Mainchain Semifluorinated Polymers with Ultra High Molecular Weight<italic style="font-style: italic">via</italic>Reaction-enhanced Reactivity of Intermediate (RERI) Mechanism

Jia-Sheng Wu; Wang-Meng Hou; Zhi-Jia Liu; Yi Shi; Yong-Ming Chen

doi:10.1007/s10118-023-2919-1

Your Location：

Home >

Browse articles >

Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism

RESEARCH ARTICLE | Updated：2023-04-21

- Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism
- Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism
- 高分子科学（英文版） 2023年41卷第5期页码：760-767
- Affiliations：
  
  School of Materials Science and Engineering, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Sun Yat-Sen University, Guangzhou 510006, China
- Author bio：
  
  shiyi6@mail.sysu.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 22071271).;Electronic supplementary information (ESI) is available free of charge in the online version of this article athttp://doi.org/10.1007/s10118-023-2919-1.
- DOI：10.1007/s10118-023-2919-1
  中图分类号：
- 收稿：2022-11-08，
  
  修回：2022-11-24，
  
  录用：2022-12-3，
  
  网络首发：2023-01-11，
  
  纸质出版：2023-05-01
- Accepted：
Scan QR Code
Wu, J. S.; Hou, W. M.; Liu, Z. J.; Shi, Y.; Chen, Y. M. Mainchain semifluorinated polymers with ultra high molecular weightviareaction-enhanced reactivity of intermediate (RERI) mechanism.Chinese J. Polym. Sci.2023,41, 760–767

Jia-Sheng Wu, Wang-Meng Hou, Zhi-Jia Liu, et al. Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism[J]. Chinese Journal of Polymer Science, 2023, 41(5): 760-767. DOI: 10.1007/s10118-023-2919-1.
Wu, J. S.; Hou, W. M.; Liu, Z. J.; Shi, Y.; Chen, Y. M. Mainchain semifluorinated polymers with ultra high molecular weightviareaction-enhanced reactivity of intermediate (RERI) mechanism.Chinese J. Polym. Sci.2023,41, 760–767 DOI： 10.1007/s10118-023-2919-1.

Jia-Sheng Wu, Wang-Meng Hou, Zhi-Jia Liu, et al. Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism[J]. Chinese Journal of Polymer Science, 2023, 41(5): 760-767. DOI: 10.1007/s10118-023-2919-1. DOI：

摘要

A rapid and highly efficient step-growth polymerization with reaction-enhanced reactivity of intermediate (RERI) mechanism based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction was developed to achieve the (ultra)high-molecular-weight mainchain semifluorinated polymers with diverse chemical compositions under a stoichiometric imbalance condition.

Abstract

Achieving the linear polymers with high molecular weight

via

step-growth polymerization of A

and B

monomers is significantly limited by the requirement of strict stoichiometry of two monomers when the reactivity of A and B groups are not changed during the polymerization. Herein

a unique step-growth polymerization based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) with reaction-enhanced reactivity of intermediate (RERI) mechanism was developed for the preparation of mainchain semifluorinated polymers with high molecular weight. The CuAAC polymerization of bis-alkynyl-terminated fluorinated monomers (A

) and 2

2-bis(azidomethyl)propane-1

3-diyl bis(2-methylpropanoate) (BiAz

) with RERI effect at different stoichiometric ratio was systematically investigated. The results indicated that the semifluorinated polymers with ultrahigh molecular weight

MALLS

g/mol

could be efficiently synthesized by using excess molar of BiAz monomers. The resultant high-molecular-weight semifluorinated polymers show good thermostability and high hydrophobicity. In addition

the glass transition temperature (

) of these mainchain semifluorinated polymers could be tuned conveniently due to the bis-alkynyl-terminated comonomers could be consumed completely when excessive BiAz monomers were used in this this step-growth polymerization.

