KR20030073308A - Fluorinated or/and Chlorinated Acetate Monomers, their Polymers and Copolymers for Optical Communuications - Google Patents

Abstract

PURPOSE: Provided are a fluorine and/or chlorine-containing acetate monomer for optical communication, and a homopolymer and a copolymer which have higher glass transition temperature, lower light absorption loss, and improved mechanical property necessary to transmission media for other optical communication, in comparison with an acrylic polymer used for optical communication. CONSTITUTION: The monomer which is represented by formula 1, is produced from 2,2-dichlorovinylacetate, and fluorine and/or chlorine-containing acid chloride. In the formula 1, R is fluorine and/or chlorine-containing acid chlorides. The copolymer is produced by introducing fluorine and/or chloride into novel acetate monomer structure, and has more improved physical property applicable to optic communication, in comparison with an existing acrylic polymer.

Description

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

The present invention relates to homopolymers and copolymers prepared using fluorine or / and chlorine-containing acetate-based novel monomers suitable for transmission media for optical communications. Incorporation of fluorine or / and chlorine into the novel acetate-based monomer structure yielded more improved properties 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 for optical communication media 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 region, 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 invention provides a monomer by esterifying 2,2-dichlorovinylacetate and fluorine or / and chlorine-containing acid chloride under a tributyltinmethoxide catalyst. 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 corresponding physical properties than the conventional acrylic optical communication polymer, and this patent has solved the problem of the conventional optical acrylic polymer for such optical communication.

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

In order to achieve the above object, 2,2-dichlorovinylacetate and fluorine or / and chlorine-containing acid chloride are esterified under a tributyl tin methoxide catalyst to prepare a new monomer, which is a homopolymer or other fluorine or / and chlorine-containing monomer. The copolymer with was obtained.

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

Wherein R is a fluorine or / and chlorine-containing acid chloride capable of inducing an esterification reaction under 2,2-dichlorovinylacetate and tributyltinmethoxide catalyst. These acid chlorides are fluoro acetic acid, chloro acetic acid, difluoro acetic acid, dichloro acetic acid, trifluoro acetic acid, trichloro acetic acid, perchloro acetic acid, perfluoro acetic acid, perfluoropropionic acid, perfluorobutyl acid, perchlorobutyl Acids, perfluorovaleric acid, perfluorocarroic acid, perfluoro-normal-heptanoic acid, perfluorocaprylic acid, perfluoroglutaric acid, chloroplatinic acid, trifluorobutyl acid, perfluor Lofentanic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluoroononanic acid, perfluorodecanoic acid, perfluorododecanoic acid, perfluorocebacic acid, 3H-decafluoro Rhodecanoic acid, 6-fluorohexanoic acid, 4,4,5,5,6,6,6-heptafluorohexanoic acid, 5,5,5-trifluorobaleric acid, 2H, 2H-heptafluoro Valeric acid, 5H-octafluorovaleric acid, 3H-octafluorovaleric acid, 4-aryl-2,3,5,6-tetrafluorobenzoic acid, 2-a No-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 (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-fluoro Benzoic 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-fluoro Benzoic 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 using thionyl chloride It can be used to prepare vinyl acetate monomers.

In addition, two or more kinds of monomers capable of preparing a copolymer with the above-mentioned acetate monomers may be prepared by transesterification of fluorine or / and chlorine-containing acid with vinyl acetate. 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 Crude 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, methyl Acrylate, styrene, acrylonitrile, acrylate and the like.

In addition, fluorine or / and chlorine-containing monomers which can be copolymerized with the above-mentioned acetate-based monomers include vinyl fluoride, arylpentafluorobenzene, aryl purple fuoro-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-dodecafluoro Roheptyl acrylate, 1H, 1H, 1H-eicosafluoroundecyl acrylate, 2-fluoroethyl acrylate, 3-fluoropropene, 2-fluorostyrene, 3-fluorostyrene, 4-fluoro Rostyrene, 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-tri Fluoroethyl acrylate, 3,3,3-trifluoropropene and the like.

