Rigidifying Cation-Tunable Nickel Catalysts Increases Activity and Polar Monomer Incorporation in Ethylene and Methyl Acrylate Copolymerization
Rigidifying Cation-Tunable Nickel Catalysts Increases Activity and Polar Monomer Incorporation in Ethylene and Methyl Acrylate Copolymerization
复制标题
刚性化阳离子可调镍催化剂可提高乙烯和丙烯酸甲酯共聚反应中的活性和极性单体的掺入
DOI：
10.1021/acs.inorgchem.1c02888
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发表时间：
2021
影响因子：
4.6
通讯作者：
Do, Loi H.
中科院分区：
文献类型：
--
作者：
Tahmouresilerd, Babak;Xiao, Dawei;Do, Loi H.
在这项研究中，我们合成并表征了两个具有构象刚性的双膦单氧化物配体的镍配合物，其中一个具有ano-甲氧基苯基（Ni 2），另一个具有ano-（2-甲氧基乙氧基）苯基（Ni 3）取代基上的P2 O部分。我们使用Ni 3进行了金属结合研究，发现它与Li+和Na+的反应最有可能分别在溶液中产生1：1和1：1/2：1的镍：碱物种。镍配合物对乙烯均聚和共聚合均表现出良好的催化活性，催化活性分别达到3.8 × 103和8.1 × 10 kgmol-1h-1。在乙烯与丙烯酸甲酯（1.0 M）的反应中，在优化条件下，Li+的加入使Ni 3的催化活性提高了5.4倍，极性单体的引入量增加了1.9倍。与其他镍催化剂报道的乙烯和丙烯酸甲酯共聚反应的比较表明，我们的镍碱催化剂是有竞争力的一些最有效的镍基系统迄今开发。
In this study, we synthesized and characterized two nickel complexes featuring conformationally rigid bisphosphine mono-oxide ligands, where one has ano-methoxyphenyl (Ni2) and the other has ano-(2-methoxyethoxy)phenyl (Ni3) substituent on the P═O moiety. We performed metal binding studies usingNi3and found that its reaction with Li+and Na+most likely produced 1:1 and 1:1/2:1 nickel:alkali species in solution, respectively. The nickel complexes were competent catalysts for ethylene homopolymerization and copolymerization, with activities up to 3.8 × 103and 8.1 × 10 kg mol–1h–1, respectively. In reactions of ethylene with methyl acrylate (1.0 M), the addition of Li+toNi3led to a 5.4-fold enhancement in catalyst activity and a 1.9-fold increase in polar monomer incorporation in comparison to those byNi3alone under optimized conditions. A comparison with other nickel catalysts reported for ethylene and methyl acrylate copolymerization revealed that our nickel–alkali catalysts are competitive with some of the most efficient Ni-based systems developed thus far.