Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers

Shu-Yu Liu; Shu-Wen Peng; Li-Jun Du; Shu-Guang Yang

doi:10.1007/s10118-025-3309-7

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Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers

RESEARCH ARTICLE | Updated：2025-07-14

- Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers
- Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers
- 高分子科学（英文） 2025年43卷第5期页码：738-744
- Affiliations：
  
  a.State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-Dimension Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, China
  b.Shanghai Huayi 3F New Materials Co., Ltd., Shanghai 200025, China
- Author bio：
  
  dulijun@shhuayi.com (L.J.D.)
  shgyang@dhu.edu.cn (S.G.Y.)
- Funds：
  
  This work was financially supported by the joint lab of Shanghai Huayi 3F New Materials Co., Ltd. and Donghua University.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3309-7.
- DOI：10.1007/s10118-025-3309-7
  中图分类号：
- 收稿日期：2024-12-07，
  
  修回日期：2025-01-20，
  
  录用日期：2025-01-23，
  
  网络出版日期：2025-03-13，
  
  纸质出版日期：2025-04-30
- Accepted：
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Liu, S. Y.; Peng, S. W.; Du, L. J.; Yang, S. G. Environment-friendly emulsion copolymerization of chlorotrifluoroethylene and vinyl ethers. Chinese J. Polym. Sci. 2025, 43, 738–744

Shu-Yu Liu, Shu-Wen Peng, Li-Jun Du, et al. Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers[J]. Chinese journal of polymer science, 2025, 43(5): 738-744.
Liu, S. Y.; Peng, S. W.; Du, L. J.; Yang, S. G. Environment-friendly emulsion copolymerization of chlorotrifluoroethylene and vinyl ethers. Chinese J. Polym. Sci. 2025, 43, 738–744 DOI： 10.1007/s10118-025-3309-7.

Shu-Yu Liu, Shu-Wen Peng, Li-Jun Du, et al. Environment-friendly Emulsion Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers[J]. Chinese journal of polymer science, 2025, 43(5): 738-744. DOI： 10.1007/s10118-025-3309-7.

摘要

The emulsion copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated. An optimized emulsifier system for FEVE is proposed

and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.

Abstract

Copolymers of fluoroethylene and vinyl ethers (FEVE) are soluble and curable at relatively low temperature

and are used as high-performance coatings and paints. Currently

most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent

and hence

volatile organic compound (VOC) emissions cause environmental issues. In this study

the emulsion copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated. In addition to mixed nonionic and ionic surfactants

macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system. The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed. An optimized emulsifier system for FEVE is proposed

and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.

关键词

Keywords

references

Boschet, F.; Améduri, B. (Co)polymers of chlorotrifluoroethylene: synthesis, properties, and applications. Chem. Rev . 2014 , 114 , 927−980..

Zhou, C. D.; Zhang, Z. X.; Li, W. P.; Chen, M. Organocatalyzed photo-controlled synthesis of ultrahigh-molecular-weight fluorinated alternating copolymers. Angew. Chem. Int. Ed. 2024 , 136 , e202314483..

Ishige, R.; Yamaguchi, H.; Shinohara, T.; Meskini, A.; Raihane, M.; Takahara, A.; Ameduri, B. Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer. Polym. J. 2013 , 45 , 1041−1046..

Chen, Y. T.; Luo, C.; Hu, F. Q.; Huang, Z. K.; Yue, K. Recent advances in fluorinated polymers: synthesis and diverse applications. Sci. China Chem. 2023 , 66 , 3347−3359..

Gong, H. H.; Zhang, Y.; Cheng, Y. P.; Lei, M. X.; Zhang, Z. C. The application of controlled/living radical polymerization in modification of PVDF based fluoropolymer. Chinese J. Polym. Sci. 2021 , 39 , 1110−1126..

Jiang, K. M.; Han, S. T.; Ma, M. Y.; Zhang, L.; Zhao, Y. C.; 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..