Copolymers of the fluorine or / and acetate-based 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, the application 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 150 ° C. Examples of the initiators include azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, Tertiary butyl peroxybenzoate, tertiary butyl peroxide, tertiary 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-chloro Phenyl) azomethane, 1, 1'-Azo-bis-1-chloro-1-phenylethane, tert-butyl 2-chloro-1,1-dimethylethyl peroxide, 5-chloro-2-theonyl peroxide, perfluoropropionyl perlock Side, 2,2,3,3-tetrafluoropropionyl peroxide, and the like.

The copolymerization ratio in the production of the copolymer was prepared in a ratio of 1% 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 800,000 g / mol and generally 8,000 g / mol to 300,000 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 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 C-D, C-D, C-F, and C-F bonds, respectively.

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 acetate monomers according to the present invention, chloral, acetyl chloride and metal zinc are placed in diethyl ether and refluxed under stirring in a flask equipped with a stirrer and a condenser. Tributyltin methoxide was added to a solution obtained by distillation under reduced pressure, and the mixture was heated with stirring, followed by addition of an acid chloride, followed by a purification method suitable for each reaction.

Example 1

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, 39.25 g of acetyl chloride and 39.255 g of metal zinc were placed and refluxed for 24 hours while 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 2)

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 3

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. 6.623 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 4

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. 9.09 g of trichloroacetyl chloride is slowly added to the mixed solution. The reaction product in this mixed solution is obtained by recrystallization from cold ethanol.

Example 5

Place 10.60 g of pentafluorobenzoic 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

Place 14.72g of pentachlorobenzoic acid and 35g of vinyl acetate in a flask equipped with a condenser, a stirrer and a thermometer, and slowly drop 1.71g 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 7

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 8

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.

In addition, a general method for preparing homopolymers of fluorine or / and chlorine-containing acetate monomers according to the present invention and copolymers with other fluorine or / and chlorine-containing monomers is in the range of 1 to 99% copolymerization of two or more monomers. It was added to the tetrahydrofuran 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 9

1 g of the monomer obtained in Example 1 was polymerized in a 30 mL solution of tetrahydrofuran for 24 hours at 60 ° C. using an initiator AIBN, and the polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 40,000 / mol )

Example 10)

1 g of the monomer obtained in Example 2 was polymerized at 80 ° C. for 48 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 = 70,000 / mol)

Example 11

1 g of the monomer obtained in Example 3 was polymerized at 65 ° C. for 35 hours using an initiator tertiary-butyl peroxide 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 12)

1 g of the monomer obtained in Example 4 was polymerized at 60 DEG C for 72 hours using an initiator lauryl peroxide 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. 80, 000 / mol)

Example 13

1 g of the monomer obtained in Example 1 and 1.5 g of the monomer in Example 2 were polymerized at 100 ° C. for 7 hours using an initiator 1,1′-bis- (4-chlorophenyl) azomethane in a 30 mL solution of monochlorobenzene. , The polymer obtained by precipitation in methanol was dried in a vacuum furnace for 36 hours. (Mw = 50,000 / mol)

Example 14

0.5 g of the monomer obtained in Example 1 and 1 g of the monomer in Example 3 were subjected to polymerization at 60 ° C. for 64 hours using an initiator 1,1′-azo-bis-1-chloro-1-phenylethane in a 30 mL solution of tetrahydrofuran. The resulting polymer was precipitated in methanol and dried in a vacuum furnace for 36 hours. (Mw = 40,000 / mol)

Example 15)

2 g of the monomer obtained in Example 1 and 3 g of the monomer in Example 4 were polymerized at 90 ° C. for 60 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. (Mw = 60,000 / mol)

Example 16

1.5 g of the monomer obtained in Example 1 and 2 g of the monomer in Example 5 were polymerized for 30 hours at 60 ° C. using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and the polymer obtained by precipitating in methanol was dried in a vacuum furnace for 36 hours. Let's do it. (Mw = 50,000 / mol)

