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상세 정보
서명 / 저자	담지형 지글러-나타 촉매에 의한 프로필렌 중합에서 촉매활성점에 관한 연구 = A study on the catalytic active site of propylene polymerization over supported ziegler-natta catalyst / 최경우.
저자명	최경우 ; Choi, Kyung-Woo
발행사항	[대전 : 한국과학기술원, 1997].

online access
Online Access	/thesis_pdf_01/1997/1997D00090... 원문

서가 정보
등록번호	소장위치/청구기호	도서상태	반납예정일
8007422	학술문화관(문화관) 보존서고 DCHE 97006 SMS전송	이용가능 대출가능확인

초록

  In order to elucidate the nature of active site, the correlation between the active site of catalyst and the polymerization mechanism was investigated by using different types of catalyst system. 
  The effects of electron donor, i.e.; ethyl-benzoate(EB), di-n-butyl phthalate(DNBP) and phenyl-triethoxysilane(PTES), as internal and/or external donor on the catalytic activity in propylene polymerization over butylmagnesium chloride (BuMgCl)-based titanium catalysts have been investigated in terms of activity and stereospecificity. It was found that the polymerization rates were well correlated by a kinetic model where the activation and deactivation were assumed to be 1st and 2nd order, respectively. The catalyst with DNBP as internal donor showed the highest propagation rate constant($k_p$) and lowest deactivation rate constants($k_d$). When the PTES was used as an internal donor, the higher $k_d$ value was obtained. It seems that the titanium species in the catalytic system containing PTES as internal donor was easily reduced by triethyl aluminum(TEA). X-ray diffraction(XRD) pattern of the catalytic system including PTES as internal donor showed that $TiCl_4$ did not seem to diffuse into the interlayer of the $MgCl_2$-support matrix and did not show the highly disordered form compared with other internal donors. From the microstructure analysis of polypropylene, it was believed that the stereoregul- arity depended on the nature of internal donor and was controlled by the extent of reversible interconversion between the isospecific(predominantly) and the syndiospecific(predominantly) sites. In the case of PTES as an external donor, a number of syndiotactic stereoblocks were found for the polypropylene soluble in boiling heptane and showed less interchangeability between these active sites, resulting in the selective activation of both types of active sites. 
  Propylene was polymerized in the presence of the isospecific $rac-Et[Ind]_2ZrCl_2$(A) (Et:ethyl, Ind:indenyl) catalyst impregnated on the $SiO_2$ and $SiO_2$/MAO(MAO:methyl-aluminoxane) supports. The resulting catalysts using TMA/$Ph_3C \cdot B(C_6F_5)_4$ (TMA : trimethyl- aluminum) instead of MAO as cocatalyst showed fairly good yields and properties for isotactic polypropylene, i.e.; higher isotacticity as well as higher melting point compared with the polypropylene produced by homogeneous zirconocene catalyst. From the $^{13}C$-NMR analysis, isospecific polypropylene obtained by the catalytic system(A/MAO/$SiO_2$-TMA/ $[Ph_3C] [B(C_6F_5)_4]$) was found to have high regioregularity, and its microstructure was well correlated with enantiomorphic site model. Therefore active sites formed in the $SiO_2$ supported zirconocene catalysts seem to have more stereo-rigid single site character as compared with those in the homogeneous counterparts.

상세 정보
형태사항	xi, 165 p. : 삽도 ; 26 cm
언어	한국어
일반주기	부록 수록 저자명의 영문표기 : Kyung-Woo Choi 지도교수의 한글표기 : 임선기 지도교수의 영문표기 : Son-Ki Ihm
학위논문	학위논문(박사) - 한국과학기술원 : 화학공학과,
서지주기	참고문헌 : p. 105-121
주제	지글러-나타 촉매 프로필렌 중합 전자공여체 메탈로센 Ziegler-natta catalyst Propylene polymerization Donor Metallocene
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이전 다음

- (우리가 꼭 알아야 할) 지식속의 지식 80가지
- 매크론 ,마카엘
- 001.3 남44ㅁ
- 담지형 지글러-나타 촉매에 의
- 최경우
- {DCHE 97006
- 인공 신경망의 생물공정 시스템
- 박명석
- {DCHE 97008

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