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
- Understanding Broad Polydispersity in Step-growth Polymerization via Catalyst Competition Mechanism
- 高分子科学（英文版） 2024年42卷第12期页码：1897-1904
- 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：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 22171083), and Shanghai Leading Academic Discipline Project (No. B502). AH thanks the “Eastern Scholar Professorship” support from Shanghai local government and the Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3217-2.
- DOI：10.1007/s10118-024-3217-2
  中图分类号：
- 收稿：2024-07-04，
  
  修回：2024-08-03，
  
  录用：2024-08-15，
  
  网络首发：2024-11-07，
  
  纸质出版：2024-12-01
- 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. DOI: 10.1007/s10118-024-3217-2.
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. DOI：

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.

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references

Flory, P. J. Principles of Polymer Chemistry . Cornell University Press: Ithaca, New York, 1953 , p. 688..

Qiu, Z.; Hammer, B. A. G.; Müllen, K. Conjugated polymers – Problems and promises. Prog. Polym. Sci. 2020 , 100 , 101179..

Verheyen, L.; Leysen, P.; Van Den Eede, M. P.; Ceunen, W.; Hardeman, T.; Koeckelberghs, G. Advances in the controlled polymerization of conjugated polymers. Polymer 2017 , 108 , 521−546..

Nadgorny, M.; Gentekos, D. T.; Xiao, Z.; Singleton, S. P.; Fors, B. P.; Connal, L. A. Manipulation of molecular weight distribution shape as a new strategy to control processing parameters. Macromol. Rapid Commun. 2017 , 38 , 1700352..

Nichetti, D.; Manas-Zloczower, I. Influence of molecular parameters on material processability in extrusion processes. Polym.Eng. Sci. 1999 , 39 , 887−895..

Lu, L.; Zheng, T.; Xu, T.; Zhao, D.; Yu, L. Mechanistic studies of effect of dispersity on the photovoltaic performance of PTB7 polymer solar cells. Chem. Mater. 2015 , 27 , 537−543..

Carothers, W. H. Polymers and polyfunctionality. Trans. Faraday Soc. 1936 , 32 , 39−49..

Flory, P. J. Molecular size distribution in linear condensation polymers1. J. Am. Chem. Soc. 1936 , 58 , 1877−1885..

Sui, Y.; Deng, Y.; Du, T.; Shi, Y.; Geng, Y. Design strategies of n-type conjugated polymers f or organic thin-film transistors. Mater. Chem. Front. 2019 , 3 , 1932−1951..

Sui, Y.; Shi, Y.; Deng, Y.; Li, R.; Bai, J.; Wang, Z.; Dang, Y.; Han, Y.; Kirby, N.; Ye, L.; Geng, Y. Direct arylation polycondensation of chlorinated thiophene derivatives to high-mobility conjugated polymers. Macromolecules 2020 , 53 , 10147−10154..

Lai, Y. Y.; Yang, H. R.; Lee, H. T.; Tsai, T. L.; Sun, H. S. In vitro and in silico studies on the base effect in palladium-catalyzed direct arylation. Asian J. Org. Chem . 2020, 9 , 296-302..

Li, Z.; Shi, Q.; Ma, X.; Li, Y.; Wen, K.; Qin, L.; Chen, H.; Huang, W.; Zhang, F.; Lin, Y.; Marks, T. J.; Huang, H. Efficient room temperature catalytic synthesis of alternating conjugated copolymers via C-S bond activation. Nat. Commun. 2022 , 13 , 144−144..

Yao, X. Q.; Wang, Y. S.; Wang, J. Palladium-catalyzed carbene coupling polymerization: synthesis of E-poly(arylene vinylene)s. Chem. Commun. 2022 , 58 , 4032−4035..

Ye, L.; Thompson, B. C. Improving the efficiency and sustainability of catalysts for direct arylation polymerization (DArP). J. Polym. Sci. 2022 , 60 , 393−428..