Example 17)

2 g of the monomer obtained in Example 1 and 1.5 g of the monomer in Example 6 were polymerized at 70 DEG C for 18 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. To dry. (Mw = 30,000 / mol)

Example 18

1 g of the monomer obtained in Example 1 and 0.5 g of the monomer in Example 7 were polymerized at 65 ° C. for 96 hours using an initiator lauryl peroxide in a 30 mL solution of tetrahydrofuran, and the polymer obtained by precipitating in methanol was subjected to vacuum Dry for 36 hours (Mw = 70,000 / mol)

Example 19

2 g of the monomer obtained in Example 1 and 3 g of the monomer in Example 8 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 = 40, 000 / mol)

Example 20

0.5 g of the monomer obtained in Example 2 and 2.0 g of the monomer in Example 3 were polymerized at 70 ° C. for 48 hours using an initiator tertiary-butyl peroxide in a 30 mL solution of toluene, and then the polymer obtained by precipitating in methanol was subjected to vacuum. Dry for 36 hours. (Mw = 60,000 / mol)

Example 21)

1 g of the monomer obtained in Example 2 and 2 g of the monomer in Example 4 were polymerized at 60 ° C. for 24 hours using azodicarbonimide in a 30 mL solution of tetrahydrofuran, and then the polymer obtained by precipitating in methanol was 36 in a vacuum furnace. Time to dry (Mw = 20,000 / mol).

Example 22)

1 g of the monomer obtained in Example 2 and 0.5 g of the monomer in Example 5 were polymerized at 90 ° C. for 72 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 = 50,000 / mol)

Example 23)

The polymer obtained by polymerizing 1.5 g of the monomer obtained in Example 2 and 2.0 g of the monomer in Example 6 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 2 and 1.5 g of the monomer in Example 7 were polymerized at 50 ° C. for 60 hours using an initiator tertiary-butyl peroxide in a 30 mL solution of benzene, and then the polymer obtained by precipitating in methanol was subjected to vacuum Dry for 36 hours. (Mw = 40,000 / mol)

Example 25)

1.5 g of the monomer obtained in Example 2 and 2 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 the polymer obtained by precipitation in methanol was dried for 36 hours in a vacuum furnace. (Mw = 90,000 / mol)

Example 26)

3 g of the monomer obtained in Example 3 and 2.5 g of the monomer in Example 4 were polymerized at 90 ° C. for 120 hours using an initiator perfluoroproionyl peroxide in a 30 mL solution of monochlorobenzene, and then the polymer obtained by precipitation in methanol was obtained. Dry in vacuum furnace for 36 hours (Mw = 50,000 / mol)

Example 27)

0.8 g of the monomer obtained in Example 3 and 1.4 g of the monomer in Example 5 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 = 20,000 / mol)

Example 28)

1 g of the monomer obtained in Example 3 and 1.5 g of the monomer in Example 6 were polymerized at 60 ° C. for 80 hours using an initiator azodicarbonimide 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 = 60,000 / mol).

Example 29)

A polymer obtained by polymerizing 0.5 g of the monomer obtained in Example 3 and 2 g of the monomer in Example 7 at 90 ° C. for 48 hours using an initiator 5-chloro-2-theonyl peroxide in a 30 mL solution of toluene, followed by precipitation in methanol. Is dried in a vacuum furnace for 36 hours (Mw = 70,000 / mol).

Example 30)

2 g of the monomer obtained in Example 3 and 1 g of the monomer in Example 8 were polymerized at 90 ° C. for 96 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 = 30,000 / mol)

Example 31)

1 g of the monomer obtained in Example 4 and 1 g of the monomer in Example 5 were polymerized at 60 ° C. for 60 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 = 90,000 / mol)

Example 32

2 g of the monomer obtained in Example 4 and 1.4 g of the monomer in Example 6 were polymerized for 24 hours at 60 ° C. using an initiator AIBN in a 30 mL solution of tetrahydrofuran, and the polymer obtained by precipitating in methanol was dried in a vacuum furnace for 36 hours. Let's do it. (Mw = 70,000 / mol)

