내열성 이온교환체로서 Poly(phenylene sulfide sulfonic acid)의 합성

김남진; 손원근; 김동철; 박정기; 송해영

Polymer(Korea), Vol.20, No.2, 201-207, March, 1996

Export Citation

내열성 이온교환체로서 Poly(phenylene sulfide sulfonic acid)의 합성

Synthesis of Poly(phenylene sulfide slfonic acid) as Thermostable Ion Exchanger

김남진, 손원근, 김동철, 박정기, 송해영

초록

이온교환수지지지체인 oligo(p-phenylene sulfide) (OPS)는 diphenyl disulfide의 양이온 산화중합에 의해 합성되었다. Sulfonated oligo(p-phenylene sulfide) (SOPS) 유도체는 OPS를 진한 황산으로 술폰화하여 합성하였으며, 술폰화는 1200cm^-1에서 술폰산기에 의한 강한 흡수대에 의해 확인되었으며. 이때의 술폰산기 도입 최적반응조건은 IR 흡광도와 이온교환용량 값에 의해 반응시간 11시간, 반응온도 110℃, 그리고 9N-H₂SO₄등으로 나타났다. 또한 sulfonated poly(phenylene sulfide) (SPPS)는 보다 높은 내열성 향상을 위해 SOPS와 1,4-diiodobenzene을 반옹시켜 얻었다. 이들의 이온교환용량 값은 SOPS가 11.0, SPPS가 6.1meq/g이었다. 열안정성이 증진된 SPPS는 이온교환용량값과 술폰산기의 IR 홉광도는 감소하지만 TG 분석에서 10% 중량감소 온도 (T_d10%)는 증가하였다. 이들 결과는 내열성 이온교환수지로서 사용가능성을 증가시켰다. 이외에 금속이온흡착능에 관하여 논의하였다.

O1igo(p-phenylene sulfide) (OPS) as ion exchanger matrix was synthesized by cationic oxidative polymerization of diphenyl disutfide. Sulfonated oligo (p-phenylene sulfide ) (SOPS) derivative was prepared b)r sulfonating OPS with concentrated sulfuric acrid, the surfonation was confirmed by the presence of a high intensity band at 1200 cm^-1 due to the SO₃H group in arylene sulfonic acid, and the optimum reactive conditions introducing sulfonic acid group, which was obtained by IR absorbance and ion exchange capacity, indicated to reaction Time 11h, reaction temp. 110℃ and 9N-H₂SO₄ Also Sulfonated poly(phenylene sulfide) (SPPS) was obtained by reacting SOPS with 1,4-diiodobenzene to improve the higher thermostability. These ion exchange capacity were 11.0 meq/g for SOPS and 6.1 meq/g for SPPS. SPPS improved thermostability was decreased ion exchange capacity and IR absorbance of sulfonic acid group but increased T_d10%(temp. for 10% weight loss) in TG analysis. These results increased the possibility of use as thermostable cationic exchange resin. In addition, adsorption of various metal ions was discussed.

Keywords:thermostable poly(phenylene sulfide sulfonic acid) ion exchanger

[References]