Kleybolte, M. E.; Vagin, S. I.; Rieger, B. High-molecular-weight bisalkoxy-substituted poly(para)phenylenes by kumada polymerization. Macromolecules 2022 , 55 , 5361−5370..

Collier, G. S.; Wilkins, R.; Tomlinson, A. L.; Reynolds, J. R. Exploring isomeric effects on optical and electrochemical properties of red/orange electrochromic polymers. Macromolecules 2021 , 54 , 1677−1692..

Hwang, K.; Lee, M. H.; Kim, J.; Kim, Y. J.; Kim, Y.; Hwang, H.; Kim, I. B.; Kim, D. Y. 3,4-Ethylenedioxythiophene-based isomer-free quinoidal building block and conjugated polymers for organic field-effect transistors. Macromolecules 2020, 53 , 1977-1987..

Shida, N.; Ninomiya, K.; Takigawa, N.; Imato, K.; Ooyama, Y.; Tomita, I.; Inagi, S. Diversification of conjugated polymers via postpolymerization nucleophilic aromatic substitution reactions with sulfur-, oxygen-, and nitrogen-based nucleophiles. Macromolecules 2021 , 54 , 725−735..

Chen, T. A.; Wu, X.; Rieke, R. D. Regiocontrolled synthesis of poly(3-alkylthiophenes) mediated by rieke zinc: their characterization and solid-state properties. J. Am. Chem. Soc. 1995 , 117 , 233−244..

Jacobson, H.; Beckmann, C. O.; Stockmayer, W. H. Intramolecular reaction in polycondensations. II. Ring-chain equilibrium in polydecamethylene adipate. J. Chem. Phys. 1950 , 18 , 1607−1612..

Jacobson, H.; Stockmayer, W. H. Intramolecular reaction in polycondensations. I. The theory of linear systems. J. Chem. Phys. 1950 , 18 , 1600−1606..

Stanford, J. L.; Stepto, R. F. T.; Waywell, D. R. Rate theory of irreversible linear random polymerisation. Part 2. Application to intramolecular reaction in A-A + B-B type polymerisations. J. Chem. Soc., Faraday Trans. 1 1975 , 71 , 1308−1326..

Gordon, M.; Temple, W. B. The graph-like state of molecules. III. Ring-chain competition kinetics in linear polymerisation reactions. Makromol. Chem. 1972 , 160 , 263−276..

Gordon, M.; Temple, W. B. Ring-chain competition kinetics in linear polymers. Makromol. Chem. 1972 , 152 , 277−289..

Romero-Hernandez, J. E.; Cruz-Rosado, A.; Vivaldo-Lima, E.; Palacios-Alquisira, J.; Zolotukhin, M. G. Analysis of the competition between cyclization and linear chain growth in kinetically controlled A(2) + B(2) step-growth polymerizations using modeling tools. Macromol. Theory Simul. 2020 , 29 , 2000050..

Li, Y.; Wang, X.; He, Z.; Johnson, M.; A, S.; Lara-Sáez, I.; Lyu, J.; Wang, W. 3D macrocyclic structure boosted gene delivery: multi-cyclic poly( β -amino ester)s from step growth polymerization. J. Am. Chem. Soc . 2023, 145 , 17187-17200..

Luo, S.; Xu, Z.; Zhong, F.; Li, H.; Chen, L. Doping-induced charge transfer in conductive polymers. Chin. Chem. Lett. 2024 , 35 , 109014..

Miyakoshi, R.; Yokoyama, A.; Yokozawa, T. Catalyst-transfer polycondensation. Mechanism of Ni-catalyzed chain-growth polymerization lea ding to well-defined poly(3-hexylthiophene). J. Am. Chem. Soc. 2005 , 127 , 17542−17547..

Trznadel, M.; Pron, A.; Zagorska, M.; Chrzaszcz, R.; Pielichowski, J. Effect of molecular weight on spectroscopic and spectroelectrochemical properties of regioregular poly(3-hexylthiophene). Macromolecules 1998 , 31 , 5051−5058..