Example 33)

1 g of the monomer obtained in Example 4 and 2 g of the monomer in Example 7 were polymerized at 80 ° C. for 18 hours using an initiator 1,1′-azo-bis-isobutyrate in a 30 mL solution of toluene, followed by precipitation in methanol. Is dried in a vacuum furnace for 36 hours. (Mw = 90,000 / mol)

Example 34)

The polymer obtained by polymerizing 1.5 g of the monomer obtained in Example 4 and 1.5 g of the monomer in Example 8 at 60 ° C. with an initiator AIBN in a 30 mL solution of tetrahydrofuran was precipitated in methanol for 36 hours in a vacuum furnace. Dry (Mw = 110,000 / mol)

Example 35)

0.5 m of monomer and 2 g of 2-chlorostyrene in Example 1 were polymerized at 50 ° C. for 48 hours using an initiator azodicarbonimide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. 40,000 / mol)

Example 36)

1 g of the monomer obtained in Example 1 and 1 g of vinyltrifluoroacetate were polymerized at 60 ° C. for 72 hours using an initiator AIBN in a 60 mL solution of benzene, and then precipitated in methanol to obtain a polymer. (Mw = 120,000 / mol)

Example 37)

2 g of the monomer obtained in Example 1 and 1.5 g of vinyl fluoride 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. (Mw = 70,000 / mol)

Example 38

1 g of the monomer obtained in Example 1 and 2 g of 4-chlorostyrene were polymerized at 50 ° C. for 12 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 40,000 / mol)

Example 39)

0.5 g of the monomer obtained in Example 1 and 0.8 g of 2,3-dichloro-1-propene 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 40

In Example 2, 2 g of monomer and 0.8 g of 2-chlorostyrene were polymerized at 70 ° C. for 28 hours using an initiator perfluoropionyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. 50,000 / mol)

Example 41)

1 g of the monomer obtained in Example 2 and 2 g of vinyltrifluoroacetate were polymerized at 60 ° C. for 96 hours using an initiator azodicarbonimide in a 60 mL solution of tetrahydrofuran, followed by precipitation in methanol to obtain a polymer. = 90,000 / mol)

Example 42)

1.5 g of the monomer obtained in Example 2 and 2 g of vinyl fluoride were polymerized at 60 ° C. for 24 hours using an initiator AIBN in a 60 mL solution of benzene, followed by precipitation in methanol to obtain a polymer. (Mw = 60,000 / mol)

Example 43)

1 g of the monomer obtained in Example 2 and 2 g of 4-chlorostyrene were polymerized at 90 ° C. for 12 hours using an initiator tertiary-butylhydroperoxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. = 20,000 / mol)

Example 44

1.4 g of the monomer obtained in Example 2 and 0.8 g of 2,3-dichloro-1-propene 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 45)

In Example 3, 1 g of monomer and 2 g of 2-chlorostyrene were polymerized at 60 ° C. for 36 hours using an initiator azodicarbonimide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. (Mw = 30,000 / mol)

Example 46

0.5 g of the monomer obtained in Example 3 and 1 g of vinyltrifluoroacetate were polymerized at 80 ° C. for 30 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 47)

1 g of the monomer obtained in Example 3 and 0.5 g of vinyl fluoride were polymerized at 90 ° C. for 12 hours using an initiator BPO in a 60 mL solution of toluene, followed by precipitation in methanol to obtain a polymer. (Mw = 60,000 / mol)

Example 48)

0.5 g of the monomer obtained in Example 3 and 2 g of 4-chlorostyrene 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 49)

1 g of the monomer obtained in Example 3 and 1.4 g of 2,3-dichloro-1-propene were polymerized at 50 ° C. for 45 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. (Mw = 70,000 / mol)

Example 50)

In Example 4, 2 g of monomer and 1.5 g of 2-chlorostyrene were polymerized at 60 ° 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 = 120,000 / mol)