关键词

Keywords

references

Ma, M.; Shao, F.; Wen, P.; Chen, K.; Li, J.; Zhou, Y.; Liu, Y.; Jia, M.; Chen, M.; Lin, X . Designing weakly solvating solid main-chain fluoropolymer electrolytes: synergistically enhancing stability toward Li anodes and high-voltage cathodes . ACS Energy Lett. , 2021 , 6 4255 - 4264 . DOI: 10.1021/acsenergylett.1c02036 http://doi.org/10.1021/acsenergylett.1c02036 .

Jia, M.; Wen, P.; Wang, Z.; Zhao, Y.; Liu, Y.; Lin, J.; Chen, M.; Lin, X . Fluorinated bifunctional solid polymer electrolyte synthesized under visible light for stable lithium deposition and dendrite-free all-solid-state batteries . Adv. Funct. Mater. , 2021 , 31 2101736 DOI: 10.1002/adfm.202101736 http://doi.org/10.1002/adfm.202101736 .

Wang, R.; Yang, S.; Xiao, P.; Sun, Y.; Li, J.; Jiang, X.; Wu, W . Fluorination and betaine modification augment the blood-brain barrier-crossing ability of cylindrical polymer brushes . Angew. Chem. Int. Ed. , 2022 , 61 e202201390 .

Stein, H. L. Ultrahigh molecular weight polyethylene (UHMWPE), in Engineered Materials Handbook ; ASM International: Materials Park, OH, 1999 ; Vol. 2, pp 167−171.

Discekici, E. H.; Anastasaki, A.; Kaminker, R.; Willenbacher, J.; Truong, N. P.; Fleischmann, C.; Oschmann, B.; Lunn, D. J.; Read de Alaniz, J.; Davis, T. P.; Bates, C. M.; Hawker, C. J . Light-mediated atom transfer radical polymerization of semi-fluorinated (meth)acrylates: facile access to functional materials . J. Am. Chem. Soc. , 2017 , 139 5939 - 5945 . DOI: 10.1021/jacs.7b01694 http://doi.org/10.1021/jacs.7b01694 .

Gong, H.; Zhao, Y.; Shen, X.; Lin, J.; Chen, M . Organocatalyzed photocontrolled radical polymerization of semifluorinated (meth)acrylates driven by visible light . Angew. Chem. Int. Ed. , 2018 , 57 333 - 337 . DOI: 10.1002/anie.201711053 http://doi.org/10.1002/anie.201711053 .

Gong, H.; Gu, Y.; Zhao, Y.; Quan, Q.; Han, S.; Chen, M . Precise synthesis of ultra-high-molecular-weight fluoropolymers enabled by chain-transfer-agent differentiation under visible-light irradiation . Angew. Chem. Int. Ed. , 2020 , 59 919 - 927 . DOI: 10.1002/anie.201912698 http://doi.org/10.1002/anie.201912698 .

Zhao, Y.; Ma, M.; Lin, X.; Chen, M . Photoorganocatalyzed divergent reversible-deactivation radical polymerization towards linear and branched fluoropolymers . Angew. Chem. Int. Ed. , 2020 , 59 21470 - 21474 . DOI: 10.1002/anie.202009475 http://doi.org/10.1002/anie.202009475 .

Jiang, K.; Han, S.; Ma, M.; Zhang, L.; Zhao, Y.; Chen, M . Photoorganocatalyzed reversible-deactivation alternating copolymerization of chlorotrifluoroethylene and vinyl ethers under ambient conditions: facile access to main-chain fluorinated copolymers . J. Am. Chem. Soc. , 2020 , 142 7108 - 7115 . DOI: 10.1021/jacs.0c01016 http://doi.org/10.1021/jacs.0c01016 .

Quan, Q.; Ma, M.; Wang, Z.; Gu, Y.; Chen, M . Visible-light-enabled organocatalyzed controlled alternating terpolymerization of perfluorinated vinyl ethers . Angew. Chem. Int. Ed. , 2021 , 60 20443 - 20451 . DOI: 10.1002/anie.202107066 http://doi.org/10.1002/anie.202107066 .

