Zheng Handou, Wang Junsong, Qiu Zonglin, Feng Chunyu, Zhou Haotian, Tu Guangshui, Gao Haiyang
School of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou 510275, China.
Molecules. 2025 May 30;30(11):2402. doi: 10.3390/molecules30112402.
development of earth-abundant nickel-based catalysts is currently one of the greatest challenges for the straightforward synthesis of functionalized polyolefins. With environmental protection concerns, controllable copolymerizations of ethylene with biosourced comonomers derived from castor oil, such as methyl 10-undecenoate (U-COOMe), 10-undecen-1-ol (U-OH), or 10-undecenyl bromide (U-Br), were realized using -diimine nickel catalyst () with dibenzobarrelene backbone. Catalyst was highly tolerant toward polar comonomers, and functional polyethylenes were successfully prepared. The influences of the polar group, temperature, and comonomer concentration were studied in detail. Catalyst was able to catalyze the copolymerization of ethylene with U-OH to afford high-molecular-weight (~180 kg/mol) functional polyethylene in a controlled fashion. NMR analysis showed that the produced functional polyethylenes were highly branched and had broad melting peaks ranging from 0 to 30 °C. Water contact angle (WCA) measurements showed that the surface of the obtained hydroxyl-functionalized polyethylene changed from hydrophobic to hydrophilic with the introduction of the comonomer U-OH.
开发地球上储量丰富的镍基催化剂是目前直接合成功能化聚烯烃面临的最大挑战之一。出于环境保护的考虑，使用具有二苯并桶烯骨架的二亚胺镍催化剂（）实现了乙烯与源自蓖麻油的生物源共聚单体（如10-十一烯酸甲酯（U-COOMe）、10-十一烯-1-醇（U-OH）或10-十一烯基溴（U-Br））的可控共聚。催化剂对极性共聚单体具有高度耐受性，并成功制备了功能化聚乙烯。详细研究了极性基团、温度和共聚单体浓度的影响。催化剂能够以可控方式催化乙烯与U-OH的共聚反应，得到高分子量（约180 kg/mol）的功能化聚乙烯。核磁共振分析表明，所制备的功能化聚乙烯具有高度支化结构，熔点范围在0至30°C之间，呈宽峰分布。水接触角（WCA）测量表明，随着共聚单体U-OH的引入，所得羟基功能化聚乙烯的表面从疏水性转变为亲水性。
