acrylic polymer for optical communication, and the acrylic polymer for optical communication is due to the low hydrogen content in the monomer in terms of transmission loss, which is an important physical property of the optical communication medium. It shows physical properties that surpass.

Table 1 shows the absorption loss according to the overtone wavelength of the C-D, C-D, C-F, and C-C1 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.

A general method of preparing fluorine or / and chlorine-containing fumaric monomers according to the present invention is 2 mol of fluorine or / and chlorine-containing aliphatic alcohol and 1 mol of fumaric acid which can induce a nucleophilic reaction in a flask equipped with a stirrer and condenser , 05 mol of 4-methylaminopyridine and 11 mol of 1,3-dimethylaminopropyl-3-ethylcarbodiimide are dissolved in dichloromethane and reacted with stirring. Water is added to the reaction solution and the mixed solution is extracted with dichloromethane. The resulting solution is combined, dried over sodium sulfide, condensed, and extracted with saturated sodium carbonate solution. Consisting of drying again with sodium sulfide and condensation to obtain through purification methods suitable for the following reactions.

Example 1

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 cold dichloromethane at -20 ° C to obtain crystals, which were then dried in a vacuum furnace.

Example 2)

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 9 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 3

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 4

Place 10.60 g of pentafluorobenzoic acid and 100 g of vinyl acetate in a flask equipped with a condenser, a stirrer and a thermometer, and slowly drop 1.71 g of mercury sulfate. The mixture 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 liquid.

Example 5

Place 14.7 g of pentachlorobenzoic acid and 35 g of vinyl acetate in a flask equipped with a condenser, a stirrer, and a thermometer, and slowly drop 1.71 g of mercury sulfate. The mixture 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 liquid.

Example 6

5.70 g of trifluoroacetic acid and 35 g of vinyl acetate are placed in a flask equipped with a condenser, a stirrer, and a thermometer, and slowly drop 1.71 g of mercuric sulfate. The mixture 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 monomer.

Example 7

Place 8.17 g of trichloroacetic acid and 35 g of vinyl acetate in a flask equipped with a condenser, a stirrer, and a thermometer, and slowly drop 1.71 g of mercury sulfate. The mixture 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 monomer.

Example 8

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 9

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

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. 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 homopolymers of fluorine or / and chlorine-containing fumaric monomers according to the present invention and copolymers with other fluorine or / and chlorine-containing monomers is a copolymerization range of 1 to 99% of at least two monomers. It is added to tetrahydrofuran solution or toluene solution with and reacted for 1 to 96 hours at the temperature of 40 ~ 90 ℃ using the above-mentioned initiator or fluorine or / and chlorine-containing initiator, and then precipitated in methanol. .

Example 12)

5 g of the monomer obtained in Example 1 was polymerized at 90 ° C. for 12 hours using an initiator BPO in a 30 mL solution of toluene, and then precipitated in methanol, and the polymer obtained was dried in a vacuum furnace for 36 hours. (Mw = 50,000 / mol)

Example 13

5 g of the monomer obtained in Example 2 was polymerized for 24 hours at 60 ° C. using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours (Mw = 15,000 / mol). )

Example 14

5 g of the monomer obtained in Example 3 was polymerized in a 30 mL solution of tetrahydrofuran using an initiator AIBN at 60 ° C. for 48 hours, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 30,000 / mol )

Example 15)

1 g of the monomer obtained in Example 1 and 4 g of the monomer in Example 4 were polymerized at 90 ° C. for 12 hours using an initiator tertiary-butylhydroperoxide in a 30 mL solution of toluene, and then the polymer obtained by precipitating in methanol was subjected to vacuum. Dry for 36 hours at (Mw = 50,000 / mol).

Example 16

3 g of the monomer obtained in Example 1 and 2 g of the monomer in Example 5 were polymerized at 50 ° C. for 60 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 36 in a vacuum furnace. Dry time (Mw = 90,000 / mol)

Example 17)

1 g of the monomer obtained in Example 1 and 4 g of the monomer in Example 6 were polymerized at 90 ° C. for 36 hours using an initiator BPO in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was dried for 36 hours in a vacuum furnace. Mw = 70,000 / mol)

Example 18

2 g of the monomer obtained in Example 1 and 2 g of the monomer in Example 7 were polymerized at 60 ° C. for 64 hours 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 = 40,000 / mol)

Example 19

5 g of the monomer obtained in Example 1 and 4.5 g of the monomer in Example 8 were polymerized at 70 DEG C for 30 hours using an initiator BPO in a 30 mL solution of MEK, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 65,000 / mol)

Example 20

0.5 g of the monomer obtained in Example 1 and 0.3 g of the monomer in Example 9 were polymerized at 90 ° C. for 72 hours using an initiator tertiary-butyl peroxide in a 30 mL solution of toluene. Dry for 36 hours at (Mw = 90,000 / mol).

