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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Group 4 permethylindenyl complexes for the polymerisation of l-, d- and rac-lactide monomers
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Group 4 permethylindenyl complexes for the polymerisation of l-, d- and rac-lactide monomers

机译:第4组用于聚合L-,D-和RAC-丙交酯单体的聚甲茚基配合物

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A series of well-defined group 4 permethylindenyl complexes have been prepared and fully characterised by NMR spectroscopy and X-ray crystallography. (2SB)-S-Me(Cp,I*)ZrCl2 ({((5)-C9Me6)Me2Si((5)-C5H4)}ZrCl2; 1), (2SB)-S-Me(Cp-Me,I*)ZrCl2 ({((5)-C9Me6)Me2Si((5)-C5H3Me)}ZrCl2; 2), (2SB)-S-Me(Cp,I*)HfCl2 (3) and Z-(2SB)-S-Me(Cp,I*)ZrCl(O-2,6-Me-C6H3) (4) were investigated as initiators for the ring-opening polymerisation (ROP) of l-, d- and rac-lactide monomers in the presence of benzyl alcohol. 1-4 displayed second order dependence on monomer concentration and produced isotactic and heterotactic (P-r = 0.81) polylactides for the polymerisation of l-, d- and rac-lactide respectively. The effects of temperature, catalyst concentration, co-initiator concentration, solvent and scale were studied. At 80 degrees C, with two equivalents of benzyl alcohol, 4 was the most active initiator for the ROP of l-, d- and rac-lactide (k(obs) = 6.39, 6.38 and 5.89 M-1 h(-1) respectively). The polylactides were characterised by NMR spectroscopy, GPC and MALDI-TOF mass spectrometry.
机译:已经制备了一系列明确定义的4型渗透茚基复合物,并通过NMR光谱和X射线晶体学特征。 (2sb)-s-me(cp,i *)zrcl2({((5)-c9me6)me2si((5)-c5h4)} zrcl2; 1),(2sb)-s-me(cp-me,我*)ZrCl2({((5)-C9ME6)Me2Si((5)-C5H3ME)} ZrCl2; 2),(2SB)-S-ME(CP,I *)HFCL2(3)和Z-(2SB) - 研究了S-ME(CP,I *)ZrCl(O-2,6-ME-C6H3)(4)作为L-,D-和RAC-丙交酯单体的开环聚合(ROP)的引发剂苄醇的存在。 1-4显示第二顺序依赖于单体浓度,并分别产生的单向性和异象(P-r = 0.81)聚酰胺,分别用于聚合L-,D-和RAC-丙交酯。研究了温度,催化剂浓度,共引发剂浓度,溶剂和等级的影响。在80℃下,用两当量的苄醇,4是L-,D-和RAC-丙交酯的ROP中最活性的引发剂(K(OBS)= 6.39,6.38和5.89 m-1 H(-1)分别)。通过NMR光谱,GPC和MALDI-TOF质谱法表征聚丙环酯。

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