Améduri, B.; Hori, H. Recycling and the end of life assessment of fluoropolymers: recent developments, challenges and future trends. Chem. Soc. Rev . 2023 , 52 , 4208−4247..

Améduri, B. Fluoropolymers: the right material for the right applications. Chem. Eur. J . 2018 , 24 , 18830−18841..

Teng, H. X. Overview of the development of the fluoropolymer industry. Appl. Sci. 2012 , 2 , 496−512..

Améduri, B. The promising future of fluoropolymers. Macromol. Chem. Phys. 2020 , 221 , 1900573..

Chen, K. X.; Guo, X.; Chen, M. Controlled radical copolymerization toward well-defined fluoropolymers. Angew. Chem. Int. Ed. 2023 , 135 , e202310636..

Sumi, N.; Kimura, I.; Ataku, M.; Maekawa, T.; Parker, R. New advances in waterborne fluoropolymer technology: a water-based dispersion for industrial coatings formulations. JCT CoatingsTech 2009 , 6 , 24−28..

Puts, G.; Venner, V.; Améduri, B.; Crouse, P. Conventional and RAFT copolymerization of tetraﬂuoroethylenewith isobutyl vinyl ether. Macromolecules 2018 , 51 , 6724−6739..

Gaboyard, M.; Hervaud, Y.; Boutevin, B. Photoinitiated alternating copolymerization of vinyl ethers with chlorotrifluoroethylene. Polym. Int. 2002 , 51 , 577−584..

Carnevale, D.; Wormald, P.; Améduri, B.; Tayouo, R.; Ashbrook, S. E. Multinuclear magnetic resonance and DFT studies of the poly(chlorotrifluoroethylene- alt -ethyl vinyl ether) copolymers. Macromolecules 2009 , 42 , 5652−5659..

Tran-Do, M. L.; Habas, J. P.; Améduri, B. Oxygen-tolerant alternating copolymerization of fluorinated monomers and vinyl ethers at mild temperature. ACS Appl. Polym. Mater. 2022 , 4 , 1401−1410..

Boutevin, B.; Cersosimo, F.; Youssef, B. Studies of the alternating copolymerization of vinyl ethers with chlorotrifluoroethylene. Macromolecules 1992 , 25 , 2842−2846..

Takayanagi, T.; Yamabe, M. Progress of fluoropolymers on coating applications Development of mineral spirit soluble polymer and aque. Prog. Org. Coat. 2000 , 40 , 185−190..

Asakawa, A.; Unoki, M.; Hirono, T.,; Takayanagi, T. Waterborne fuoropolymers for paint use. J. Fluorine Chem. 2000 , 104 , 47−51..

Liang, L.; Wen, T.; Xin, J.; Su, C.; Song, K.; Zhao, W.; Liu, H. W.; Su, G. Fluoropolymer: a Review on its emulsion preparation and wettability to solid-liquid interface. Molecules 2023 , 28 , 905..

Schutzius, T. M.; Bayer, I. S.; Qin, J.; Waldroup, D.; Megaridis, C. M. Water-based, nonfluorinated dispersions for environmentally benign, large-area, superhydrophobic coatings. ACS Appl. Mater. Interfaces 2013 , 5 , 13419−13425..

GB 37824-2019. Emission standard of air pollutants for paint, ink and adhesive industry[S ] . 2019 .

Liu, Z. J.; Ren, L. N.; Zhang, B. S.; Jing, J.; Zhang, X. G.; Li, M. L.; Fu, Y. X.; Wang, H. Y. Eco-friendly waterborne superhydrophobic/superoleophilic FEVE composite coating with prolonged mechanochemical and anti-scaling properties. Chem. Eng. J. 2023 , 451 , 13869 3..

