Chen Shi-Yu, Ren Bai-Hao, Li Shi-Huan, Song Yu-Hang, Jiao Shuang, Zou Chen, Chen Changle, Lu Xiao-Bing, Liu Ye
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116024, China.
Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, 230026, China.
Angew Chem Int Ed Engl. 2022 Jul 18;61(29):e202204126. doi: 10.1002/anie.202204126. Epub 2022 May 31.
Transition-metal-catalyzed copolymerization of ethylene with carbon monoxide affords polyketones materials with excellent mechanical strength, photodegradability, surface and barrier properties. Unlike the widely used and rather expensive Pd catalysts, Ni-catalyzed carbonylative polymerization is very difficult since the strong binding affinity of CO to Ni deactivates the highly electrophilic metal center easily. In this study, various cationic P,O-coordinated Ni complexes were synthesized using the electronic modulation strategy, and the catalyst with strong electron-donating substituents exhibits an excellent productivity of 10 g polymer (g Ni) , which represents a rare discovery that a Ni complex could operate with such exceptional efficiency in comparison with Pd catalysts. Notably, those Ni catalysts were also efficient for terpolymerization of ethylene, propylene with CO for producing commercial polyketone materials with low melting temperatures and easy processibility.
过渡金属催化乙烯与一氧化碳的共聚反应可得到具有优异机械强度、光降解性、表面性能和阻隔性能的聚酮材料。与广泛使用且相当昂贵的钯催化剂不同，镍催化的羰基化聚合非常困难，因为一氧化碳与镍的强结合亲和力很容易使高亲电金属中心失活。在本研究中，采用电子调制策略合成了各种阳离子P，O配位的镍配合物，具有强供电子取代基的催化剂表现出优异的生产率，达到10 g聚合物/（g镍），这是一个罕见的发现，与钯催化剂相比，镍配合物能够以如此卓越的效率运行。值得注意的是，这些镍催化剂对于乙烯、丙烯与一氧化碳的三元共聚反应也很有效，可用于生产具有低熔点和易加工性的商业聚酮材料。