Daglar, O.; Cakmakci, E.; Gunay, U . S.; Hizal, G.; Tunca, U.; Durmaz, H. A straightforward method for fluorinated polythioether synthesis . Macromolecules , 2020 , 53 2965 - 2975 . DOI: 10.1021/acs.macromol.0c00548 http://doi.org/10.1021/acs.macromol.0c00548 .

Wang, X.; Hong, M . Precise control of molecular weight and stereospecificity in Lewis pair polymerization of semifluorinated methacrylates: mechanistic studies and stereocomplex formation . Macromolecules , 2020 , 53 4659 - 4669 . DOI: 10.1021/acs.macromol.0c00553 http://doi.org/10.1021/acs.macromol.0c00553 .

Gong, H.; Zhang, Y.; Cheng, Y.; Lei, M.; Zhang, Z . The application of controlled/living radical polymerization in modification of PVDF-based fluoropolymer . Chinese J. Polym. Sci. , 2021 , 39 1110 - 1126 . DOI: 10.1007/s10118-021-2616-x http://doi.org/10.1007/s10118-021-2616-x .

Carmean, R. N.; Becker, T. E.; Sims, M. B.; Sumerlin, B. S . Ultra-high molecular weights via aqueous reversible-deactivation radical polymerization . Chem , 2017 , 2 93 - 101 . DOI: 10.1016/j.chempr.2016.12.007 http://doi.org/10.1016/j.chempr.2016.12.007 .

Bai, Y.; He, J.; Zhang, Y . Ultra-high-molecular-weight polymers produced by the immortal phosphine-based catalyst system . Angew. Chem. Int. Ed. , 2018 , 57 17230 - 17234 . DOI: 10.1002/anie.201811946 http://doi.org/10.1002/anie.201811946 .

Liu, Z.; Lv, Y.; An, Z . Enzymatic cascade catalysis for the synthesis of multiblock and ultrahigh-molecular-weight polymers with oxygen tolerance . Angew. Chem. Int. Ed. , 2017 , 56 13852 - 13856 . DOI: 10.1002/anie.201707993 http://doi.org/10.1002/anie.201707993 .

Li, R.; An, Z . Achieving ultrahigh molecular weights with diverse architectures for unconjugated monomers through oxygen-tolerant photoenzymatic RAFT polymerization . Angew. Chem. Int. Ed. , 2020 , 59 22258 - 22264 . DOI: 10.1002/anie.202010722 http://doi.org/10.1002/anie.202010722 .

Carmean, R. N.; Sims, M. B.; Figg, C. A.; Hurst, P. J.; Patterson, J. P.; Sumerlin, B. S . Ultrahigh molecular weight hydrophobic acrylic and styrenic polymers through organic-phase photoiniferter-mediated polymerization . ACS Macro Lett. , 2020 , 9 613 - 618 . DOI: 10.1021/acsmacrolett.0c00203 http://doi.org/10.1021/acsmacrolett.0c00203 .

Kihara, N.; Komatsu, S . I.; Takata, T.; Endo, T. Significance of stoichiometric imbalance in step polymerization via reactive intermediate . Macromolecules , 1999 , 32 4776 - 4783 . DOI: 10.1021/ma981835l http://doi.org/10.1021/ma981835l .

Dutta, T.; Woody, K. B.; Watson, M. D . Transition-metal-free synthesis of poly(phenylene ethynylene)s with alternating aryl-perfluoroaryl units . J. Am. Chem. Soc. , 2008 , 130 452 - 453 . DOI: 10.1021/ja710564b http://doi.org/10.1021/ja710564b .

Goto, E.; Ando, S.; Ueda, M.; Higashihara, T . Nonstoichiometric stille coupling polycondensation for synthesizing naphthalene-diimide-based π -conjugated polymers . ACS Macro Lett. , 2015 , 4 1004 - 1007 . DOI: 10.1021/acsmacrolett.5b00532 http://doi.org/10.1021/acsmacrolett.5b00532 .

