Article
  • Polymerization Behavior and Thermal Properties of PPS and Poly( arylene sulfide)s
  • Lee SC, Park LS
  • PPS와 Poly(arylene sulfide)s의 중합반응 특성 및 열적성질
  • 이수창, 박이순
Abstract
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℃.

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.

Keywords: poly(p-phenylene sulfide); poly(arylene sulfide)s; reaction conditions; thermal properties

References
  • 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)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1995; 19(6): 867-874

    Published online Nov 25, 1995