스티렌과 불소함유 아크릴레이트의 공중합 및 공중합체의 특성

김상신; 이상원; 허정림; 허완수; Sang-Shin Kim; Sang-Won Lee; Jung-Lim Haw; WanSoo Huh

Polymer(Korea), Vol.26, No.1, 9-17, January, 2002

Export Citation

스티렌과 불소함유 아크릴레이트의 공중합 및 공중합체의 특성

Copolymerization and Characteristics of Styrene and Fluorine-Containing Acrylate

김상신, 이상원, 허정림¹, 허완수^†

숭실대학교 환경ㆍ화학공학과
¹건국대학교 신소재공학과

Sang-Shin Kim, Sang-Won Lee, Jung-Lim Haw¹, and WanSoo Huh^†

Department of Chemical & Environmental Engineering, Soongsil University, Seoul, Korea
¹RDepartment of Materials Chemistry & Engineering, Konkuk University, Seoul, Korea

E-mail:

초록

탄화수소의 수소 부분이 불소로 치환된 과불소알킬기(perfluoro group : CF3(CF2)nCH2CH2- ; n=5, 7, 9, 11)를 함유하고 있는 perfluoroalkylethyl acrylate(FA)와 styrene을 bulk 상태에서 60 ℃를 유지하며 α,a'-azobisisobutyronitrile(AIBN)을 개시제로 하여 각각의 단량체의 반응 몰비를 변화시키며 전환율을 10% 이내로 제한하여 공중합체를 합성하였다. 또한 반응 몰비의 변화에 따른 중합된 공중합체내의 반복단위의 함량사이의 관계와 Kelen-Tudos법을 이용하여 단량체 반응성비 r1, r2를 구하였다. FT-IR과 1H-NMR을 통해 두 단량체의 공중합 여부와 구조를 정성적으로 확인하였고 공중합체의 조성은 1H-NMR분석을 통해 구하였다. 단량체의 비율에 따른 열적 특성은 DSC와 TGA를 통하여 분석하였으며 공중합체와 소량의 공중합체가 첨가된 PMMA의 접촉각을 측정하여 공중합체의 표면특성을 나타내는 표면자유에너지를 계산하였다.

The free radical bulk copolymerizations of perfluoroalkylethyl acrylate(FA) containing perfluoro group (CF3(CF2)nCH2CH2 ; n = 5, 7, 9, 11) with styrene were conducted at 60 ℃ using AIBN as an initiator. Reactivity ratios(r1, r2) were determined from monomer feed compositions and the NMR spectroscopically measured copolymer compositions using Kelen-Tudos method. The structures of copolymers were characterized with FT-IR and 1H-NMR analysis. Their thermal properties investigated with DSC and TGA were decreased with increasing the content of fluorinated acrylate in the copolymer. Their surface free energies were calculated with measuring contact angles of the copolymers and PMMA blends with a small amount of them.

Keywords:perfluoroalkyl acrylate;radical copolymerization;monomer reactivity ratio;contact angle;surface free energy

[References]

Hercules DM, Hercules SH, J. Chem. Educ., 61, 402 (1984)
Bouteiller V, Garnault AM, Tetssie D, Boileau S, Moller M, Polym. Int., 48, 765 (1999)
Cottington RL, Shafrin EG, Zisman WA, J. Phys. Chem., 62, 513 (1958)
Shafrin EG, Zisman WA, J. Phys. Chem., 66, 740 (1962)
Bernett MK, Zisman WA, J. Phys. Chem., 66, 1207 (1962)
Kim DK, Lee SB, Doh KS, J. Colloid Interface Sci., 205(2), 417 (1998)
Ishiwari K, Ohmori A, Koizumi S, Nippon Kagaku Kaishi, 10, 1924 (1985)
Budovskaya LD, Ivanova VN, Oskar LN, Lukasov SV, Baklagina YG, Sidorovich AV, Nasledov DM, Vysokovmol. Soedin. Ser. A, 32, 561 (1990)
Koizumi S, Tanano K, Tanaka Y, Shimizu T, Kutsumizu S, Yano S, Macromolecules, 25, 1316 (1992)
Shimizu T, Tanaka Y, Kutsumizu S, Yano S, Macromolecules, 29(1), 156 (1996)
Fernandez-Garcia M, Fernandez-Sanz M, Madruga EL, Cuervo-Rodriguez R, Hernandez-Gordo V, Fernandez-Monreal MC, J. Polym. Sci. A: Polym. Chem., 38(1), 60 (2000)
Maars W, Peters RH, Still RH, J. Appl. Polym. Sci., 23, 1063 (1979)

[Referenced By]

[1] Hercules DM, Hercules SH, J. Chem. Educ., 61, 402 (1984)

[2] Bouteiller V, Garnault AM, Tetssie D, Boileau S, Moller M, Polym. Int., 48, 765 (1999)

[3] Cottington RL, Shafrin EG, Zisman WA, J. Phys. Chem., 62, 513 (1958)

[4] Shafrin EG, Zisman WA, J. Phys. Chem., 66, 740 (1962)

[5] Bernett MK, Zisman WA, J. Phys. Chem., 66, 1207 (1962)

[6] Kim DK, Lee SB, Doh KS, J. Colloid Interface Sci., 205(2), 417 (1998)

[7] Ishiwari K, Ohmori A, Koizumi S, Nippon Kagaku Kaishi, 10, 1924 (1985)

[8] Budovskaya LD, Ivanova VN, Oskar LN, Lukasov SV, Baklagina YG, Sidorovich AV, Nasledov DM, Vysokovmol. Soedin. Ser. A, 32, 561 (1990)

[9] Koizumi S, Tanano K, Tanaka Y, Shimizu T, Kutsumizu S, Yano S, Macromolecules, 25, 1316 (1992)

[10] Shimizu T, Tanaka Y, Kutsumizu S, Yano S, Macromolecules, 29(1), 156 (1996)

[11] Fernandez-Garcia M, Fernandez-Sanz M, Madruga EL, Cuervo-Rodriguez R, Hernandez-Gordo V, Fernandez-Monreal MC, J. Polym. Sci. A: Polym. Chem., 38(1), 60 (2000)

[12] Maars W, Peters RH, Still RH, J. Appl. Polym. Sci., 23, 1063 (1979)