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A N-bridged strategy enables hemilabile phosphine–carbonyl palladium and nickel catalysts to mediate ethylene polymerization and copolymerization with polar vinyl monomers
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-08-28 , DOI: 10.1039/d0py01106a Lei Cui 1, 2, 3, 4, 5 , Zhongbao Jian 1, 2, 3, 4, 5
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-08-28 , DOI: 10.1039/d0py01106a Lei Cui 1, 2, 3, 4, 5 , Zhongbao Jian 1, 2, 3, 4, 5
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Hemilabile phosphine–carbonyl (P^O) Pd(II) and Ni(II) catalysts usually feature ethylene oligomerization due to the weakly coordinated nature of the carbonyl C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O group. In this contribution, with the aim of designing a new structural P^O catalyst for the improvement on olefin (co)polymerization, we developed a N-bridged strategy to overcome this issue. Therefore, a novel family of N-bridged phosphine–carbonyl Pd(II) catalysts Pd1–Pd6 and Ni(II) catalysts Ni1–Ni6 bearing various electronic nature and steric bulk were prepared and studied for ethylene polymerization. Compared with the previously reported C-bridged phosphine-ketone Pd(II) and Ni(II) catalysts as references, these N-bridged phosphine-amide catalysts showed obviously enhanced molecular weights, which reach a 200 times higher value of 83.2 kg mol−1 that is comparable to those using pioneering bisphosphine-monoxide P^O catalysts. More significantly, not only preferred cationic Pd(II) catalysts but also the more challenging Ni(II) catalysts enabled ethylene copolymerizations with challenging polar vinyl monomers such as methyl acrylate, acrylic acid, and n-butyl vinyl ether with good catalytic activities, molecular weights (14.1 kg mol−1), and comonomer incorporation (3.3 mol%). This work adds a new and effective member to the electronically asymmetric P^O-type late transition metal catalyst family applied in olefin (co)polymerization.
中文翻译：
N桥联策略使半不稳定的膦-羰基钯和镍催化剂能够介导乙烯聚合和与极性乙烯基单体的共聚
半不稳定的膦-羰基（P ^ O）Pd（II）和Ni（II）催化剂通常由于羰基CO基团的弱配位性质而具有乙烯低聚的特点。在此贡献中，为了设计一种新的结构化P 2 O催化剂以改善烯烃（共）聚合反应，我们开发了一种N桥策略来克服这一问题。因此，制备了一种新型的N桥膦-羰基Pd（II）催化剂Pd1-Pd6和Ni（II）催化剂Ni1-Ni6，它们具有各种电子性质和空间体积，并用于乙烯聚合。与先前报道的碳桥膦酮Pd（II）和Ni（II）催化剂作为参考，这些N-桥膦酰胺催化剂显示出明显提高的分子量，其值达到83.2 kg mol -1的200倍，这是使用开创性的双膦一氧化碳P ^ O催化剂可比的。更重要的是，不仅优选的阳离子Pd（II）催化剂，而且更具挑战性的Ni（II）催化剂都可以使乙烯与具有挑战性的极性乙烯基单体（例如丙烯酸甲酯，丙烯酸和正丁基乙烯基醚）具有良好的催化活性进行共聚，重量（14.1 kg mol -1）和共聚单体掺入（3.3 mol％）。这项工作为应用于烯烃（共）聚合反应的电子不对称P ^ O型后期过渡金属催化剂家族增加了新的有效成员。
更新日期：2020-10-06
O group. In this contribution, with the aim of designing a new structural P^O catalyst for the improvement on olefin (co)polymerization, we developed a N-bridged strategy to overcome this issue. Therefore, a novel family of N-bridged phosphine–carbonyl Pd(II) catalysts Pd1–Pd6 and Ni(II) catalysts Ni1–Ni6 bearing various electronic nature and steric bulk were prepared and studied for ethylene polymerization. Compared with the previously reported C-bridged phosphine-ketone Pd(II) and Ni(II) catalysts as references, these N-bridged phosphine-amide catalysts showed obviously enhanced molecular weights, which reach a 200 times higher value of 83.2 kg mol−1 that is comparable to those using pioneering bisphosphine-monoxide P^O catalysts. More significantly, not only preferred cationic Pd(II) catalysts but also the more challenging Ni(II) catalysts enabled ethylene copolymerizations with challenging polar vinyl monomers such as methyl acrylate, acrylic acid, and n-butyl vinyl ether with good catalytic activities, molecular weights (14.1 kg mol−1), and comonomer incorporation (3.3 mol%). This work adds a new and effective member to the electronically asymmetric P^O-type late transition metal catalyst family applied in olefin (co)polymerization.
中文翻译：
N桥联策略使半不稳定的膦-羰基钯和镍催化剂能够介导乙烯聚合和与极性乙烯基单体的共聚
半不稳定的膦-羰基（P ^ O）Pd（II）和Ni（II）催化剂通常由于羰基C
O基团的弱配位性质而具有乙烯低聚的特点。在此贡献中，为了设计一种新的结构化P 2 O催化剂以改善烯烃（共）聚合反应，我们开发了一种N桥策略来克服这一问题。因此，制备了一种新型的N桥膦-羰基Pd（II）催化剂Pd1-Pd6和Ni（II）催化剂Ni1-Ni6，它们具有各种电子性质和空间体积，并用于乙烯聚合。与先前报道的碳桥膦酮Pd（II）和Ni（II）催化剂作为参考，这些N-桥膦酰胺催化剂显示出明显提高的分子量，其值达到83.2 kg mol -1的200倍，这是使用开创性的双膦一氧化碳P ^ O催化剂可比的。更重要的是，不仅优选的阳离子Pd（II）催化剂，而且更具挑战性的Ni（II）催化剂都可以使乙烯与具有挑战性的极性乙烯基单体（例如丙烯酸甲酯，丙烯酸和正丁基乙烯基醚）具有良好的催化活性进行共聚，重量（14.1 kg mol -1）和共聚单体掺入（3.3 mol％）。这项工作为应用于烯烃（共）聚合反应的电子不对称P ^ O型后期过渡金属催化剂家族增加了新的有效成员。
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