화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.19, No.5, 707-714, September, 1995
Export Citation
PPS, PBS 및 PPSE의 중합반응 특성 및 열적성질
Polymerization Behavior of PPS, PBS, and PPSE Thermal Properties
이수창, 박이순
초록
Sodium sulfide를 p-dichlorobenzene과 중합시켜 poly(p-phenylene sulfide), PPS를 그리고 4,4'-dibromobipheny1 또는 4-bromophenylether와 중합시켜 각각 poly(p-biphenylene sufide), PBS 및 Poly(p-phenylene sulfide ether), PPSE를 합성하였으며 중합온도, 단량체 mole비, 중합계 내 물의 함량이 중합체의 수율 및 분자량에 미치는 영향을 비교 조사하였다. 또한 이들 최적 중합 조건을 토대로 하여 PPS/PBS 및 PPS/PPSE의 공중합 반응 특성에 대해서도 조사하였다. 먼저 중합온도에 있어서 PPS가 250℃에서 최고 수율을 나타낸 반면에 PBS 및 PPSE는 각각 270℃와 290℃에서 최대 수율을 보였으며, 이들 모두 단량체의 stoichiometric unbalance에 대해 통상의 축중합보다 훨씬 덜 민감한 특성을 보였다. 또 첨가제로서 물의 함량이 변함에 따라 PPS, PBS 및 PPSE는 모두 [H2O]/[sodium sulfide]=9:1에서 최고의 수율을 보였다. 이들 중합체의 분자량은 1-chloronaphthalene을 eluent로 고온(210℃) GPC를 사응하여 측정하였고, 열적 성질은 DSC 및 TGA로 조사하였다. DSC 열분석으로 부터 PPS와 PPSE는 융점이 각각 279℃ 및 195℃인 결정성 고분자의 특성을 나타내었고, TGA 실험 결과 열안정성은 PPSE
Poly(p-phenylene sulfide) (PPS), poly(p-biphenylene sulfide) (PBS), and poly(p-phenylene sulfide ether) (PPSE) were synthesized from sodium sulfide and p- dichlorobenzene, 4,4'-dibromobipheny1, and 4-bromopheny1 ether, respectively, using N-methyl pyrrolidinone (NMP) as solvent under high temperature (≥250℃) and pressure (≥ 150psi). From the study of reaction conditions, the optimum reaction temperatures were found to be increased in the ordeal of 250℃ < 270℃ < 290℃ for the synthesis of PPS, PBS, and PPSE. All these polymer forming reactions showed less influence on stoichiometric imbalance of corresponding monomer ratios than normal polycondensation reactions such as polyesterification or polyamidation. The effect of water as an additive in the NMP solvent was found to give maximum yields of all three polymers at [H2O]/[sodium sulfide]= 9 : 1 level. The copolymerization behavior of PPS/PBS and PPS/PPSE combination was also studied according to the optimum homopolymerization reaction conditions. The molecular weights of polymers were determined by the high temperature (210℃) GPC with 1-chloronaphthalene as eluent. Thermal analysis (DSC) of polymers showed Tm= 279℃, 195℃ for PPS and PPSE, respectively. The thermal stability of polymers was found to be increased in the order of PPSE
Keywords:poly(p-phenylene sulfide);poly(arylene sulfide);poly(p-phenylene sulfide ether);poly(p-biphenylene sulfide);thermal properties
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