유화 중합법에 의한 불소아크릴레이트 공중합체 제조

김동옥; 김지현; Dong Ok Kim; Ji Hyun Kim

Polymer(Korea), Vol.27, No.6, 528-535, November, 2003

Export Citation

유화 중합법에 의한 불소아크릴레이트 공중합체 제조

Preparation and Characterization of Fluoroacrylate Copolymer by Emulsion Polymerization

김동옥^†, 김지현

SK Chemicals 중앙연구소

Dong Ok Kim^†, and Ji Hyun Kim

SK Chemicals Research Institute, 600, Jungja-dong, Changan-ku, Suwon-si,Kyungki-do 440-745, Korea

E-mail:

초록

불소계 섬유용 발수·발유제의 제조에 일반적으로 쓰이는 과불소알킬아크릴레이트 및 노말알킬아크릴레이트의 공중합체를 유화 중합법으로 제조할 시 계면활성제, 유기용매, 내구성 향상 목적으로 소량 첨가되는 기능성 단량체 및 공중합체의 결정 용융 온도(T_m)변화에 따른 고분자 라텍스의 입자 직경 변화와 그들의 표면 특성(접촉각 및 발수도)의 변화를 관찰하였다. 또한 WAXD 실험을 통해 공중합체의 T_m의 변화에 따른 공중합체의 곁사슬의 채움구조 변화를 조사하였으며 이를 통해 표면 특성과의 관계를 연구하였다. 그리고 과불소알킬아크릴레이트와 더불어 말단기가 약간 다른 불소아크릴레이트, [CH₂=CHCO₂CH₂(CF₂CF₂)_nH] (n=4,5,6)를 사용한 불소아크릴레이트 공중합체도 동시에 합성하여 공중합체의 곁사슬의 채움구조, 말단기(CH_3-, CF_3-, CHF_2-)의 종류 및 농도변화에 따른 표면 특성 (접촉각, 발수도 등)의 변화를 관찰하였다.

The effects of surfactants, organic solvents, and functional monomers on the emulsion polymerization of perfluoroalkylethylacryaltes and n-alkylacrylates were investigated. In particular, the dependence of the surface properties, contact angle and water repellency on the crystal melting temperature (T_m) of the fluorocopolymer and the variation of polymer latex particle sizes was investigated. Using WAXD experiments and synthesizing different types of fluorocopolymers which have following fluoroacrylaytes [CH₂=CHCO₂CH₂(CF₂CF₂)_nH] (n=4,5,6), the relationship between the molecular packing structure of pendent side groups of fluorocopolymers and the surface properties was also investigated. We observed that the structure of primary carbon atoms of pendent side groups of fluorocopolymers plays key role in determining the surface properties.

Keywords:fluoroacrylate;surface;water repellency;latex;emulsion polymerization

[References]

U.S. Patent, 3,062,765 (Nov. 6), Patsy O. Sherman (to Minesota Mining and Manufacturing Company) (1962)
U.S. Patent, 3,277,039 (Oct. 4), Frank Joseph Marascia and Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1966)
U.S. Patent, 3,378,609 (Apr. 16), Ross Wade Fasick and Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1968)
U.S. Patent, 3,462,296 (Aug. 19), Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1969)
U.S. Patent, 3,491,169 (Jan. 20), Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1970)
U.S. Patent, 3,838,104 (Sep. 24) Takao Hayashi and Hiroaki Kojima (to Asahi Glass Company, Japan) (1974)
U.S. Patent, 3,920,614 (Nov. 18) Kazusuke Kirimoto and Takao Hayashi (to Asahi Glass Company, Japan) (1975)
U.S. Patent, 4,296,224 (Oct. 20) Shosin Fukui and Tadashi Akazawa (to Daikin Industries, Japan) (1981)
U.S. Patent, 4,795,793 (Jan. 3) Yoshio Amimoto and Masayoshi Shinjo (to Daikin Industries, Japan) (1989)
U.S. Patent, 4,859,754 (Aug. 22) Takashige Maekawa and Kazuya Oharu (to Asahi Glass Company, Japan) (1989)
U.S. Patent, 5,055,538 (Oct. 8) Yoshio Amimoto and Masayoshi Shinjo (to Daikin Industries, Japan) (1991)
U.S. Patent, 6,126,849 (Oct. 3) Masayuki Yamana and Norimasa Uesugi (to Daikin Industries, Japan) (2000)
U.S. Patent, 6,177,531 (Jan. 23) Toyomichi Shimada and Kyoichi Kaneko (to Asahi Glass Company, Japan) (2001)
U.S. Patent, 6,218,464 (Apr. 17), Hsing-Yeh Parker and Willie Lau (to Rohm and Haas Company, U.S.A.) (2001)
Pittman AG, Ludwig BA, J. Polym. Sci. A: Polym. Chem., 7, 3053 (1969)
Park IJ, Lee SB, Choi CK, J. Appl. Polym. Sci., 54(10), 1449 (1994)
Park IJ, Lee SB, Choi CK, Kim KJ, J. Colloid Interface Sci., 181(1), 284 (1996)
Katano Y, Tomono H, Nakajima T, Macromolecules, 27(8), 2342 (1994)
Morita M, Ogisu H, Kubo M, J. Appl. Polym. Sci., 73(9), 1741 (1999)
Cheng S, Chen Y, Chen Z, "Core-Shell Latex Ontaining a Fluorinated Polymer in Shell," in Fluorine in Coatings IV, Brussels (2001)
Wall LA, Fluoropolymers, John Wiley & Sons, New York (1972)