McCulloch, B.; Ho, V.; Hoarfrost, M.; Stanley, C.; Do, C.; Heller, W. T.; Segalman, R. A. Polymer chain shape of poly(3-alkylthiophenes) in solution using small-angle neutron scattering. Macromolecules 2013 , 46 , 1899−1907..

Nagai, M.; Huang, J.; Zhou, T.; Huang, W. Effect of molecular weight on conformational characteristics of poly(3-hexyl thiophene). J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1273−1277..

Gu, K.; Onorato, J.; Xiao, S. S.; Luscombe, C. K.; Loo, Y. L. Determination of the molecular weight of conjugated polymers with diffusion-ordered NMR spectroscopy. Chem. Mater. 2018 , 30 , 570−576..

Pouliot, J.-R.; Wakioka, M.; Ozawa, F.; Li, Y.; Leclerc , M. Structural analysis of poly(3-hexylthiophene) prepared via direct heteroarylation polymerization. Macrom. Chem. Phys. 2016 , 217 , 1493−1500..

O'Brien, C. J.; Kantchev, E. A. B.; Valente, C.; Hadei, N.; Chass, G. A.; Lough, A.; Hopkinson, A. C.; Organ, M. G. Easily prepared air- and moisture-stable Pd-NHC (NHC=N-heterocyclic carbene) complexes: a reliable, user-friendly, highly active palladium precatalyst for the Suzuki-Miyaura reaction. Chem. Eur. J. 2006 , 12 , 4743−4748..

Wu, Y.; Ding, M.; Wang, J.; Zhao, B.; Wu, Z.; Zhao, P.; Tian, D.; Ding, Y.; Hu, A. Controlled step-growth polymerization. CCS Chem. 2020 , 2 , 64−70..

Phan, N. T. S.; Van Der Sluys, M.; Jones, C. W. On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura Couplings--homogeneous or heterogeneous catalysis, a critical review. Adv. Synth. Catal. 2006, 348 , 609-679..

Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An overview of N -heterocyclic carbenes. Nature 2014 , 510 , 485−96..

Lo, C. K.; Wolfe, R. M. W.; Reynolds, J. R. From monomer to conjugated polymer: a perspective on best practices for synthesis. Chem. Mater. 2021 , 33 , 4842−4852..

Zhang, P.; Weng, Z.; Guo, J.; Wang, C. Solution-dispersible, colloidal, conjugated porous polymer networks with entrapped palladium nanocrystals for heterogeneous catalysis of the Suzuki-Miyaura coupling reaction. Chem. Mater. 2011 , 23 , 5243−5249..

Arduengo, A. J. Looking for stable carbenes: the difficulty in starting anew. Acc. Chem. Res. 1999 , 32 , 913−921..

Arduengo, A. J., III; Harlow, R. L.; Kline, M. A stable crystalline carbene. J. Am. Chem. Soc. 1991 , 113 , 361−363..

Xu, S. J.; Song, K. P.; Li, T.; Tan, B. Palladium catalyst coordinated in knitting N -heterocyclic carbene porous polymers for efficient Suzuki-Miyaura coupling reactions. J. Mater. Chem. A 2015 , 3 , 1272−1278..

Wang, W.; Cui , L.; Sun, P.; Shi, L.; Yue, C.; Li, F. Reusable N -heterocyclic carbene complex catalysts and beyond: a perspective on recycling strategies. Chem. Rev. 2018 , 118 , 9843−9929..

Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Palladium complexes of N -heterocyclic carbenes as catalysts for cross-coupling reactions—a synthetic chemist's perspective. Angew. Chem. Int. Ed. 2007 , 46 , 2768−2813..

Wang, J.; Tian, D.; Zhang, X.; Pan, H.; Ding, Y.; Wang, G.; Hu, A. Synthesis of narrowly distributed α,ω -bifunctionalized conjugated polymers. Macromolecules 2023 , 56 , 5835−5842..