Example 21)

2 g of the monomer obtained in Example 1 and 1.5 g of the monomer in Example 10 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 dried in a vacuum furnace for 36 hours. (Mw = 80,000 / mol)

Example 22)

3 g of the monomer obtained in Example 1 and 7 g of the monomer in Example 11 were polymerized at 50 ° C. for 48 hours using an initiator azodicarbonamide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was subjected to 36 in a vacuum furnace. Time to dry. (Mw = 120,000 / mol)

Example 23)

3 g of the monomer obtained in Example 2 and 3 g of the monomer in Example 4 were polymerized at 80 ° C. for 60 hours using an initiator perfluoropropionyl peroxide in a 30 mL solution of MEK, and then the polymer obtained by precipitating in methanol was vacuum-treated. Dry for 36 hours (Mw = 70,000 / mol)

Example 24)

0.5 g of the monomer obtained in Example 2 and 1 g of the monomer in Example 5 were polymerized at 90 ° C. for 32 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 = 60,000 / mol)

Example 25)

2 g of the monomer obtained in Example 2 and 2 g of the monomer in Example 6 were polymerized at 90 ° 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 dried in a vacuum furnace for 36 hours. (Mw = 90,000 / mol)

Example 26)

1 g of the monomer obtained in Example 2 and 1 g of the monomer in Example 7 were polymerized at 60 ° C. for 48 hours using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 20,000 / mol)

Example 27)

1 g of the monomer obtained in Example 2 and 0.7 g of the monomer in Example 8 were polymerized at 90 ° C. for 18 hours using an initiator BPO in a toluene 30 mL solution, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 60,000 / mol)

Example 28)

3.2 g of the monomer obtained in Example 2 and 4.8 g of the monomer in Example 9 were polymerized at 60 ° C. for 36 hours using an initiator AIBN in a benzene 30 mL solution, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 30,000 / mol)

Example 29)

1.2 g of the monomer obtained in Example 2 and 1.5 g of the monomer in Example 10 were polymerized at 50 ° C. for 36 hours using an initiator azodicarbonamide in a 30 ml solution of tetrahydrofuran, and the polymer obtained by precipitating in methanol was subjected to vacuum. Dry for 36 hours at (Mw = 25,000 / mol).

Example 30)

3g of the monomer obtained in Example 2 and 2g of the monomer in Example 11 were polymerized at 80 ° C. for 42 hours using an initiator tertiary-butylperoxybenzoate in a toluene 3OmL solution, and then the polymer obtained by precipitating in methanol was subjected to vacuum. Dry for 36 hours at (Mw = 110,000 / mol).

Example 31)

1 g of the monomer obtained in Example 2 and 0.8 g of the monomer in Example 4 were polymerized at 75 ° C. for 42 hours using an initiator perfluoropropionyl peroxide in a 30 mL solution of MEK, and then the polymer obtained by precipitation in methanol was subjected to vacuum. Dry for 36 hours at (Mw = 80,000 / mol).

Example 32

0.5 g of the monomer obtained in Example 2 and 1 g of the monomer in Example 5 were polymerized at 80 ° C. for 24 hours using an initiator BPO in a 30 mL solution of MEK, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 60,000 / mol)

Example 33)

1 g of the monomer obtained in Example 2 and 2 g of the monomer in Example 6 were polymerized at 90 ° C. for 60 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 = 90,000 / mol)

Example 34)

1.5 g of the monomer obtained in Example 2 and 2.5 g of the monomer in Example 7 were polymerized at 80 ° C. for 96 hours using an initiator 5-chloro-2-theonyl peroxide in a 30 mL solution of toluene, followed by precipitation in methanol. The polymer is dried in a vacuum furnace for 36 hours (Mw = 40,000 / mol).