[Referenced By]

[1] U.S. Patent, 3,062,765 (Nov. 6), Patsy O. Sherman (to Minesota Mining and Manufacturing Company) (1962)

[2] U.S. Patent, 3,277,039 (Oct. 4), Frank Joseph Marascia and Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1966)

[3] U.S. Patent, 3,378,609 (Apr. 16), Ross Wade Fasick and Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1968)

[4] U.S. Patent, 3,462,296 (Aug. 19), Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1969)

[5] U.S. Patent, 3,491,169 (Jan. 20), Stuart Raynolds (to E.I. Dupont de Nemours, U.S.A.) (1970)

[6] U.S. Patent, 3,838,104 (Sep. 24) Takao Hayashi and Hiroaki Kojima (to Asahi Glass Company, Japan) (1974)

[7] U.S. Patent, 3,920,614 (Nov. 18) Kazusuke Kirimoto and Takao Hayashi (to Asahi Glass Company, Japan) (1975)

[8] U.S. Patent, 4,296,224 (Oct. 20) Shosin Fukui and Tadashi Akazawa (to Daikin Industries, Japan) (1981)

[9] U.S. Patent, 4,795,793 (Jan. 3) Yoshio Amimoto and Masayoshi Shinjo (to Daikin Industries, Japan) (1989)

[10] U.S. Patent, 4,859,754 (Aug. 22) Takashige Maekawa and Kazuya Oharu (to Asahi Glass Company, Japan) (1989)

[11] U.S. Patent, 5,055,538 (Oct. 8) Yoshio Amimoto and Masayoshi Shinjo (to Daikin Industries, Japan) (1991)

[12] U.S. Patent, 6,126,849 (Oct. 3) Masayuki Yamana and Norimasa Uesugi (to Daikin Industries, Japan) (2000)

[13] U.S. Patent, 6,177,531 (Jan. 23) Toyomichi Shimada and Kyoichi Kaneko (to Asahi Glass Company, Japan) (2001)

[14] U.S. Patent, 6,218,464 (Apr. 17), Hsing-Yeh Parker and Willie Lau (to Rohm and Haas Company, U.S.A.) (2001)

[15] Pittman AG, Ludwig BA, J. Polym. Sci. A: Polym. Chem., 7, 3053 (1969)

[16] Park IJ, Lee SB, Choi CK, J. Appl. Polym. Sci., 54(10), 1449 (1994)

[17] Park IJ, Lee SB, Choi CK, Kim KJ, J. Colloid Interface Sci., 181(1), 284 (1996)

[18] Katano Y, Tomono H, Nakajima T, Macromolecules, 27(8), 2342 (1994)

[19] Morita M, Ogisu H, Kubo M, J. Appl. Polym. Sci., 73(9), 1741 (1999)

[20] Cheng S, Chen Y, Chen Z, "Core-Shell Latex Ontaining a Fluorinated Polymer in Shell," in Fluorine in Coatings IV, Brussels (2001)

[21] Wall LA, Fluoropolymers, John Wiley & Sons, New York (1972)