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Synthesis of Anthracene-Bridged Dinuclear Phenoxyiminato Organotitanium Catalysts with Enhanced Activity, Thermal Stability, and Comonomer Incorporation Ability toward Ethylene (Co)polymerization
Organometallics ( IF 2.5 ) Pub Date : 2020-08-28 , DOI: 10.1021/acs.organomet.0c00477 Shaofeng Liu 1 , Yanhong Xing 1 , Quande Zheng 1 , Yutong Jia 1 , Zhibo Li 1
Organometallics ( IF 2.5 ) Pub Date : 2020-08-28 , DOI: 10.1021/acs.organomet.0c00477 Shaofeng Liu 1 , Yanhong Xing 1 , Quande Zheng 1 , Yutong Jia 1 , Zhibo Li 1
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Dinuclear titanium complexes syn-Ti2 and anti-Ti2 bearing anthracene-bridged bisphenoxyimine ligands (syn-L and anti-L) have been prepared and characterized by NMR and elemental analyses. The molecular structure of syn-Ti2 was defined by X-ray diffraction, revealing a separation of 7.183 Å between the two Ti centers. The mononuclear complex [(2,6-iPr2-C6H3N═CH-C6H2-3,5-tBu-2-O)TiCl3(THF)] (Ti1) was also prepared for control experiments. In the presence of MAO as a cocatalyst, syn-Ti2 and anti-Ti2 were active toward ethylene homopolymerization but had distinct catalytic properties. The complex syn-Ti2 with a shorter metal–metal separation exhibited higher activity and produced polymers with higher molecular weights, in comparison to anti-Ti2, having a longer metal–metal separation, and the mononuclear catalyst control Ti1 under identical conditions. More importantly, the complex syn-Ti2 exhibited excellent thermal stability and thus the a greater activity can be obtained at 100 °C, which is a preferred temperature for industrial operations. For ethylene/1-hexene copolymerization, the activity, Mw, and incorporation of 1-hexene by syn-Ti2 were 2.3×, 3.2×, and 6.0× those of anti-Ti2 under identical conditions.
中文翻译：
具有增强的活性，热稳定性和对乙烯（Co）聚合的共聚单体结合能力的蒽桥双核苯氧基亚胺基有机钛催化剂的合成
已经制备了带有蒽桥联的双苯氧基亚胺配体的双核钛配合物syn -Ti 2和抗-Ti 2（syn -L和抗-L），并通过NMR和元素分析对其进行了表征。X射线衍射确定了syn -Ti 2的分子结构，揭示了两个Ti中心之间的间距为7.183Å。的单核配合物[（2,6-我镨2 -C 6 H ^ 3 N = CH-C 6 H ^ 2 -3,5-吨卜-2-O）的TiCl 3（THF）]（还制备了Ti 1）用于对照实验。在MAO作为助催化剂的存在下，syn -Ti 2和抗-Ti 2对乙烯均聚具有活性，但是具有独特的催化性能。与具有较长金属-金属分离的抗-Ti 2相比，具有较短金属-金属分离的复杂syn -Ti 2表现出更高的活性并生产出具有更高分子量的聚合物，并且单核催化剂在相同条件下控制Ti 1。更重要的是，复杂的syn -Ti 2由于具有优异的热稳定性，因此可以在100°C的条件下获得更大的活性，这是工业操作的优选温度。对于乙烯/ 1-己烯共聚，在相同条件下，抗-Ti 2的活性，M w和1-己烯通过顺-Ti 2的掺入分别为抗-Ti 2的2.3倍，3.2倍和6.0倍。
更新日期：2020-09-14
中文翻译：
具有增强的活性，热稳定性和对乙烯（Co）聚合的共聚单体结合能力的蒽桥双核苯氧基亚胺基有机钛催化剂的合成
已经制备了带有蒽桥联的双苯氧基亚胺配体的双核钛配合物syn -Ti 2和抗-Ti 2（syn -L和抗-L），并通过NMR和元素分析对其进行了表征。X射线衍射确定了syn -Ti 2的分子结构，揭示了两个Ti中心之间的间距为7.183Å。的单核配合物[（2,6-我镨2 -C 6 H ^ 3 N = CH-C 6 H ^ 2 -3,5-吨卜-2-O）的TiCl 3（THF）]（还制备了Ti 1）用于对照实验。在MAO作为助催化剂的存在下，syn -Ti 2和抗-Ti 2对乙烯均聚具有活性，但是具有独特的催化性能。与具有较长金属-金属分离的抗-Ti 2相比，具有较短金属-金属分离的复杂syn -Ti 2表现出更高的活性并生产出具有更高分子量的聚合物，并且单核催化剂在相同条件下控制Ti 1。更重要的是，复杂的syn -Ti 2由于具有优异的热稳定性，因此可以在100°C的条件下获得更大的活性，这是工业操作的优选温度。对于乙烯/ 1-己烯共聚，在相同条件下，抗-Ti 2的活性，M w和1-己烯通过顺-Ti 2的掺入分别为抗-Ti 2的2.3倍，3.2倍和6.0倍。
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