Rabolt JF, Clarke TC, Kanazawa KK, Reynolds JR, Street GB, J. Chem. Soc.-Chem. Commun., 347 (1980)
Chance RR, Shacklette LW, Miller GG, Ivory DM, Sowa JM, Elsenbaumer RL, Baughman RH, J. Chem. Soc.-Chem. Commun., 348 (1980)
Schoch KF, Chance JF, Pfeiffer KF, Macromolecules, 18, 2389 (1985)
Kazama S, Arai K, Maekawa E, Synth. Met., 15, 299 (1986)
Kazama S, Synth. Met., 16, 77 (1986)
Shimizu H, Kanetsuna H, Tanabe Y, Polym. J., 19, 915 (1987)
Fox DW, Popkin S, U.S. Patent, 3,259,592 (1966)
Kimura SG, Ind. Eng. Chem. Prod. Res. Dev., 10(3), 335 (1971)
Chludzinski PJ, Fickett AP, Lacanti AB, Am. Chem. Soc. Div. Polym. Chem. Polym. Prepr., 12(2), 276 (1971)
Ward WJ, Salemme RM, U.S. Patent, 3,780,496 (1973)
Noshay A, Robenson LM, J. Appl. Polym. Sci., 20, 1885 (1976)
Ueno J, Watanabe M, Tanaka Y, Japan Patent, 24998 (1965)
Kibler CJ, Lappin GR, U.S. Patent, 373,487 (1973)
Salle R, Sillion B, FR Patent, 2212356 (1974)
Son WG, Moon SM, Baek JH, Kim DC, Park JK, Song HY, Polym.(Korea), 19(4), 433 (1995)
Song HY, Polym.(Korea), 18(3), 292 (1994)
Oyaizu K, Katoh J, Suzuki F, Jikei M, Yamamoto K, Nishide H, Tsuchida E, Polym. Adv. Technol., 2, 155 (1991)
Kim DW, Kim KS, Kim HS, J. Korean Chem. Soc., 30, 60 (1986)
Heigh J, Bell M, White J, Anal. Chem., 19, 293 (1947)
Joo CR, "Analytical Chemistry," 2nd Ed., p. 570, Heyong Sul Pub. Comp. (1975)
Park GC, "Quantitative Analytical Chemistry,"5th ed., p. 223, Tam Ku Dang (1976)
Lee MY, "Quantitative Analytical Chemistry," p. 235, Dong Meyong, Pub. Comp. (1967)
Tsuchida E, Yamamoto K, Nishide H, Yoshida S, Jikei M, Macromolecules, 23, 2101 (1990)
Tsuchida E, Yamamoto K, Nishide H, Jikei M, Macromolecules, 23, 930 (1990)
Song HY, Miyatake K, Yamamoto K, Polym. Adv. Technol., 5, 309 (1994)
Mark HF, Bikales NM, Overberger CG, Menges G, Kroschwitz JI, "Encyclopedia of Polymer Science and Engineering," vol. 8, p. 363, 365, A Wiley-Interscience Pub. (1988)

[Referenced By]

[1] Rabolt JF, Clarke TC, Kanazawa KK, Reynolds JR, Street GB, J. Chem. Soc.-Chem. Commun., 347 (1980)

[2] Chance RR, Shacklette LW, Miller GG, Ivory DM, Sowa JM, Elsenbaumer RL, Baughman RH, J. Chem. Soc.-Chem. Commun., 348 (1980)

[3] Schoch KF, Chance JF, Pfeiffer KF, Macromolecules, 18, 2389 (1985)

[4] Kazama S, Arai K, Maekawa E, Synth. Met., 15, 299 (1986)

[5] Kazama S, Synth. Met., 16, 77 (1986)

[6] Shimizu H, Kanetsuna H, Tanabe Y, Polym. J., 19, 915 (1987)

[7] Fox DW, Popkin S, U.S. Patent, 3,259,592 (1966)

[8] Kimura SG, Ind. Eng. Chem. Prod. Res. Dev., 10(3), 335 (1971)

[9] Chludzinski PJ, Fickett AP, Lacanti AB, Am. Chem. Soc. Div. Polym. Chem. Polym. Prepr., 12(2), 276 (1971)

[10] Ward WJ, Salemme RM, U.S. Patent, 3,780,496 (1973)

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

[12] Ueno J, Watanabe M, Tanaka Y, Japan Patent, 24998 (1965)

[13] Kibler CJ, Lappin GR, U.S. Patent, 373,487 (1973)

[14] Salle R, Sillion B, FR Patent, 2212356 (1974)

[15] Son WG, Moon SM, Baek JH, Kim DC, Park JK, Song HY, Polym.(Korea), 19(4), 433 (1995)

[16] Song HY, Polym.(Korea), 18(3), 292 (1994)

[17] Oyaizu K, Katoh J, Suzuki F, Jikei M, Yamamoto K, Nishide H, Tsuchida E, Polym. Adv. Technol., 2, 155 (1991)

[18] Kim DW, Kim KS, Kim HS, J. Korean Chem. Soc., 30, 60 (1986)

[19] Heigh J, Bell M, White J, Anal. Chem., 19, 293 (1947)

[20] Joo CR, "Analytical Chemistry," 2nd Ed., p. 570, Heyong Sul Pub. Comp. (1975)

[21] Park GC, "Quantitative Analytical Chemistry,"5th ed., p. 223, Tam Ku Dang (1976)

[22] Lee MY, "Quantitative Analytical Chemistry," p. 235, Dong Meyong, Pub. Comp. (1967)

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

[24] Tsuchida E, Yamamoto K, Nishide H, Jikei M, Macromolecules, 23, 930 (1990)

[25] Song HY, Miyatake K, Yamamoto K, Polym. Adv. Technol., 5, 309 (1994)

[26] Mark HF, Bikales NM, Overberger CG, Menges G, Kroschwitz JI, "Encyclopedia of Polymer Science and Engineering," vol. 8, p. 363, 365, A Wiley-Interscience Pub. (1988)