Heteronuclear, Monomer-Selective Zn/Y Catalyst Combines Copolymerization of Epoxides and CO2 with Group-Transfer Polymerization of Michael-Type Monomers,ACS Macro Letters

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Heteronuclear, Monomer-Selective Zn/Y Catalyst Combines Copolymerization of Epoxides and CO2 with Group-Transfer Polymerization of Michael-Type Monomers
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-03-27 , DOI: 10.1021/acsmacrolett.9b01025
Alina Denk ₁ , Sebastian Kernbichl ₁ , Andreas Schaffer ₁ , Moritz Kränzlein ₁ , Thomas Pehl ₁ , Bernhard Rieger ₁

Affiliation

Terpolymerizations of cyclohexene oxide (CHO), CO₂, 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 (3). Its β-diiminate zinc moiety allows the ring-opening copolymerization of CHO and CO₂, 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-block(b)-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)-b-PCHC.

中文翻译：

异核单体选择性 Zn/Y 催化剂将环氧化物和 CO2 的共聚与迈克尔型单体的基团转移聚合相结合

介绍了环己烯氧化物 (CHO)、CO ₂和迈克尔型单体 2-乙烯基吡啶 (2VP) 的三元聚合。异双功能复合物 ( 3 ) 的合成使两种不同聚合机制的结合成为可能。它的 β-二亚胺锌部分允许 CHO 和 CO _{2的开环共聚}，而钇茂金属催化极性乙烯基单体的稀土金属介导的基团转移聚合。两个单元通过吡啶基醇盐接头的 CH 键激活连接。基质辅助激光解吸/电离飞行时间质谱 (MALDI-TOF-MS) 揭示了连接体成功转移到各自均聚物聚(环己烯碳酸酯) (PCHC) 和聚 (2VP) 的端基(P2VP) 是共聚物形成的先决条件。等分凝胶渗透色谱 (GPC) 分析和溶解行为测试证实了 P2VP-块( b)-PCHC 三元共聚物通过两种途径形成，顺序和一锅法。此外，通过引入 2-异丙烯基-2-恶唑啉 (IPOx) 作为产生三元共聚物聚 (IPOx) -b -PCHC 的第二种迈克尔型单体，证明了该方法的多功能性。

更新日期：2020-04-23

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