<italic style="font-style: italic">N</italic>-Bridged Phosphine Carbonyl Palladium Complex Catalysts for Nonalternating Copolymerization of Ethylene and Carbon Monoxide

Xin-Jun Li; Shi-Huan Li; Shi-Yu Chen; Ye Liu

doi:10.11777/j.issn1000-3304.2025.25031

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N-Bridged Phosphine Carbonyl Palladium Complex Catalysts for Nonalternating Copolymerization of Ethylene and Carbon Monoxide

Research Article | 更新时间：2025-07-08

- N-Bridged Phosphine Carbonyl Palladium Complex Catalysts for Nonalternating Copolymerization of Ethylene and Carbon Monoxide
- Acta Polymerica Sinica Vol. 56, Issue 7, Pages: 1180-1191(2025)
- 作者机构：
  
  精细化工国家重点实验室大连理工大学化工学院大连 116024
- 作者简介：
  
  Ye Liu, E-mail: liuye@dlut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25031
  CLC：
- CSTR：32057.14.GFZXB.2025.7380
- Received：04 February 2025，
  
  Accepted：11 March 2025，
  
  Published Online：19 May 2025，
  
  Published：20 July 2025
- 稿件说明：
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李欣俊, 李世环, 陈世瑜, 刘野. N-桥膦羰基钯配合物催化乙烯/一氧化碳非交替共聚反应. 高分子学报, 2025, 56(7), 1180-1191

Li, X. J.; Li, S. H.; Chen, S. Y.; Liu, Y. N-Bridged phosphine carbonyl palladium complex catalysts for nonalternating copolymerization of ethylene and carbon monoxide. Acta Polymerica Sinica, 2025, 56(7), 1180-1191
李欣俊, 李世环, 陈世瑜, 刘野. N-桥膦羰基钯配合物催化乙烯/一氧化碳非交替共聚反应. 高分子学报, 2025, 56(7), 1180-1191 DOI： 10.11777/j.issn1000-3304.2025.25031. CSTR： 32057.14.GFZXB.2025.7380.

Li, X. J.; Li, S. H.; Chen, S. Y.; Liu, Y. N-Bridged phosphine carbonyl palladium complex catalysts for nonalternating copolymerization of ethylene and carbon monoxide. Acta Polymerica Sinica, 2025, 56(7), 1180-1191 DOI： 10.11777/j.issn1000-3304.2025.25031. CSTR： 32057.14.GFZXB.2025.7380.

摘要

脂肪族聚酮是一类由乙烯和一氧化碳(CO)共聚而成的绿色高性能材料，具有广泛的应用范围. 然而，完全交替聚酮的熔融温度(

)高达260 ℃，且与分解温度(270 ℃)相近，导致其加工窗口受限，通过非交替共聚降低聚酮的

值是解决此加工问题的重要方法之一. 实现乙烯/CO非交替共聚的关键在于提高催化剂对CO的耐受性以及削弱CO迁移插入的倾向性. 基于此，本研究设计了一系列

-桥膦羰基型(PNCO)型钯配合物，并将其应用于乙烯/CO共聚反应中，实现了羰基含量和熔融温度可调控的非交替聚酮制备. 其中，胺端为苄基、膦端为2

6-二甲氧基苯基和羰基端为4-三氟甲基苯基的配合物表现出最高的活性，可催化制备羰基含量低至44.6%的非交替聚酮，使该材料的熔融温度降至223 ℃，从而有效改善了脂肪族聚酮的加工性能. 该工作为非交替聚酮领域提供了一种新的催化体系.

Abstract

Aliphatic polyketone is a class of high-performance polymer materials obtained through the copolymerization of ethylene with carbon monoxide (CO)

which has a wide range of applications. However

the completely alternating structure suffers from narrow processing temperature window because of its high melting temperature (

) of 260 ℃ and a close decomposition temperature of

270 ℃. Nonalternating copolymerization is a very promising method to circumvent this processing issue

and enhancing CO tolerance of catalyst and weakening the tendency for CO migration insertion are the key to nonalternating preference. In the contribution

a series of

-bridged phosphine carbonyl (PNCO)-Pd(II) complexes were designed and employed for copolymerization of ethylene with CO

affording nonalternating polyketones with controllable carbonyl contents and melting temperatures. The installations of benzyl on amine

6-dimethoxyl phenyl on phosphorus and 4-trifluoromethylphenyl on carbonyl moieties were discovered to be highly reactive for producing nonalternating polyketones with carbonyl content of 44.6%

thereby lowing the

values to 223 ℃ effectively. This work provides a new catalytic system for the nonalternating polyketone field.

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references

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精细化工国家重点实验室大连理工大学化工学院

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N-Bridged Phosphine Carbonyl Palladium Complex Catalysts for Nonalternating Copolymerization of Ethylene and Carbon Monoxide

DOI：10.11777/j.issn1000-3304.2025.25031

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