Direct Synthesis of Polyethylene Containing Two Kinds of Heteroatoms by Scandium Complexes

IF 4.1 2区 化学 Q2 POLYMER SCIENCE Polymer Chemistry Pub Date : 2025-01-20 DOI:10.1039/d4py01393j
Hui Tian, Yifan Wang, Chunji Wu, Xiaohui Kang, Baoli Wang
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Abstract

Polar polyolefins are of fundamental interest and practical significance. The direct synthesis of polyethylene containing two kinds of heteroatoms by early transition catalysts is still rare due to the complicated poisoning action, but these novel copolymers may behave superposed and unexpected characteristic. Herein we report the production of polyethylene containing two distinct polar groups (such as O, S and F) by scandium complexes. Sc-2 with bulkier ligand can raise polar olefin incorporation. S and F atoms on comonomer 1g (2S/F-o) shows significantly positive effect during copolymerization with ethylene and results in high incorporation ratio (17.2 to 44.9 mol%), high activity (69.0 to 211 kg molSc–1 h–1 bar–1) and high molecular weight (Mn) up to 33.3 × 104 g mol–1. The polymerization mechanistic aspect of cooperative action between S and F atoms on 1g has been elucidated by DFT studies. We expect that our new findings could guide the synthesis of polyolefins containing multi-functional groups.
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钪配合物直接合成含两种杂原子的聚乙烯
极性聚烯烃具有重要的现实意义。由于中毒作用复杂,用早过渡催化剂直接合成含两种杂原子的聚乙烯尚属罕见,但这些新型共聚物可能表现出叠加性和意想不到的特性。在这里,我们报道了用钪配合物生产含有两个不同极性基团(如O, S和F)的聚乙烯。配体较大的Sc-2能提高极性烯烃的结合。共聚单体1g (2S/F-o)上的S和F原子在乙烯共聚过程中表现出显著的正向作用,并获得了高掺入比(17.2 ~ 44.9 mol%)、高活性(69.0 ~ 211 kg molSc-1 h-1 bar-1)和高分子量(Mn) (33.3 × 104 g mol - 1)。通过DFT研究阐明了S和F原子在1g上协同作用的聚合机理。我们期望我们的新发现可以指导含多官能团聚烯烃的合成。
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来源期刊
Polymer Chemistry
Polymer Chemistry POLYMER SCIENCE-
CiteScore
8.60
自引率
8.70%
发文量
535
审稿时长
1.7 months
期刊介绍: Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.
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