Olefin Polymerization and Ring-Opening Metathesis Polymerization of Norbornene by (Arylimido)(aryloxo)vanadium(V) Complexes of the Type VX2(NAr)(OAr`). Remarkable Effect of Aluminum Cocatalyst for the Coordination and Insertion and Ring-Opening Metathesis
Olefin Polymerization and Ring-Opening Metathesis Polymerization of Norbornene by (Arylimido)(aryloxo)vanadium(V) Complexes of the Type VX2(NAr)(OAr`). Remarkable Effect of Aluminum Cocatalyst for the Coordination and Insertion and Ring-Opening Metathesis
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DOI：
10.1021/ma0117413
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发表时间：
2002-01
期刊：
影响因子：
5.5
通讯作者：
K. Nomura;A. Sagara;Y. Imanishi
中科院分区：
文献类型：
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作者：
K. Nomura;A. Sagara;Y. Imanishi
VCl2(NAr)(OAr‘) 类型的各种（芳基酰亚胺基）（芳氧基）钒 (V) 配合物 [NAr = N-2,6-Me2C6H3 (2), N-2,6-iPr2C6H3 (3)； OAr‘ = O-2,6-Me2C6H3 (a)、O-2,6-iPr2C6H3 (b)、O-2,6-tBu2-4-MeC6H2 (c)] 由 VCl3(NAr) 与 Ar‘OH 在正己烷中以高产率制备。 2b在甲基铝氧烷（MAO）存在下对乙烯聚合表现出显着的催化活性，得到具有单峰分子量分布的高分子量聚合物（Mw = 2.92×106，Mw/Mn = 2.88）。 V(CH2Ph)2(N-2,6-Me2C6H3)(O-2,6-iPr2C6H3) (4) 在没有助催化剂的情况下引发降冰片烯的开环复分解聚合(ROMP)，得到具有单峰分子量分布的高分子量聚合物(Mw = 4.69 × 106，Mw/Mn = 1.93)。如果 2b 或 2c 在甲苯中用 AlMe3（5−10 当量）处理，ROMP 也会有效进行，并且 2b 观察到所得聚合物的烯属双键具有高立构规整性（反式/顺式 = 91/9）。另一方面，显着的催化活性...
Various (arylimido)(aryloxo)vanadium(V) complexes of the type VCl2(NAr)(OAr‘) [NAr = N-2,6-Me2C6H3 (2), N-2,6-iPr2C6H3 (3); OAr‘ = O-2,6-Me2C6H3 (a), O-2,6-iPr2C6H3 (b), O-2,6-tBu2-4-MeC6H2 (c)] have been prepared in high yields from VCl3(NAr) with Ar‘OH in n-hexane. 2b exhibited remarkable catalytic activity for ethylene polymerization in the presence of methylaluminoxane (MAO), affording high molecular weight polymer with unimodal molecular weight distribution (Mw = 2.92 × 106, Mw/Mn = 2.88). V(CH2Ph)2(N-2,6-Me2C6H3)(O-2,6-iPr2C6H3) (4) initiated ring-opening metathesis polymerization (ROMP) of norbornene without cocatalyst, affording high molecular weight polymer with unimodal molecular weight distribution (Mw = 4.69 × 106, Mw/Mn = 1.93). The ROMP also proceeded efficiently if 2b or 2c was treated with AlMe3 (5−10 equiv) in toluene, and high stereoregularity (trans/cis = 91/9) in the olefinic double bond for the resultant polymer was observed by 2b. On the other hand, remarkable catalytic activities by...