서지주요정보
프로필렌 중합용 지글러-나타 촉매의 특성 = Characteristics of ziegler-natta catalysts for propylene polymerization
서명 / 저자 프로필렌 중합용 지글러-나타 촉매의 특성 = Characteristics of ziegler-natta catalysts for propylene polymerization / 송원득.
저자명 송원득 ; Song, Won-Deuk
발행사항 [대전 : 한국과학기술원, 1993].
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등록번호

8003305

소장위치/청구기호

학술문화관(문화관) 보존서고

DCHE 93013

SMS전송

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초록정보

Different kinds of supports and catalysts for propylene polymerization were prepared by ball-milling with different mole ratio (0.1~0.8) of ethyl benzoate(EB)/$MgCl_2$ and different Ti content in the catalyst (1~8 wt%) to understand the nature of the $MgCl_2-EB-TiCl_4$ complex. Carbonyl (C=O) bonds of EB in the supports and catalysts were investigated through infrared(IR) spectrophotometer. When small amount of EB (EB/Mg<0.4) was added to the $MgCl_2$, the carbonyl bonds were detected simultaneously at $\nu_1=1690$ and $\nu_2=1636cm^{-1}$. With the amount of EB in the support increasing, however, the carbonyl bond at $\nu_2$=1636cm^{-1}$ disappeared gradually while the one at $\nu_1=1690cm^{-1}$ remained. If small amount of $TiCl_4$ is impregnated to the support with carbonyl band at $\nu_1$ and $\nu_2$, only one carbonyl characteristic band of was detected at $\nu_1^\prime=1685cm^{-1}$, which is near to $\nu_1$. With large amount of $TiCl_4$, the bands for carbonyl group were detected simultaneously at $\nu_1^\prime=1685$, $\nu_3=1600$ and $\nu_4=1564cm^{-1}$. For the support with carbonyl band only at $\nu_1=1690cm^{-1}$, the activation could be made even with small amount of $TiCl_4$, and the carbonyl bands were also identified simultaneously at $\nu_1^\prime$, $\nu_3$ and $\nu_4$. From these results, a model for the $MgCl_4-EB-TiCl_4$ complex was proposed as follow. The bands at $\nu_1=1690cm^{-1}$ and $\nu_2=1636cm^{-1}$ represent the characteristic peaks of linear $EB-MgCl_2$ and bridge and $EB<^{MgCl_2}_{MgCl_2}$ complex, respectively. With small amount of EB added on $MgCl_2$, both(linear and bridged) $EB/MgCl_2$ complexes could be formed. Further increase in the amount of EB will make all of the complexes to be linear type. The active site for propylene polymerization seems to be the $TiCl_4$-$MgCl_2$ complex generated by activation with $TiCl_4$ of the bridged $EB<^{MgCl_2}_{MgCl_2}$ complex, part of which is converted to the linear $EB-MgCl_2$ complex. However, the linear $EB-MgCl_2$ complex will make inactive $EB-TiCl_4$ complex. The activity pattern could be well interpreted with the aforementioned argument, and there seems to be optimum composition of EB and $TiCl_4$ for the $MgCl_2$ support, respectively ; i.e., $EB/MgCl_2<0.4$, $Ti< 4$wt%. Ti valence state was investigated with electron paramagnetic resonance(EPR) spectrum. With increasing Ti contents (1, 2, 4 and 8 wt%), the peak intensity at g=1.97 decreased slightly but the peak at g=1.94 increased. It is known for that the peaks at g=1.94 and 1.97 represent the $Ti^{+3}$ states for the Ti-Ti and Mg-Ti cluster, respectively. Addition of $TiCl_4$ seems to favor the formation of inactive Ti-Ti cluster rather than active Mg-Ti cluster.

서지기타정보

서지기타정보
청구기호 {DCHE 93013
형태사항 xii, 108 p. : 삽도 ; 26 cm
언어 한국어
일반주기 부록 : Data acquisition program for polymerization rate curves
저자명의 영문표기 : Won-Deuk Song
지도교수의 한글표기 : 임선기
지도교수의 영문표기 : Son-Ki Ihm
학위논문 학위논문(박사) - 한국과학기술원 : 화학공학과,
서지주기 참고문헌 : p. 82-93
주제 Catalysts.
Ziegler-Natta catalysts.
Polymerization.
Carbonyl compounds.
촉매. --과학기술용어시소러스
중합. --과학기술용어시소러스
지글러-나타 촉매.
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