Denk Alina, Kernbichl Sebastian, Schaffer Andreas, Kränzlein Moritz, Pehl Thomas, Rieger Bernhard
WACKER-Chair of Macromolecular Chemistry, Catalysis Research Center, Technical University Munich, Lichtenbergstr. 4, 85748 Garching, Germany.
ACS Macro Lett. 2020 Apr 21;9(4):571-575. doi: 10.1021/acsmacrolett.9b01025. Epub 2020 Mar 27.
Terpolymerizations of cyclohexene oxide (CHO), CO, and the Michael-type monomer 2-vinylpyridine (2VP) are presented. The combination of two distinct polymerization mechanisms was enabled by the synthesis of a heterobifunctional complex (). Its β-diiminate zinc moiety allows the ring-opening copolymerization of CHO and CO, whereas the yttrium metallocene catalyzed the rare earth metal-mediated group-transfer polymerization of the polar vinyl monomer. Both units were connected via the CH-bond activation of a pyridyl-alkoxide linker. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) revealed the successful transfer of the linker to the end-group of the respective homopolymers poly(cyclohexene carbonate) (PCHC) and poly(2VP) (P2VP) being the prerequisite for copolymer formation. Aliquot gel-permeation chromatography (GPC) analysis and solubility behavior tests confirmed the P2VP-()-PCHC terpolymer formation via two pathways, a sequential and a one-pot procedure. Furthermore, the versatility of the method was demonstrated by introducing 2-isopropenyl-2-oxazoline (IPOx) as the second Michael-type monomer that yielded the terpolymer poly(IPOx)--PCHC.
本文介绍了氧化环己烯（CHO）、CO与迈克尔型单体2-乙烯基吡啶（2VP）的三元共聚合反应。通过合成一种异双功能配合物（），实现了两种不同聚合机理的结合。其β-二亚胺锌部分可使CHO和CO进行开环共聚，而钇金属茂催化极性乙烯基单体的稀土金属介导的基团转移聚合反应。两个单元通过吡啶醇盐连接基的C-H键活化相连。基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF-MS）表明，连接基成功转移至各自均聚物聚（环己烯碳酸酯）（PCHC）和聚（2VP）（P2VP）的端基，这是形成共聚物的前提条件。等分试样凝胶渗透色谱（GPC）分析和溶解性行为测试证实，通过顺序法和一锅法两种途径形成了P2VP-（）-PCHC三元共聚物。此外，通过引入2-异丙烯基-2-恶唑啉（IPOx）作为第二种迈克尔型单体，得到了三元共聚物聚（IPOx）--PCHC，证明了该方法的通用性。
