술폰화된 Poly(phenylene sulfide)의 합성과 특성

김현석; 손원근; 황택성; 박정기; 송해영

Polymer(Korea), Vol.23, No.1, 8-16, January, 1999

Export Citation

술폰화된 Poly(phenylene sulfide)의 합성과 특성

The Synthesis and Characterstics of Sulfonated Poly(phenylene sulfide)

김현석, 손원근, 황택성, 박정기, 송해영

초록

본 연구에서는 유기용매에 용해되는 poly[methy[4-(phenylthio)pheny]sulfonium trifluormethanesulfonate](PPST)를 methyl-(phenylthio) phenyl sulfoxide의 자가축중합으로 합성하였다. 술폰화된 PPS는 PPST를 발연황산 (10% SO₃-H₂SO₄으로 술폰화한 후 NaOH 수용액으로 demethylation 하여 제조되었다. IR 흡광도와 이온교환용량으로 얻어진 술폰화의 최적조건은 반응시간 12시간. 반응온도 150 ℃ 이었다. IR 흡광도로 얻어진 이온교환용량 값은 11.5meq/g이었고, 반복단위에 대한 술폰화 정도는 2.19였다. 150 ℃ 이상의 술폰화반응에서 술폰산기와 인접페닐기 사이의 탈수 축합에 의해 가교화가 일어나기 때문에 술폰화정도가 낮은 결과를 초래하게 된다. PPS가 술폰화됨에 따라 유리전이돈도(T g)가 증가하였고, 초기 열분해 온도는 감소하였다.

In theis work th soluble poly[methyl[4-(phenylthio)phenyl]sulfonium trifluoromethanesulfonate] (PPST) in organic solvents was synthesized by self-condensation polymerization of methyl-(phenylthio)phenyl sulfoxide. Sulfonated poly(phenylene sulfide) (SPPS) was prepared by sulfonating PPST with fumic sulfonic acid (10% SO₃-H₂SO₄)and demethylation with aqueous NaOH solution. The optimum conditions of the slfonation of PPS whih was determined by ion exchange capacity and IR absorbance were reaction time of 12hr and reaction temperature at 150 ℃. Ion exchange capacties for SPPS measured by IR spectroscopy was 11.5 meq/g and the degree of sulfonation per repeating unit was 2.19. The sulfonation reaction above 150 ℃ resulted in a decrease in the degree of sulfonation because the crosslinking reaction took place through dehydration between the sulfonic acid and near phenyl groups. As PPS was sulfonated, glass temperature (Tg) increased and initial degradation temperature decreased.

Keywords:thermostable ion exchanger;sulfonated poly(phenylene sulfide);poly(phenylene sulfide)

[References]

Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)
Hochenstein WP, Mark H, J. Polym. Sci., 1, 126 (1946)
Koch W, Heitz W, Macromol. Chem., 184, 779 (1983)
Hawkins RT, Macromolecules, 9, 189 (1976)
Hill HW, Brady DG, Polym. Eng. Sci., 16, 832 (1976)
Short JN, Hill HW, Chem. Tech., 2, 481 (1972)
Hill HW, Brady DG, J. Coat. Technol., 49, 627 (1977)
Hill HW, Edmonds JT, Adv. Chem. Ser., 60, 129 (1973)
Idel K, Merten J, U.S. Patent, 4,303,781 (1979)
Asakura T, Noguchi Y, Kobayashi H, U.S. Patent, 4,286,018 (1990)
Tsuchida E, Yamamoto K, Jikei M, Nishide H, Macromolecules, 23, 2101 (1990)
Gagnon DG, Capistran JD, Karasz FE, Lenz RW, Polym. Bull., 12, 293 (1984)
Ballard DG, Courtis A, Shirley IM, Taylor SC, Macromolecules, 21, 294 (1988)
Kelsey DR, Robeson LM, Clendinning RA, Blackwell SC, Macromolecules, 20, 1204 (1987)
Lyon KR, McGrath JE, Geibel JF, Polym. Mater. Sci. Eng., 65, 249 (1995)
Tsuchida E, Shouji E, Yamamoto K, Macromolecules, 26, 7144 (1993)
Miyatake K, Iyotani H, Yamamoto K, Tsuchida E, Macromolecules, 29(21), 6969 (1996)
Hisayama H, Takamizawa Y, Higouzaki T, Chem. Soc. Jpn., 10, 1350 (1974)
Noshay A, Robeson LM, J. Appl. Polym. Sci., 20, 1885 (1976)

[Referenced By]

[1] Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)

[2] Hochenstein WP, Mark H, J. Polym. Sci., 1, 126 (1946)

[3] Koch W, Heitz W, Macromol. Chem., 184, 779 (1983)

[4] Hawkins RT, Macromolecules, 9, 189 (1976)

[5] Hill HW, Brady DG, Polym. Eng. Sci., 16, 832 (1976)

[6] Short JN, Hill HW, Chem. Tech., 2, 481 (1972)

[7] Hill HW, Brady DG, J. Coat. Technol., 49, 627 (1977)

[8] Hill HW, Edmonds JT, Adv. Chem. Ser., 60, 129 (1973)

[9] Idel K, Merten J, U.S. Patent, 4,303,781 (1979)

[10] Asakura T, Noguchi Y, Kobayashi H, U.S. Patent, 4,286,018 (1990)

[11] Tsuchida E, Yamamoto K, Jikei M, Nishide H, Macromolecules, 23, 2101 (1990)

[12] Gagnon DG, Capistran JD, Karasz FE, Lenz RW, Polym. Bull., 12, 293 (1984)

[13] Ballard DG, Courtis A, Shirley IM, Taylor SC, Macromolecules, 21, 294 (1988)

[14] Kelsey DR, Robeson LM, Clendinning RA, Blackwell SC, Macromolecules, 20, 1204 (1987)

[15] Lyon KR, McGrath JE, Geibel JF, Polym. Mater. Sci. Eng., 65, 249 (1995)

[16] Tsuchida E, Shouji E, Yamamoto K, Macromolecules, 26, 7144 (1993)

[17] Miyatake K, Iyotani H, Yamamoto K, Tsuchida E, Macromolecules, 29(21), 6969 (1996)

[18] Hisayama H, Takamizawa Y, Higouzaki T, Chem. Soc. Jpn., 10, 1350 (1974)

[19] Noshay A, Robeson LM, J. Appl. Polym. Sci., 20, 1885 (1976)