Example 35)

1 g of the monomer obtained in Example 2 and 1 g of the monomer in Example 8 were polymerized at 60 ° C. for 36 hours using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 50,000 / mol)

Example 36)

4 g of the monomer obtained in Example 2 and 2.5 g of the monomer obtained in Example 9 were polymerized at 90 ° C. for 48 hours using an initiator tertiary-butylhydroperoxide in a 30 mL solution of toluene, and then the polymer obtained by precipitation in methanol was vacuumed. Dry in a furnace for 36 hours. (Mw = 90,000 / mol)

Example 37)

2 g of the monomer obtained in Example 2 and 1 g of the monomer in Example 10 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 polymerization in a vacuum furnace. Time to dry. (Mw = 100,000 / mol)

Example 38

After polymerizing 1.5 g of the monomer obtained in Example 2 and 0.5 g of the monomer in Example 11 at 80 ° C. for 12 hours using an initiator perfluoropropionyl peroxide in a 30 mL solution of toluene, the polymer obtained by precipitation in methanol was vacuumed. Dry for 36 hours in a furnace (Mw = 60,000 / mol).

Example 39)

In Example 1, a polymer of 0.5 g of monomer and 2 g of 2-chlorostyrene was polymerized at 60 ° C. for 45 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 15,000 / mol)

Example 40

2 g of the monomer obtained in Example 1 and 3 g of vinyltrifluoroacetate were polymerized at 60 ° C. for 20 hours using an initiator tertiary butyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 90,000 / mol)

Example 41)

1.5 g of the monomer obtained in Example 1 and 2 g of vinyl fluoride were polymerized at 50 ° C. for 96 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 42)

1 g of the monomer obtained in Example 1 and 1.5 g of 4-chlorostyrene were polymerized at 90 ° C. for 28 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 55,000 / mol)

Example 43)

2 g of the monomer obtained in Example 1 and 3 g of 2,3-dichloro-1-propene were polymerized at 70 ° C. for 24 hours using an initiator lauryl peroxide in a 60 mL solution of cyclohexane, and then precipitated in methanol to obtain a polymer. (Mw = 80,000 / mol)

Example 44

In Example 2, 1 g of monomer and 0.5 g of 2-chlorostyrene were polymerized at 50 ° C. for 64 hours using an initiator AIBN in a 60 mL solution of benzene, followed by precipitation in methanol to obtain a polymer. (Mw = 72,000 / mol)

Example 45)

2.5 g of the monomer obtained in Example 2 and 2 g of vinyltrifluoroacetate were polymerized at 90 ° C. for 15 hours using an initiator perfluoropropionyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. Mw = 100,000 / mol)

Example 46

1 g of the monomer obtained in Example 2 and 0.8 g of vinyl fluoride were polymerized for 96 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 = 20,000 / mol)

Example 47)

3 g of the monomer obtained in Example 2 and 1.5 g of 4-chlorostyrene were polymerized at 80 ° C. for 60 hours using an initiator BPO in a 40 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 110,000 / mol)

Example 48)

1 g of the monomer obtained in Example 2 and 2 g of 2,3-dichloro-1-propene were polymerized for 48 hours at 60 ° C. using an initiator AIBN in a 60 mL solution of MEK, followed by precipitation in methanol to obtain a polymer. 70,000 / mol)

Example 49)

In Example 3, 1 g of monomer and 2 g of 2-chlorostyrene were polymerized at 60 ° C. for 60 hours using an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 20,000 / mol)

Example 50)

3 g of the monomer obtained in Example 3 and 1 g of vinyltrifluoroacetate were polymerized at 80 ° C. for 90 hours using an initiator tertiary-butylperoxybenzoate in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. Mw = 40,000 / mol)

Example 51)

1 g of the monomer obtained in Example 3 and 1.5 g of vinyl fluoride were polymerized at 75 ° C. for 24 hours using an initiator lauryl peroxide in a 60 mL solution of cyclohexane, and then precipitated in methanol to obtain a polymer. (Mw = 60,000 / mol)

Example 52)

3 g of the monomer obtained in Example 3 and 2 g of 4-chlorostyrene were polymerized at 55 ° C. for 72 hours using an initiator 5-chloro-2-theonyl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. (Mw = 60,000 / mol)

Example 53)

1 g of the monomer obtained in Example 3 and 1.5 g of 2,3-dichloro-1-propene were polymerized at 75 ° C. for 48 hours using an initiator perfluoropropionyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol. Obtain a polymer (Mw = 80,000 / mol).

