화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Polymer(Korea), Vol.21, No.2, 193-200, March, 1997
Export Citation
결정성 폴리스티렌의 제조 및 성질 Ⅲ.공중합
Preparation and Properties of Crystalline Polystyrene Ⅲ.Copolrmerization
이동호, 윤근병, 이태영, 노석균
초록
Mononuclear half-titanocene인 CpTiC13, IndTiC13 및 Cp*TiC13 그리고 siloxane-bridged dinuclear half-titanocene인 Cl3Ti-CpSi(CH3)2-O-Si(CH3)2-O-Si-(CH3)2Cp-TiC13 등과 modified methylaluminoxane 공촉매를 이용한 스티렌과 에틸렌, p-메틸스티렌 및 비닐나프탈렌 등과의 공중합에서 각 촉매에 따른 중합거동과 생성 중합체의 성질을 조사하였다. 스티렌과 에틸렌의 공중합에서는 주로 단독중합체의 혼합물이 생성되고 극히 소량의 공중합체를 얻을 수 있었다. 따라서 이들 촉매는 스티렌과 에틸렌의 공중합에 비효과적이었다. 스티렌과 p-메틸스티렌의 공중합에서는 p-메틸스티렌의 양이 증가됨에 따라 촉매활성이 향상되었고, 공중합체의 녹는점 (Tm)과 초기분해온도(Tdi)는 감소하였다. 그리고 p-메틸스티렌의 양에 따라 공중합체의 Tm과 Tdi의 차이를 조정할 수 있었다. 스티렌파 비닐나프탈렌의 공중합에서는 소량의 비닐나프탈렌 첨가로 촉매활성 및 공중합체의 Tm이 크게 감소하였다.
With mononuclear half-titanocenes such as CpTiCl3, IndTiCl3, Cp(*)TiCl3 and a siloxane-bridged dinuclear half-titanocene, Cl3Ti-CpSi(CH3)2-O-Si(CH3)2-O-Si-(CH3)2CpTiCl3 cocatalyzed by modified methylaluminoxane, the copolymerization of styrene (St) with ethylene (E), p-methylstyrene (PMS) and vinyl naphthalene (VN) was carried out, and copolymerization behavior as well as properties of the obtained polymer were examined for each catalyst. In copolymerization of St and E, the mixture of homopolymers, syndiotactic polystyrene and polyethylene, was obtained mainly with a less amount of copolymer, which intimated that these titanocenes are unsuitable for St/E copolyemer preparation. By copolymerization of St with PMS, the copolymer was prepared with a enhanced catalyst activity. The melting temperature (Tm) and initial decomposition temperature (Tdi) of copolymer decreased and the difference of Tm and Tdi could be controlled with the amount of added PMS. For copolymerization of St and VN, the catalyst activity and Tm of copolymer decreased drastically even with a small amount of VN.
Keywords:styrene copolymerization;mononuclear and dinuclear titanocenes;catalyst activity;transition temperature
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