Zhang, Z.; Wang, Z.; He, S.; Wang, C.; Jin, M.; Yin, Y. Redox reaction induced Ostwald ripening for size- and shape-focusing of palladium nanocrystals. Chem. Sci. 2015 , 6 , 5197−5203..

Wang, D. P.; Yuan, Y.; Mardiyati, Y.; Bubeck, C.; Koynov, K. From single chains to aggregates, how conjugated polymers behave in dilute solutions. Macromolecules 2013 , 46 , 6217−6224..

Kwok, J. J.; Park, K. S.; Patel, B. B.; Dilmurat, R.; Beljonne, D.; Zuo, X. B.; Lee, B.; Diao, Y. Understanding solution state conformation and aggregate structure of conjugated polymers via small angle X-ray scattering. Macromolecules 2022 , 55 , 4353−4366..

Denisova, E. A.; Kostyukovich, A. Y.; Fakhrutdinov, A. N.; Korabelnikova, V. A.; Galushko, A. S.; Ananikov, V. P. “Hidden” nanoscale catalysis in alkyne hydrogenation with well-defined molecular Pd/NHC complexes. ACS Catal . 2022, 12 , 6980-6996..

Deraedt, C.; Astruc, D. “Homeopathic” palladium nanoparticle catalysis of cross carbon–carbon coupling reactions. Acc. Chem. Res . 2013, 47 , 494-503..

Xu, J.; Wu, H.-C.; Mun, J.; Ning, R.; Wang, W.; Wang, G. J. N.; Nikzad, S.; Yan, H.; Gu, X.; Luo, S.; Zhou, D.; Tok, J. B. H.; Bao, Z. Tuning conjugated polymer chain packing for stretchable semiconductors. Adv. Mater. 2022 , 34 , 2104747..

Villa, M.; Cannata, V.; Rosi, A.; Allegrini, P.; Sasso, M. WO9851646-A1; ZA9804039-A; AU9875302-A; NO9905528-A; EP981507-A1; CZ9904013-A3; SK9901539-A3; BR9808795-A; CN1255912-A; HU200002119-A2; NZ500565-A; US6239301-B1; MX9910410-A1; IT1291356-B; AU739778-B; JP2001524977-W; SK282370-B6; NO312509-B1; HU222599-B1; EP981507-B1; DE69825745-E; MX215483-B; CZ294236-B6; IL132561-A; ES2227832-T3; CN1092624-C; DE69825745-T2; RO119714-B1; CA2288647-C; EA2285-B1.

Rudenko, A. E.; Thompson, B. C. Optimization of direct arylation polymerization (DArP) through the identification and control of defects in polymer structure. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53 , 135−147..

Kappaun, S.; Zelzer, M.; Bartl, K.; Saf, R.; Stelzer, F.; Slugovc, C. Preparation of poly(fluorene)s using trans-bis(dicyclohexylamine)palladium diacetate as a catalyst: scope and limitations. J. Polym. Sci., Part A: Polym. Chem. 2006 , 44 , 2130−2138..

Chinchilla, R.; Najera, C. The sonogashira reaction: a booming methodology in synthetic organic chemistry. Chem. Rev. 2007 , 107 , 874−922..

Rudenko, A. E.; Wiley, C. A.; Tannaci, J. F.; Thompson, B. C. Optimization of direct arylation polymerization conditions for the synthesis of poly(3-hexylthiophene). J. Polym. Sci., Part A: Polym. Chem. 2013 , 51 , 2660−2668..

Liversedge, I. A.; Higgins, S. J.; Giles, M.; Heeney, M.; McCulloch, I. Suzuki route to regioregular polyalkylthiophenes using Ir-catalysed borylation to make the monomer, and Pd complexes of bulky phosphanes as coupling catalysts for polymerisation. Tetra. Lett. 2006 , 47 , 5143−5146..

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

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