화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.19, No.6, 867-874, November, 1995
Export Citation
PPS와 Poly(arylene sulfide)s의 중합반응 특성 및 열적성질
Polymerization Behavior and Thermal Properties of PPS and Poly( arylene sulfide)s
이수창, 박이순
초록
Sodium sulfide nonahydrate(SS)를 p-dichlorobenzene (DCB)과 중합시켜 poly(p-phenylene sulfide), PPS를 그리고 4-chlorophenylsulfone (CPS) 또는 4,4'-dichlorobenzophenone (DCBP)와 중합시켜 poly(p-phenylene sulfide sulfone), PPSS 및 poly(p-phenylene sulfide ketone), PPSK를 각각 합성하고 중합온도, 단량체 몰비, 중합계내 물의 함량 등이 중합체들의 수율 및 분자량에 미치는 영향을 비교 조사하였다. 이들 중합체의 분자량은 1-chloronaphthalene을 이동상으로 고온(210℃) GPC를 사용하여 측정하였고, 열적 성질은 DSC 및 TGA로 조사하였다. 먼저 중합온도에 있어서는 PPS가 250℃에서 최고 수율을 보인 반면, PPSS 및 PPSK는 200℃에서 최대 수율을 나타내었다. 단량체 몰비에 있어서는 [SS]/[DCB]의 몰비가 0.75/1∼1.25/1로 변하여도 83% 이상의 높은 수율을 나타낸 PPS의 경우와는 달리, PPSK(특히 PPSS)는 매우 민감하게 수율이 변하였다. 또 첨가제로서 물 함량이 변함에 따라 PPS 및 PPSK는 크게 수율이 변하지 않았지만 PPSS는 [H2O]/[SS]=4.5/1 이하에서는 중합체가 얻어지지 않았으며 13.5/1에서 최고 분자량을 보였다. DSC 열분석으로부터 PPSK(Tm=344℃)는 PPS(Tm=279℃)와 마찬가지로 결정성 고분자이었고 PPSS(Tg=201℃)는 무정형 고분자였다.
Poly(p-phenylene sulfide), PPS and related polymers such as poly(p-phenylene sulfide sulfone), PPSS and poly(p-phenylene sulfide ketone), PPSK were prepared from sodium sulfide (SS) and three different comonomers p-dichlorobenzene (DCB), 4-chlorophenylsulfone(CPS) and 4,4'-dichlorobenzophenone(DCBP), respectively, employing N-methyl pyrrolidinone (NMP) as solvent under high temperature (250∼290 ℃) and pressure (120∼180 psi). The molecular weight of polymers were determined by high temperature (210℃) GPC with 1-chloronaphthalene as eluent against polystyrene standards. The thermal transition temperatures and thermal stability of polymers, were studied by DSC and TGA. PPS showed maximum yield at 250℃ of reaction temperature, whereas PPSS and PPSK which have electron-withdrawing groups gave maximum yield at 200℃. As for the stoichiometry of comonomers, PPS exhibited highest yield of 83% in the range of [SS]/[DCB]=0.75/1∼1.25/1. The yield of PPSK and especially PPSS were highly sensitive to stoichiometric ratio of [SS]/[DCBP] and [SS]/[CPS] decreased sharply. As for the content of water as additive in the reaction mixture, PPS and PPSK showed maximum yield at [H2O]/[Na2S]=9/1. PPSS could not be obtained under [H2O]/[Na2S]=4.5/1, but the maximum yield was shown at [H2O]/[Na2S]=13.5/1. From the DSC study, PPS and PPSK were crystalline materials with Tm=279 and Tm=344℃, respectively. PPSS was amorphous material with only Tg being detected at 210℃.
Keywords:poly(p-phenylene sulfide);poly(arylene sulfide)s;reaction conditions;thermal properties
  1. Brady DG, J. Appl. Polym. Sci., 20, 2541 (1976) 
  2. Hill HW, Brady DG, Chem. Tech., 49, 33 (1977)
  3. Short JN, Hill HW, Chem. Tech., 2, 481 (1972)
  4. Lenz RW, Handlovits CE, Smith HA, J. Polym. Sci., 58, 351 (1962) 
  5. Tsuchida E, Nishide H, Yammamoto K, Jikei M, Nishide H, Macromolecules, 22, 4138 (1989) 
  6. Tsuchida E, Suzuki F, Shouji E, Yamamoto K, Macromolecules, 27(4), 1057 (1994) 
  7. Wang ZY, Hey AS, Macromolecules, 24, 333 (1991) 
  8. Lyon KR, McGrath JE, Geibel JF, Polym. Mater. Sci. Eng., 65, 249 (1991)
  9. Durvasula VR, Stuber FA, Bhattacharjee D, J. Polym. Sci. A: Polym. Chem., 27, 661 (1989) 
  10. Senn DR, J. Polym. Sci. A: Polym. Chem., 32(6), 1175 (1994) 
  11. Fahey DR, Ash CE, Macromolecules, 24, 4242 (1991) 
  12. Park LS, Seo KH, Chang JG, Kwon YH, Han SK, Cha IH, Polym.(Korea), 13(10), 866 (1989)
  13. Koch W, Heitz W, Makromol. Chem., 184, 779 (1983) 
  14. Annenkova VZ, Zysokomol. Soed. Ser. B, 28, 137 (1986)
  15. Fahey DR, Hemsley HD, Ash CE, Senn DR, Polym. Mater. Sci. Eng., 67, 468 (1992)
  16. U.S. Patent, 4,645,826, to Kureha Co. (1977)