Zou, L.; Cao, X.; Zhang, Q.; Dodds, M.; Guo, R.; Gao, H . Friedel-crafts A 2 +B 4 polycondensation toward regioselective linear polymer with rigid triphenylmethane backbone and its property as gas separation membrane . Macromolecules , 2018 , 51 6580 - 6586 . DOI: 10.1021/acs.macromol.8b01394 http://doi.org/10.1021/acs.macromol.8b01394 .

Lindner, J. P . Imidazolium-based polymers via the poly-Radziszewski reaction . Macromolecules , 2016 , 49 2046 - 2053 . DOI: 10.1021/acs.macromol.5b02417 http://doi.org/10.1021/acs.macromol.5b02417 .

Zhang, L.; Ren, X.; Zhang, Y.; Zhang, K . Step-growth polymerization method for ultrahigh molecular weight polymers . ACS Macro Lett. , 2019 , 8 948 - 954 . DOI: 10.1021/acsmacrolett.9b00475 http://doi.org/10.1021/acsmacrolett.9b00475 .

Chen, J . Q.; Xiang, L.; Liu, X.; Liu, X.; Zhang, K. Self-accelerating click reaction in step polymerization . Macromolecules , 2017 , 50 5790 - 5797 . DOI: 10.1021/acs.macromol.7b01173 http://doi.org/10.1021/acs.macromol.7b01173 .

Miyatake, K.; Hlil, A. R.; Hay, A. S . High Molecular weight aromatic polyformals free of macrocyclic oligomers. A condensative chain polymerization reaction . Macromolecules , 2001 , 34 4288 - 4290 . DOI: 10.1021/ma002020r http://doi.org/10.1021/ma002020r .

Olvera, L. I.; Zolotukhin, M. G.; Hernández-Cruz, O.; Fomine, S.; Cárdenas, J.; Gaviño-Ramírez, R. L.; Ruiz-Trevino, F. A . Linear, single-strand heteroaromatic polymers from superacid-catalyzed step-growth polymerization of ketones with bisphenols . ACS Macro Lett. , 2015 , 4 492 - 494 . DOI: 10.1021/acsmacrolett.5b00164 http://doi.org/10.1021/acsmacrolett.5b00164 .

Xiang, L.; Li, Z.; Liu, J . A.; Chen, J.; Zhang, M.; Wu, Y.; Zhang, K. Periodic Polymers Based on a Self-accelerating Click Reaction . Polym. Chem. , 2018 , 9 4036 - 4043 . DOI: 10.1039/C8PY00645H http://doi.org/10.1039/C8PY00645H .

Liu, X.; Xiang, L.; Li, J.; Wu, Y.; Zhang, K . Stoichiometric imbalance-promoted step-growth polymerization based on self-accelerating 1,3-dipolar cycloaddition click reactions . Polym. Chem. , 2020 , 11 125 - 134 . DOI: 10.1039/C9PY01362H http://doi.org/10.1039/C9PY01362H .

Cruz, A. R.; Hernandez, M. C. G.; Guzmán-Gutiérrez, M. T.; Zolotukhin, M. G.; Fomine, S.; Morales, S. L.; Kricheldorf, H.; Wilks, E . S.; Cárdenas, J.; Salmón, M. Precision synthesis of narrow polydispersity, ultrahigh molecular weight linear aromatic polymers by A 2 + B 2 nonstoichiometric step-selective polymerization . Macromolecules , 2012 , 45 6774 - 6780 . DOI: 10.1021/ma301691f http://doi.org/10.1021/ma301691f .

Guzmán-Gutiérrez, M. T.; Nieto, D. R.; Fomine, S.; Morales, S. L.; Zolotukhin, M. G.; Hernandez, M. C. G.; Kricheldorf, H.; Wilks, E. S . Dramatic enhancement of superacid-catalyzed polyhydroxyalkylation reactions . Macromolecules , 2011 , 44 194 - 202 . DOI: 10.1021/ma102267f http://doi.org/10.1021/ma102267f .

Kolb, H. C.; Finn, M. G.; Sharpless, K. B . Click chemistry: diverse chemical function from a few good reactions . Angew. Chem. Int. Ed. , 2001 , 40 2004 - 2021 . DOI: 10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5 http://doi.org/10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5 .