Example 51)

1 g of the monomer obtained in Example 4 and 0.5 g of vinyltrifluoroacetate were polymerized at 60 ° C. for 12 hours using an initiator 5-chloro-2-theonyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol. (Mw = 50,000 / mol)

Example 52)

1 g of the monomer obtained in Example 4 and 0.5 g of vinyl fluoride were polymerized at 90 ° C. for 60 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 53)

1 g of the monomer obtained in Example 4 and 0.5 g of 4-chlorostyrene were polymerized at 60 ° C. for 24 hours using an initiator azodicarbonimide in a 60 mL solution of benzene, and then precipitated in methanol to obtain a polymer. (Mw = 20,000 / mol)

Example 54)

0.5 g of the monomer obtained in Example 4 and 1 g of 2,3-dichloro-1-propene 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 = 70,000 / mol)

Example 55)

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 perfluoropropionyl peroxide in a 60 mL solution of toluene, and then precipitated in methanol to obtain a polymer. = 90,000 / mol)

Example 56)

0.5 g of the monomer obtained in Example 2 and 1 g of methyl methacrylate were polymerized at 50 ° C. for 36 hours using an initiator lauryl peroxide in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. 30,000 / mol)

Example 57)

0.5 g of the monomer obtained in Example 3 and 1 g of styrene 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 = 60,000 / mol)

Example 58)

0.5 g of the monomer obtained in Example 4 and 1 g of styrene were polymerized at 50 ° C. for 48 hours using an initiator tertiary-butylperoxybenzoate in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol to obtain a polymer. = 20,000 / mol)

Example 59)

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 60 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 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. with an initiator AIBN in a 60 mL solution of tetrahydrofuran, and then precipitated in methanol. To obtain a polymer. (Mw = 110,000 / 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 60 ° C. for 18 hours using an initiator azodicarbonimide in a 60 mL solution of tetrahydrofuran. , Precipitated in methanol to obtain a polymer. (Mw = 40,000 / 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 90 ° C. for 36 hours using an initiator BPO in a 60 mL solution of toluene, and then precipitated in methanol. (Mw = 70,000 / mol)

The fluorine- and / or chlorine-containing acetate-based novel homopolymers and new 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)

A monomer prepared from 2,2-dichlorovinylacetate and a fluorine or / and chlorine-containing acid chloride having a structure represented by the following formula (1). Wherein R is a fluorine and / or chlorine-containing acid chloride as fluoroacetic acid, chloroacetic acid, difluoroacetic acid, dichloroacetic acid, trifluoroacetic acid, trichloroacetic acid, perfluoropropionic acid, perfluorobutylic acid, perchlorobutyl Acids, perfluorovaleric acid, perfluorocarroic acid, perfluoro-normal-heptanoic acid, perfluorocaprylic acid, perfluoroglutaric acid, chloroplatinic acid, trifluorobutyl acid, perfluor Lofentanic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluoroononanic acid, perfluorodecanoic acid, perfluorododecanoic acid, perfluorocebacic acid, 3H-decafluoro Rhodecanoic acid, 6-fluorohexanoic acid, 4,4,5,5,6,6,6-heptafluorohexanoic acid, 5,5,5-trifluorobaleric acid, 2H, 2H-heptafluoro Valeric 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 (trifluoro) Methyl) benzoic acid, 2,6-bis (trifluoromethyl) benzoic acid, 3,5-bis (trifluoromethyl) benzoic acid, 2,2-bis (trifluoromethyl) -2-hydric 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-flu Orobenzoic acid, 3-chlorozoic 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- (tri Acid chlorides prepared using fluoromethyl) benzoic acid, 2-chloro-5- (trifluoromethyl) benzoic acid, and the like A homopolymer of the monomers according to claim 1 and a copolymer of two or more fluorine or / and chlorine-containing monomers mentioned above. A homopolymer and a copolymer of two or more of the aforementioned fluorine and / or chlorine-containing monomers, characterized by being used as a transmission medium for optical communication according to claim 2.