Example 54)

0.5 g of the monomer obtained in Example 1 and 1 g of methyl methacrylate 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 55)

0.5 g of the monomer obtained in Example 2 and 1 g of methyl methacrylate were polymerized at 90 ° C. for 40 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. (Mw = 30,000 / mol)

Example 56)

0.5 g of the monomer obtained in Example 2 and 1 g of styrene were polymerized for 96 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 57)

0.5 g of the monomer obtained in Example 3 and 1 g of the style were polymerized in a 60 mL solution of tetrahydrofuran for 24 hours at 60 ° C. using an initiator AIBN, and then precipitated in methanol to obtain a polymer. (Mw = 90,000 / mol)

Example 58)

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 100 ° C. for 14 hours using an initiator tertiary-butyl peroxide in a 60 mL solution of toluene, and then methanol. To precipitate to obtain a polymer (Mw = 30,000 / mol)

Example 59)

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 7 were polymerized at 50 ° C. for 48 hours using an initiator AIBN in a 60 mL solution of benzene, and then precipitated in methanol. (Mw = 70,000 / mol)

Example 60

0.5 g of the monomer obtained in Example 3, 1 g of the monomer obtained in Example 5, and 2.5 g of the monomer obtained in Example 8 were polymerized at 90 ° C. for 84 hours using an initiator tertiary-butylhydroperoxide in a 60 mL solution of toluene. After that, it is precipitated in methanol to obtain a polymer (Mw = 110,000 / mol).

Example 61

0.5 g of the monomer obtained in Example 3, 1 g of the monomer obtained in Example 6, and 2.5 g of the monomer obtained in Example 8 were polymerized at 75 ° C. for 48 hours using an initiator BPO in a 60 mL solution of MEK, and then precipitated in methanol. (Mw = 70,000 / mol)

Fluorine and / or chlorine-containing fumaric novel homopolymers and novel copolymers prepared through the present invention have improved both high glass transition temperature and low absorption loss compared to 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)

Monomer prepared by reacting fumaric acid with a fluorine or / and chlorine-containing aliphatic alcohol capable of inducing a nucleophilic reaction having a structure represented by Formula 1 below Formula 1 In the formula, R is a fluorine or / and chlorine-containing aliphatic alcohol that can induce a nucleophilic reaction, such as trifluoroethanol, difluoroethanol, hexafluoroflopanol, heptafluorobutanol, heptafluoropentanol, hexafluoro Roisopropanol, methyltrifluorobutanol, octafluoropentanol, perfluorodecanol, 2,2-difluoroethanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, 2,2 , 3,4,4,4-heptafluorobutan-1-ol, hexafluoroisopropanol, 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-heptaflu Oro-1-butanol, 2,2,3,3-tetrafluoro-1-propanol, 2,2,2-trifluoroethanol, 1,1,1-trifluoro-2-octanol, 2 , 2,3,3,3-pentafluoro Ropanol, 1,1,1,2,2-pentafluoro-3-propanol, 2-fluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 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-trifluoromethyl-2-propanol , 1H, 1H-perfluoropentan-1-ol, 4,4,4-trifluoro-3- (trifluoromethyl) butanol, 4,4,5,5,5-pentafluoropentanol, 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-traflu Lephenol, 3,4,5-trifluorophenol, 2.3-difluorophenol, 2.4-difluorophenol, 2.5-difluorophenol, 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- (trifluoro Chloromethyl) phenol, 2-fluoro-6- (trifluoromethyl) phenol, 3-fluoro-4- (trifluoromethyl) phenol, 3-fluoro-5- (trifluoromethyl) phenol, 4-fluoro-2- (trifluoromethyl) phenol, 4-fluoro-3- (trifluorome4-fluoro-2- (trifluoromethyl) phenol, 4-fluoro-3- (tri Fluoromethyl) 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-propanol, 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 A homopolymer of the monomers according to claim 1 and a copolymer of two or more kinds of fluorine or / and chlorine-containing monomers mentioned above. The homopolymer and copolymer, characterized in that used as the transmission medium for optical communication according to claim 2