Shi, Y.; Chen, Y.; Liang, Y.; Andrews, J.; Dong, H.; Yuan, M.; Ding, W.; Banerjee, S.; Ardebili, H.; Robertson, M. L.; Cui, X.; Yao, Y . Chemically inert covalently networked triazole-based solid polymer electrolytes for stable all-solid-state lithium batteries . J. Mater.Chem. A , 2019 , 7 19691 - 19695 . DOI: 10.1039/C9TA05885K http://doi.org/10.1039/C9TA05885K .

Shi, Y.; Zhu, W.; Yao, D.; Long, M.; Peng, B.; Zhang, K.; Chen, Y . Disk-like Micelles with a highly ordered pattern from molecular bottlebrushes . ACS Macro Lett. , 2014 , 3 70 - 73 . DOI: 10.1021/mz400619g http://doi.org/10.1021/mz400619g .

Sun, H.; Haque, F. M.; Zhang, Y.; Commisso, A.; Mohamed, M. A.; Tsianou, M.; Cui, H.; Grayson, S. M.; Cheng, C . Linear-dendritic alternating copolymers . Angew. Chem. Int. Ed. , 2019 , 58 10572 - 10576 . DOI: 10.1002/anie.201903402 http://doi.org/10.1002/anie.201903402 .

Xu, L.; Zhang, Q.; Lu, L.; Shi, Y.; Liu, L.; Shen, J.; Chen, Y . Unimolecular nano-contrast agent with ultrahigh relaxivity and very long retention for magnetic resonance lymphography . Nano Lett. , 2022 , 22 4090 - 4096 . DOI: 10.1021/acs.nanolett.2c00796 http://doi.org/10.1021/acs.nanolett.2c00796 .

Zhang, M.; Wu, J.; Li, Z.; Hou, W.; Li, Y.; Shi, Y.; Chen, Y . Synthesis and visualization of bottlebrush-shaped segmented hyperbranched polymers . Polym. Chem. , 2022 , 13 4895 - 4900 . DOI: 10.1039/D2PY00898J http://doi.org/10.1039/D2PY00898J .

Shi, Y.; Cao, X.; Gao, H . The use of azide-alkyne click chemistry in recent syntheses and applications of polytriazole-based nanostructured polymers . Nanoscale , 2016 , 8 4864 - 4881 . DOI: 10.1039/C5NR09122E http://doi.org/10.1039/C5NR09122E .

Huang, D.; Liu, Y.; Qin, A.; Tang, B. Z . Recent advances in alkyne-based click polymerizations . Polym. Chem. , 2018 , 9 2853 - 2867 . DOI: 10.1039/C7PY02047C http://doi.org/10.1039/C7PY02047C .

Li, B.; Huang, D.; Qin, A.; Tang, B. Z . Progress on catalytic systems used in click polymerization . Macromol. Rapid Commun. , 2018 , 39 1800098 DOI: 10.1002/marc.201800098 http://doi.org/10.1002/marc.201800098 .

Huang, Z.; Zhou, Y.; Wang, Z.; Li, Y.; Zhang, W.; Zhou, N.; Zhang, Z.; Zhu, X. L . Recent advances of CuAAC click reaction in building cyclic polymer . Chinese J. Polym. Sci. , 2017 , 35 317 - 341 . DOI: 10.1007/s10118-017-1902-0 http://doi.org/10.1007/s10118-017-1902-0 .

Li, H.; Sun, J.; Qin, A.; Tang, B. Z . Azide-alkyne click polymerization: an update . Chinese J. Polym. Sci. , 2012 , 30 1 - 15 . DOI: 10.1007/s10118-012-1098-2 http://doi.org/10.1007/s10118-012-1098-2 .

Rodionov, V. O.; Fokin, V. V.; Finn, M. G . Mechanism of the ligand-free CuI-catalyzed azide-alkyne cycloaddition reaction . Angew. Chem. Int. Ed. , 2005 , 44 2210 - 2215 . DOI: 10.1002/anie.200461496 http://doi.org/10.1002/anie.200461496 .

