고분자량 PPS의 합성 및 물성

박이순; 이수창; 이태형; 전재영

Polymer(Korea), Vol.21, No.3, 369-374, May, 1997

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고분자량 PPS의 합성 및 물성

Synthesis of High Molecular Weight PPS and Its Properties

박이순, 이수창, 이태형, 전재영

초록

선형 고분자량 PPS의 합성을 위한 중합 조건의 조사를 통하여 최적 조건은 단량체의 농도 2.5mole/L, 첨가제로서의 NaOH 투입량 0.01∼0.03mo1/1mol Na₂S, 단량체 몰비 ([Na₂S]/[DCB]) 1.01/1∼1/1.03로 나타났다. 선형 PPS의 중합조건을 토대로 가지형 PPS의 합성시 TCB의 함량이 증가됨에 따라 분자량(M_w)은 TCB가 Na₂S 1 mole 대비 0.005, 0.01, 0.02mo1로 증가할수록 분자량(M_w)이 각각 25300, 49100 및 144000g/mo1로 현저히 증가하였다. TCB 단량체를 이용하여 210℃ 1-chloronaphthalene 용매에 가용인 성질을 가진 가지형 구조의 PPS를 합성하면 가공성의 향상(T_m의 감소), 내열성의 향상(T_g의 증가) 등의 이점이 있으며, 선형 PPS 대비 결정성의 감소는 약 25% 정도로 크게 나타나지 않았다.

From the reaction condition study of linear high molecular weight poly(p-phenylene sulfide) (PPS), the optimum conditions were found to be monomer concentration 2.5 mol/L NMP, NaOH content as additive 0.01 ∼0.03mo1/1mol Na₂S, and [Na₂S]/[DCB]mol ratio 1.0l/l∼1/1.03. Under these reaction conditions, substitution of a small amount of 1,4-dichlorobenzene (DCB) with 1,2,4-trichlorobenzene (TCB), for example 0.005, 0.01, 0.02 mol TCB, gave branched type PPS with M_w of 25300, 49100, 144000g/mol, respectively. Branched type PPS which was competely soluble in 1-chloronaphthalene at 210℃ had lower T_m higher T_g and 25% lower degree of crystallinity compared to linear PPS.

Keywords:poly(p-phenylene sulfide);PPS;high molecular weight;branched type PPS

[References]

Margolis JM, "Engineering Thermoplastics," Marcel Dekker, New York (1985)
Sandler SR, Karo W, "Polymer Synthesis," vol. 3, Academic Press, New York (1980)
Edmonds JT, Hill HW, U.S. Patent, 3,354,129 (1967)
Lenz RW, Handlovits CE, Smith HA, J. Polym. Sci., 58, 351 (1962)
Tsuchida E, Nishide H, Yamamoto K, Yoshida S, Macromolecules, 20, 2030 (1987)
Tsuchida E, Nishide H, Yamamoto K, Yoshida S, Macromolecules, 20, 2315 (1987)
Tsuchida E, Suzuki F, Shouji E, Yamamoto K, Macromolecules, 27, 1057 (1994)
Fagerburg DR, Watkins JJ, Lawrence PB, Macromolecules, 24, 4033 (1991)
Wang YF, Hay AS, Macromolecules, 29(14), 5050 (1996)
Stacy CJ, J. Appl. Polym. Sci., 32(32), 3959 (1986)
Wejchan-Judek M, Perkowska B, Polym. Degrad. Stabil., 38, 261 (1992)
Ito M, Onda M, Ona S, Inoue H, Bull. Chem. Soc. Jpn., 63, 1484 (1990)
Campbell RW, Yelton HD, U.S. Patent, 4,024,118 (1977)
Campbell RW, Edmonds JT, U.S. Patent, 4,038,259 (1977)
Campbell RW, U.S. Patent, 3,919,177 (1975)
Iizuka Y, Iwasaki T, Katto T, Shiiki Z, U.S. Patent, 4,645,826 (1987)
Brady DG, J. Appl. Polym. Sci., 20, 2541 (1976)
Lee SC, Park LS, Polym.(Korea), 19(5), 707 (1995)
Lee SC, Park LS, Polym.(Korea), 19(6), 867 (1995)
Port AB, Still RH, J. Appl. Polym. Sci., 24, 1145 (1979)
Fahey DR, Ash CE, Macromolecules, 24, 4242 (1991)

[Referenced By]

[1] Margolis JM, "Engineering Thermoplastics," Marcel Dekker, New York (1985)

[2] Sandler SR, Karo W, "Polymer Synthesis," vol. 3, Academic Press, New York (1980)

[3] Edmonds JT, Hill HW, U.S. Patent, 3,354,129 (1967)

[4] Lenz RW, Handlovits CE, Smith HA, J. Polym. Sci., 58, 351 (1962)

[5] Tsuchida E, Nishide H, Yamamoto K, Yoshida S, Macromolecules, 20, 2030 (1987)

[6] Tsuchida E, Nishide H, Yamamoto K, Yoshida S, Macromolecules, 20, 2315 (1987)

[7] Tsuchida E, Suzuki F, Shouji E, Yamamoto K, Macromolecules, 27, 1057 (1994)

[8] Fagerburg DR, Watkins JJ, Lawrence PB, Macromolecules, 24, 4033 (1991)

[9] Wang YF, Hay AS, Macromolecules, 29(14), 5050 (1996)

[10] Stacy CJ, J. Appl. Polym. Sci., 32(32), 3959 (1986)

[11] Wejchan-Judek M, Perkowska B, Polym. Degrad. Stabil., 38, 261 (1992)

[12] Ito M, Onda M, Ona S, Inoue H, Bull. Chem. Soc. Jpn., 63, 1484 (1990)

[13] Campbell RW, Yelton HD, U.S. Patent, 4,024,118 (1977)

[14] Campbell RW, Edmonds JT, U.S. Patent, 4,038,259 (1977)

[15] Campbell RW, U.S. Patent, 3,919,177 (1975)

[16] Iizuka Y, Iwasaki T, Katto T, Shiiki Z, U.S. Patent, 4,645,826 (1987)

[17] Brady DG, J. Appl. Polym. Sci., 20, 2541 (1976)

[18] Lee SC, Park LS, Polym.(Korea), 19(5), 707 (1995)

[19] Lee SC, Park LS, Polym.(Korea), 19(6), 867 (1995)

[20] Port AB, Still RH, J. Appl. Polym. Sci., 24, 1145 (1979)

[21] Fahey DR, Ash CE, Macromolecules, 24, 4242 (1991)