Understanding Broad Polydispersity in Step-growth Polymerization <italic style="font-style: italic">via</italic> Catalyst Competition Mechanism

Donglai Tian; Jie Wang; Xiaohua Huang; Yun Ding; Aiguo Hu

doi:10.1007/s10118-024-3217-2

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Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism

RESEARCH ARTICLE | Updated：2024-12-03

- Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism
- Chinese Journal of Polymer Science Vol. 42, Issue 12, Pages: 1897-1904(2024)
- Affiliations：
  
  Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  yunding@ecust.edu.cn (Y.D.)
  hagmhsn@ecust.edu.cn (A.H.)
- Funds：
- DOI：10.1007/s10118-024-3217-2
  CLC：
- Published：01 December 2024，
  
  Published Online：07 November 2024，
  
  Received：04 July 2024，
  
  Revised：03 August 2024，
  
  Accepted：15 August 2024
- Accepted：
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Tian, D.; Wang, J.; Huang, X.; Ding, Y.; Hu, A. Understanding broad polydispersity in step-growth polymerization via catalyst competition mechanism. Chinese J. Polym. Sci. 2024, 42, 1897–1904

DONGLAI TIAN, JIE WANG, XIAOHUA HUANG, et al. Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism. [J]. Chinese journal of polymer science, 2024, 42(12): 1897-1904.
Tian, D.; Wang, J.; Huang, X.; Ding, Y.; Hu, A. Understanding broad polydispersity in step-growth polymerization via catalyst competition mechanism. Chinese J. Polym. Sci. 2024, 42, 1897–1904 DOI： 10.1007/s10118-024-3217-2.

DONGLAI TIAN, JIE WANG, XIAOHUA HUANG, et al. Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism. [J]. Chinese journal of polymer science, 2024, 42(12): 1897-1904. DOI： 10.1007/s10118-024-3217-2.

摘要

We proposed a catalyst competition mechanism through experimental validation and computational simulations

successfully elucidating the origins of broad molecular weight distributions in step-growth polymerization

which holds significant guidance for the synthesis and processing of conjugated polymers.

Abstract

Conjugated polymers are mainly synthesized by cross-coupling polymerizations catalyzed with transition metal (Pd

Ni) catalysts through step-growth polymerization (SGP) mechanism. According to the classical theory of SGP

the polymer dispersion index (

) of the synthesized polymers will never be higher than 2. However

the cases where conjugated polymers synthesized with

value far exceeding 2 are very common in reality

which severely limits their processing property

performance and applications. To investigat

e the reason behind the

value deviation from the theoretical value of SGP

direct arylation polycondensation (DArP) of 2-bromo-3-hexylthiophene (3HT) was chosen as the model reaction

and the reaction process was tracked using gel permeation chromatography analysis. When Pd(OAc)

was used as the catalyst

the

value linearly increased with the increase of the weight-average molecular weight (

) of polymer (P3HT) after a short period and reached up to 7.2 at prolonged reaction time. Scanning transmission electron microscopic images of the reaction mixture showed the fibril-like aggregation of P3HT and assembling of Pd species in P3HT aggregates. A catalyst competition mechanism was thus proposed

together with numerical calculation

giving a good fitting to the experimental results

which is believed to have far-reaching significance for guiding the design

synthesis and processing of conjugated polymers.

关键词

Keywords

Step-growth polymerizationConjugated polymerPolymer dispersion indexCatalyst competition mechanism

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⁰

Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism

DOI：10.1007/s10118-024-3217-2

摘要

Abstract

关键词

Keywords

references