Rodionov, V. O.; Presolski, S. I.; Díaz Díaz, D.; Fokin, V. V.; Finn, M. G . Ligand-accelerated Cu-catalyzed azide-alkyne cycloaddition: a mechanistic report . J. Am. Chem. Soc. , 2007 , 129 12705 - 12712 . DOI: 10.1021/ja072679d http://doi.org/10.1021/ja072679d .

Cao, X.; Shi, Y.; Gao, H . A novel chain-growth CuAAC polymerization: one-pot synthesis of dendritic hyperbranched polymers with well-defined structures . Synlett , 2017 , 28 391 - 396 .

Shi, Y.; Graff, R . W.; Cao, X.; Wang, X.; Gao, H. Chain-growth click polymerization of AB 2 monomers for the formation of hyperbranched polymers with low polydispersities in a one-pot process . Angew. Chem. Int. Ed. , 2015 , 54 7631 - 7635 . DOI: 10.1002/anie.201502578 http://doi.org/10.1002/anie.201502578 .

Shi, Y.; Cao, X.; Hu, D.; Gao, H . Highly branched polymers with layered structures that mimic light-harvesting processes . Angew. Chem. Int. Ed. , 2018 , 57 516 - 520 . DOI: 10.1002/anie.201709492 http://doi.org/10.1002/anie.201709492 .

Cao, X.; Shi, Y.; Wang, X.; Graff, R. W.; Gao, H . Design a highly reactive trifunctional core molecule to obtain hyperbranched polymers with over a million molecular weight in one-pot click polymerization . Macromolecules , 2016 , 49 760 - 766 . DOI: 10.1021/acs.macromol.5b02678 http://doi.org/10.1021/acs.macromol.5b02678 .

Shi, Y.; Cao, X.; Luo, S.; Wang, X.; Graff, R . W.; Hu, D.; Guo, R.; Gao, H. Investigate the glass transition temperature of hyperbranched copolymers with segmented monomer sequence . Macromolecules , 2016 , 49 4416 - 4422 . DOI: 10.1021/acs.macromol.6b01144 http://doi.org/10.1021/acs.macromol.6b01144 .

Gan, W.; Shi, Y.; Jing, B.; Cao, X.; Zhu, Y.; Gao, H . Produce molecular brushes with ultrahigh grafting density using accelerated CuAAC grafting-onto strategy . Macromolecules , 2017 , 50 215 - 222 . DOI: 10.1021/acs.macromol.6b02388 http://doi.org/10.1021/acs.macromol.6b02388 .

Shi, Y.; Wang, X.; Graff, R. W.; Phillip, W. A.; Gao, H . Synthesis of degradable molecular brushes via a combination of ring-opening polymerization and click chemistry . J. Polym. Sci., Part A: Polym. Chem. , 2015 , 53 239 - 248 .

Xu, J.; Prifti, F.; Song, J . A versatile monomer for preparing well-defined functional polycarbonates and poly(ester-carbonates) . Macromolecules , 2011 , 44 2660 - 2667 . DOI: 10.1021/ma200021m http://doi.org/10.1021/ma200021m .

浏览量

247

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Poly(thiocarbonate) Synthesis from Carbonyl Sulfide (or Carbon Disulfide), Diol, and Dichlorides: A Step Growth Route to PE-like Sulfur-containing Polymers

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

Synthesis of Functional Hyperbranched Poly(methyltriazolylcarboxylate)s by Catalyst-free Click Polymerization of Butynoates and Azides

AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

Enhancing Processability of Phenylethynyl-terminated Imide Oligomers and Properties of Cured Polyimides via ―CF3 Incorporation

Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism

Mainchain Semifluorinated Polymers with Ultra High Molecular WeightviaReaction-enhanced Reactivity of Intermediate (RERI) Mechanism

DOI：10.1007/s10118-023-2919-1

摘要

Abstract

关键词

Keywords

references