Metal-size influence in isoselective 2-vinylpyridine polymerization

Metal-size influence in isoselective 2-vinylpyridine polymerization
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金属尺寸对同选择性 2-乙烯基吡啶聚合的影响

DOI:
10.1016/j.poly.2019.03.011
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发表时间:
2019-06
期刊:
影响因子:
2.6
通讯作者:
Li Chang-Hong
Li Chang-Hong
中科院分区:
化学3区
文献类型:
--
作者:
Xu Tie-Qi;Yu Zhi-Qi;Li Chang-Hong

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以三烷基稀土配合物Ln(CH2SiMe3)3(THF)2(Ln = Y, Lu, Ho, Dy)与四齿酚醚配体反应得到8个新的有机金属配合物。其中与Lu配合物的结构通过单晶x射线衍射得到了证实。这些配合物在甲苯环境温度下具有中高的2-VP聚合活性。络合物5的催化活性最高,周转频率为1714 h−1。值得注意的是,2-VP聚合也是立体定向的,产生的等规聚(2-VP)的等规性为mm= 0.44-0.99。催化实验结果表明,金属原子的大小对聚合物生长链的立体规整性有明显影响,含Ho原子的催化剂比其他金属催化剂具有更好的等规选择性。
Eight new organometallic complexes were obtained by the reaction of trialkyl rare earth complexes Ln(CH2SiMe3)3(THF)2(Ln = Y, Lu, Ho, Dy) with tetradentate phenol ether ligands. Among them the structure of complex7with Lu was confirmed by single crystal X-ray diffraction. These complexes exhibited moderate to high activity for 2-VP polymerization at ambient temperature in toluene. Complex5showed the highest catalytic activity, with a turnover frequency of 1714 h−1. Significantly, the 2-VP polymerization is also stereospecific, producing isotactic poly(2-VP) with an isotacticity ofmm= 0.44–0.99. The catalytic experimental results indicate that the size of metal atom obviously influences the stereoregularity of the growing polymer chain, and catalysts with Ho atom exhibit better isotactic selectivity than other metal catalysts.
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