School of Chemistry and Chemical Engineering, Hefei Normal University, Hefei 230061, China.
School of Chemical and Environmental Engineering, Anhui Polytechnic University, Wuhu 241000, China.
Molecules. 2023 Feb 28;28(5):2266. doi: 10.3390/molecules28052266.
Recently, polyolefin thermoplastic elastomers can be obtained directly using ethylene as a single feedstock via α-diimine nickel-catalyzed ethylene chain walking polymerization. Here, a new range of bulky acenaphthene-based α-diimine nickel complexes with hybrid -phenyl and -diarylmethyl anilines were constructed and applied to ethylene polymerization. All the nickel complexes under the activation of excess EtAlCl exhibited good activity (level of 10 g mol h) and produced polyethylene with high molecular weight (75.6-352.4 kg/mol) as well as proper branching densities (55-77/1000C). All the branched polyethylenes obtained exhibited high strain (704-1097%) and moderate to high stress (7-25 MPa) at break values. Most interestingly, the polyethylene produced by the methoxy-substituted nickel complex exhibited significantly lower molecular weights and branching densities, as well as significantly poorer strain recovery values (48% vs. 78-80%) than those by the other two complexes under the same conditions.
最近，通过α-二亚胺镍催化的乙烯链行走聚合，可以直接将乙烯作为单一原料获得聚烯烃热塑性弹性体。在此，构建了一系列新型的、基于苊的、带有混合 -苯基和 -二芳基甲胺的、体积庞大的α-二亚胺镍配合物，并将其应用于乙烯聚合。所有镍配合物在过量 EtAlCl 的活化下均表现出良好的活性（10 g mol h 的水平），并能得到高分子量（75.6-352.4 kg/mol）和适当支化密度（55-77/1000C）的聚乙烯。所得到的所有支化聚乙烯均表现出高应变（704-1097%）和中等至高的断裂应力（7-25 MPa）值。最有趣的是，在相同条件下，甲氧基取代的镍配合物所制备的聚乙烯分子量和支化密度明显较低，应变恢复值也明显较差（48%对 78-80%）。
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