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  • 09월 04일 17시 이후 : 초록수정 불가능, 일정확인 및 검색만 가능

제114회 대한화학회 학술발표회, 총회 및 기기전시회 안내 Study of Chromium Precursor in Ethylene Trimerization Catalyst

2014년 8월 28일 16시 54분 29초
INOR.P-253 이곳을 클릭하시면 발표코드에 대한 설명을 보실 수 있습니다.
10월 15일 (수요일) 16:00~19:00
저자 및
전종엽, 박동식, 이분열*
아주대학교 분자과학기술학과, Korea
The Phillips ethylene trimerization catalyst system prepared by reacting Cr(EH)3 (EH = 2-ethylhexanoate), 2,5-dimethylpyrrole (Me2C4H2NH), Et3Al, and Et2AlCl in an aromatic hydrocarbon solvent was rectified to a congener composed of a new chromium precursor (EH)2CrOH, (Me2C4H2N)AlEt2, and Et3Al?ClAlEt2. Reaction of CrCl3 with 3 equiv Na(EH) in water did not generate Cr(EH)3, but unexpectedly produced the new chromium precursor (EH)2CrOH. In comparison with the erratic catalytic performance of the original Phillips system due to ill-defined nature of the Cr(EH)3 source, the rectified system exhibited consistently high activity. Solution structure of (EH)2CrOH was inferred to be an adamantane skeleton composed of four (EH)2CrOH units and two water molecules (6) based on the cryoscopy measurement of the molecular weight and the revealed crystal structure of a side product obtained from the catalyst solution: a tetranuclear chromium(III) cluster (5) coordinated by three ?3-CH2 , one ?2-CH3, two ?2-OH, and three (?5-Me2C4H2N)AlMe2Cl ligands. Reaction of (EH)2CrOH with Me2AlCl in benzene afforded precipitates of MeCrCl2, the structure of which was revealed to be a THF adduct: MeCrCl2(THF)3. Reaction of (EH)2CrOH with (Me2C4H2N)AlMe2?OEt2 afforded the dimeric Cr(II)-complex (3) coordinated by (?5-Me2C4H2N)AlMe2(NC4H2Me2) and ?2-?1:?2-Me2C4H2N ligands, which provided highly active species when activated with Et3Al?ClAlEt2, indicating that 3 was a key intermediate in the Phillips catalyst preparation.