Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Phenylene-Bridged OSSO-Type Titanium Complexes in the Polymerization of Ethylene and Propylene
ACS Omega ( IF 3.7 ) Pub Date : 2018-09-21 00:00:00 , DOI: 10.1021/acsomega.8b01550 Rosita Lapenta 1 , Antonio Buonerba 1, 2 , Ermanno Luciano 1 , Francesco Della Monica 1 , Assunta De Nisi 3 , Magda Monari 3 , Alfonso Grassi 1, 2 , Carmine Capacchione 1, 2 , Stefano Milione 1, 2
ACS Omega ( IF 3.7 ) Pub Date : 2018-09-21 00:00:00 , DOI: 10.1021/acsomega.8b01550 Rosita Lapenta 1 , Antonio Buonerba 1, 2 , Ermanno Luciano 1 , Francesco Della Monica 1 , Assunta De Nisi 3 , Magda Monari 3 , Alfonso Grassi 1, 2 , Carmine Capacchione 1, 2 , Stefano Milione 1, 2
Affiliation
|
The dichloro titanium complexes (OSSOtBu)TiCl2 (1) and (OSSOCum)TiCl2 (2) bearing o-phenylene-bridged OSSO-type ligands [OSSOtBu-H = 6,6′-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-di-tert-butyphenol) and OSSOCum-H = 6,6′-((1,2-phenylenebis(sulfanediyl))bis(methylene))bis(2,4-bis(2-phenylpropan-2-yl)phenol)] were prepared and characterized. The X-ray structure of 1 revealed that Ti atom has an octahedral coordination geometry with an fac–fac wrapping of the [OSSO] ligand. In solution at 25 °C, 1 mainly retains the C2 symmetric structure, whereas 2 shows an equilibrium between C2- and C1-symmetric stereoisomers. Activation of 2 with (Ph3C)[B(C6F5)4] led to a highly active catalytic system with an activity of 238 kgPE·molcat–1·bar–1·h–1; linear polyethylene with a Tm of 122 °C and Mw of 107 kDa were obtained under these conditions. Catalyst 1 displayed the moderate activity of 59 kgPE·molcat–1·bar–1·h–1. Gel permeation chromatography analysis revealed the formation of high-molecular-weight polyethylenes with very large distributions of the molecular weights, indicating a low control of the polymerization process, probably becaue of the presence of different active species in solution. Density functional theory investigation provides a rational for the relative high-molecular-weight polymers obtained with these complexes. The precatalyst 2 was also active in propylene polymerization producing atactic oligomers terminated with unsaturated end groups.
中文翻译：
乙烯和丙烯聚合中亚苯基桥 OSSO 型钛配合物
二氯钛配合物 (OSSO t Bu )TiCl 2 ( 1 ) 和 (OSSO Cum )TiCl 2 ( 2 ) 带有邻亚苯基桥联的 OSSO 型配体 [OSSO t Bu -H = 6,6′-((1, 2-亚苯基双(硫二基))双(亚甲基))双(2,4-二叔丁基苯酚)和OSSO Cum -H = 6,6′-((1,2-亚苯基双(硫二基))双(亚甲基) )双(2,4-双(2-苯基丙-2-基)苯酚)]的制备和表征。1的 X 射线结构表明 Ti 原子具有八面体配位几何形状，[OSSO] 配体以fac - fac包裹。在25℃的溶液中，1主要保留C 2对称结构，而2则显示出C 2和C 1对称立体异构体之间的平衡。用(Ph 3 C)[B(C 6 F 5 ) 4 ]活化2得到高活性催化体系，活性为238 kg PE ·mol cat –1 ·bar –1 ·h –1；在这些条件下获得了T m为 122 °C、M w为 107 kDa 的线性聚乙烯。催化剂1显示出59 kg PE ·mol cat –1 ·bar –1 ·h –1的中等活性。凝胶渗透色谱分析揭示了高分子量聚乙烯的形成，其分子量分布非常大，表明聚合过程的控制程度低，可能是因为溶液中存在不同的活性物质。密度泛函理论研究为用这些配合物获得的相对高分子量聚合物提供了合理性。预催化剂2在产生以不饱和端基封端的无规低聚物的丙烯聚合中也具有活性。
更新日期：2018-09-21
中文翻译：
乙烯和丙烯聚合中亚苯基桥 OSSO 型钛配合物
二氯钛配合物 (OSSO t Bu )TiCl 2 ( 1 ) 和 (OSSO Cum )TiCl 2 ( 2 ) 带有邻亚苯基桥联的 OSSO 型配体 [OSSO t Bu -H = 6,6′-((1, 2-亚苯基双(硫二基))双(亚甲基))双(2,4-二叔丁基苯酚)和OSSO Cum -H = 6,6′-((1,2-亚苯基双(硫二基))双(亚甲基) )双(2,4-双(2-苯基丙-2-基)苯酚)]的制备和表征。1的 X 射线结构表明 Ti 原子具有八面体配位几何形状，[OSSO] 配体以fac - fac包裹。在25℃的溶液中，1主要保留C 2对称结构，而2则显示出C 2和C 1对称立体异构体之间的平衡。用(Ph 3 C)[B(C 6 F 5 ) 4 ]活化2得到高活性催化体系，活性为238 kg PE ·mol cat –1 ·bar –1 ·h –1；在这些条件下获得了T m为 122 °C、M w为 107 kDa 的线性聚乙烯。催化剂1显示出59 kg PE ·mol cat –1 ·bar –1 ·h –1的中等活性。凝胶渗透色谱分析揭示了高分子量聚乙烯的形成，其分子量分布非常大，表明聚合过程的控制程度低，可能是因为溶液中存在不同的活性物质。密度泛函理论研究为用这些配合物获得的相对高分子量聚合物提供了合理性。预催化剂2在产生以不饱和端基封端的无规低聚物的丙烯聚合中也具有活性。
京公网安备 11010802027423号