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Effect of para-Substituents in Ethylene Copolymerizations with 1-Decene, 1-Dodecene, and with 2-Methyl-1-Pentene Using Phenoxide Modified Half-Titanocenes-MAO Catalyst Systems
ChemistryOpen ( IF 2.5 ) Pub Date : 2021-07-05 , DOI: 10.1002/open.202100047 Suphitchaya Kitphaitun 1 , Qing Yan 1 , Kotohiro Nomura 1
ChemistryOpen ( IF 2.5 ) Pub Date : 2021-07-05 , DOI: 10.1002/open.202100047 Suphitchaya Kitphaitun 1 , Qing Yan 1 , Kotohiro Nomura 1
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Effect of para-substituents in the ethylene (E) copolymerization with 1-decene (DC), 1-dodecene (DD), and with 2-methyl-1-pentene (2M1P) using a series of Cp*TiCl2(O-2,6-iPr2-4-R-C6H2) [R=H (1), tBu (2), Ph (3), CHPh2 (4), CPh3 (5), SiMe3 (6), SiEt3 (7), and newly prepared 4-tBuC6H4 (8) and 3,5-Me2C6H3 (9)]-MAO catalyst systems has been studied. The activities in these copolymerization reactions were affected by the para-substituent, and the SiMe3 (6), SiEt3 (7) and 3,5-Me2C6H3 (9) analogues showed the higher activities at 50 °C in the E copolymerization reactions with DC (1.06–1.44×106 kg-polymer/mol-Ti⋅h), DD (1.04–1.88×106 kg-polymer/mol-Ti⋅h) than the others, whereas no significant differences were observed in the comonomer incorporations. Complexes 6 and 7 also showed the higher activities at 50 °C in the E/2M1P copolymerization, and the 2M1P incorporation was affected by the para-substituent and the polymerization temperature; complex 9 showed better 2M1P incorporation at 25 °C.
中文翻译：
使用酚盐改性半二茂钛-MAO 催化剂体系对位取代基对乙烯与 1-癸烯、1-十二烯和 2-甲基-1-戊烯共聚的影响
使用一系列 Cp*TiCl 2 (O-) 的乙烯 (E) 与 1-癸烯 (DC)、1-十二烯 (DD) 和 2-甲基-1-戊烯 (2M1P) 共聚中对位取代基的影响2,6- i Pr 2 -4-RC 6 H 2 ) [R=H ( 1 ), t Bu ( 2 ), Ph ( 3 ), CHPh 2 ( 4 ), CPh 3 ( 5 ), SiMe 3 ( 6 ) )、SiEt 3 ( 7 )以及新制备的4- t BuC 6 H 4 ( 8 )和3,5-Me 2 C 6 H 3 ( 9 )]-MAO催化剂体系进行了研究。这些共聚反应的活性受到对位取代基的影响，SiMe 3 ( 6 )、SiEt 3 ( 7 ) 和 3,5-Me 2 C 6 H 3 ( 9 ) 类似物在 50 °C 时表现出更高的活性E 与 DC (1.06–1.44×10 6 kg-polymer/mol-Ti⋅h)、DD (1.04–1.88×10 6 kg-polymer/mol-Ti⋅h) 的共聚反应优于其他反应，而没有显着性在共聚单体掺入中观察到差异。配合物6和7在E/2M1P共聚中在50℃下也表现出较高的活性，并且2M1P的掺入受到对位取代基和聚合温度的影响；复合物9在 25 °C 下表现出更好的 2M1P 掺入。
更新日期：2021-09-01
中文翻译：
使用酚盐改性半二茂钛-MAO 催化剂体系对位取代基对乙烯与 1-癸烯、1-十二烯和 2-甲基-1-戊烯共聚的影响
使用一系列 Cp*TiCl 2 (O-) 的乙烯 (E) 与 1-癸烯 (DC)、1-十二烯 (DD) 和 2-甲基-1-戊烯 (2M1P) 共聚中对位取代基的影响2,6- i Pr 2 -4-RC 6 H 2 ) [R=H ( 1 ), t Bu ( 2 ), Ph ( 3 ), CHPh 2 ( 4 ), CPh 3 ( 5 ), SiMe 3 ( 6 ) )、SiEt 3 ( 7 )以及新制备的4- t BuC 6 H 4 ( 8 )和3,5-Me 2 C 6 H 3 ( 9 )]-MAO催化剂体系进行了研究。这些共聚反应的活性受到对位取代基的影响，SiMe 3 ( 6 )、SiEt 3 ( 7 ) 和 3,5-Me 2 C 6 H 3 ( 9 ) 类似物在 50 °C 时表现出更高的活性E 与 DC (1.06–1.44×10 6 kg-polymer/mol-Ti⋅h)、DD (1.04–1.88×10 6 kg-polymer/mol-Ti⋅h) 的共聚反应优于其他反应，而没有显着性在共聚单体掺入中观察到差异。配合物6和7在E/2M1P共聚中在50℃下也表现出较高的活性，并且2M1P的掺入受到对位取代基和聚合温度的影响；复合物9在 25 °C 下表现出更好的 2M1P 掺入。
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