无机化学学报
無機化學學報
무궤화학학보
JOURNAL OF INORGANIC CHEMISTRY
2005年
12期
1775-1783
,共9页
钛%锆%N,O配体%均相催化剂%乙烯聚合
鈦%鋯%N,O配體%均相催化劑%乙烯聚閤
태%고%N,O배체%균상최화제%을희취합
titanium%zirconium%N,O ligands%homogeneous catalysts%ethylene polymerization
选择含有烯丙基亚胺酚为辅助配体,设计合成了5个ⅣB族钛锆金属络合物[{CH2=CHCH2N=CH-C6H3(3-R)O}2MCl2](4a:R=t-Bu,M=Zr;4b:R=t-Bu,M=Ti;4c:R=Rh,M=Zr;4d:R=Ph,M=Ti)和[{(CH3)2CHCH2N=CH-C6H3(3-t-Bu)O}2rCl2(5),对它们进行了红外光谱、核磁共振及元素分析表征.并用X-射线单晶衍射法测定了化合物4a和4d的晶体结构.部分配合物在助催化剂MMAO的作用下对烯烃聚合显示了较好的催化活性,其中自固载催化剂4a生成了双峰分布的聚烯烃产品(Mw/Mn=15.3～31.9).
選擇含有烯丙基亞胺酚為輔助配體,設計閤成瞭5箇ⅣB族鈦鋯金屬絡閤物[{CH2=CHCH2N=CH-C6H3(3-R)O}2MCl2](4a:R=t-Bu,M=Zr;4b:R=t-Bu,M=Ti;4c:R=Rh,M=Zr;4d:R=Ph,M=Ti)和[{(CH3)2CHCH2N=CH-C6H3(3-t-Bu)O}2rCl2(5),對它們進行瞭紅外光譜、覈磁共振及元素分析錶徵.併用X-射線單晶衍射法測定瞭化閤物4a和4d的晶體結構.部分配閤物在助催化劑MMAO的作用下對烯烴聚閤顯示瞭較好的催化活性,其中自固載催化劑4a生成瞭雙峰分佈的聚烯烴產品(Mw/Mn=15.3～31.9).
선택함유희병기아알분위보조배체,설계합성료5개ⅣB족태고금속락합물[{CH2=CHCH2N=CH-C6H3(3-R)O}2MCl2](4a:R=t-Bu,M=Zr;4b:R=t-Bu,M=Ti;4c:R=Rh,M=Zr;4d:R=Ph,M=Ti)화[{(CH3)2CHCH2N=CH-C6H3(3-t-Bu)O}2rCl2(5),대타문진행료홍외광보、핵자공진급원소분석표정.병용X-사선단정연사법측정료화합물4a화4d적정체결구.부분배합물재조최화제MMAO적작용하대희경취합현시료교호적최화활성,기중자고재최화제4a생성료쌍봉분포적취희경산품(Mw/Mn=15.3～31.9).
Five Group ⅣB phenol-imine complexes, [{CH2=CHCH2N=CH-C6H3(3-R)O}2MCl2] (4a: R=t-Bu, M=Zr;4b: R=t-Bu, M=Ti; 4c: R=Ph, M=Zr; 4d: R=Ph, M=Ti) and [{(CH3)2CHCH2N=CH-C6H3(3-t-Bu)O}2ZrCl2] (5) have been synthesized and characterized by IR, 1H NMR spectra and elemental analysis. The molecular structures of complex 4a and 4d have been determined by X-ray crystallographic analysis. All these compounds have been investigated for ethylene polymerization. Self-immobilized catalyst 4a exhibits high activity to afford bimodal distribution of polyethylene (Mw/Mn=1S.3～31.9) in the presence of modified methylaluminoxane (MMAO) as a co-catalyst. CCDC: 249504, 4a; 274994, 4d.