Matsusaka, N., Suzuki, T. Okubo, M. Effect of partitioning of monomer and emulsifier in aqueous media on particle formation in emulsion homopolymerization of hydrophobic and hydrophilic monomers with a nonionic emulsifier. Polym. J. 2013 , 45 , 153−159..

Wang, Z.; Liao, S. L.; Wang, Y. P. Supramolecular polymer emulsifiers for one-step complex emulsions. Chinese J. Polym. Sci. 2018 , 36 , 288−296..

Liu, X. J.; Lu, Y. C.; Luo, G. S. Continuous flow synthesis of polystyrene nanoparticles via emulsion polymerization stabilized by a mixed nonionic and anionic emulsifier. Ind. Eng. Chem. Res. 2017 , 56 , 9489−9495..

Lin, S. Y.; Capek, I.; Hsu, T. J.; Chern, C. S. Nonconventional emulsion polymerization of styrene with mixed anionic and nonionic emulsifiers. Polym. J. 2000 , 32 , 932−940..

Shinoda, K.; Saito, H.; Arai, H. The effect of the size and the distribution of the oxyethylene chain lengths of nonionic emulsifiers on the stability of emulsions. J. Colloid Interface Sci. 1971 , 35 , 624−630..

McClements, D. J.; Jafari, S. M. Improving emulsion formation, stability and performance using mixed emulsifiers: a review. Adv Colloid. Interfa. 2018 , 251 , 55−79..

Chern, C. S. Emulsion polymerization mechanisms and kinetics. Prog. Polym. Sci. 2006 , 31 , 443−486..

Liu, X. J.; Tian, Y. H.; Lu, Y. C. A comparative study on emulsion polymerization processes of styrene initiated by water-soluble and oil-soluble initiators. Chinese J. Polym. Sci. 2019 , 37 , 142−148..

Lu, Y. T.; Zhu, W. W.; Wu, Y. S.; Xu, Y. T.; Shao, L. P.; Zhang, H. B.; Chen, J. X.; Zhang, J. J.; Ling, J. Novel non-fluorinated surfactants for emulsion polymerization of fluorinated monomers. Polymer 2024 , 311 , 127520..

Yang, L.; He, L. Y.; Xue, J. M.; Ma, Y. F.; Xie, Z. Y.; Wu, L.; Huang, M.; Zhang, Z. L. Persulfate-based degradation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in aqueous solution: Review on influences, mechanisms and prospective. J. Hazard. Mater. 2020 , 393 , 122405..

Tan, X.; Dewapriya, P.; Prasad, P.; Chang, Y. X.; Huang, X. M.; Wang, Y. Q.; Gong, X. K.; Hopkins, T. E.; Fu, C. K.; Thomas, K. V.; Peng, H.; Whittaker, A. K.; Zhang, C. Efficient removal of perfluorinated chemicals from contaminated water sources using magnetic fluorinated polymer sorbents. Angew. Chem. Int. Ed. 2022 , 61 , e202213071..

Améduri, B.; Sales, J.; Schlipf, M. Developments in fluoropolymer manufacturing technology to remove intentional use of PFAS as polymerization aids. Intern. Chem. Regul. Law Rev. 2023 , 6 , 18−28..

Liu, H. Z.; Bian, J. M.; Wang, Z. G.; Hou, C. J. Synthesis and characterization of waterborne fluoropolymers prepared by the one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate, veova 10 and acrylic acid. Molecules 2017 , 22 , 184..

Qu, A. L.; Wen, X. F.; Pi, P.; Cheng, C.; Yang, Z. R. Preparation of hybrid film with superhydrophobic surfaces based on irregularly structure by emulsion polymerization. Appl. Surf. Sci. 2007 , 253 , 9430−9434..

HJ 2537-2014, Technical requirement for environmental labeling products, Water based coatings [S ] . 2014

Yang, H. B.; Kang, W. L.; Yu, Y.; Yin, X.; Wang, P. X.; Zhang, X. F. A new approach to, evaluate the particle growth and sedimentation of dispersed polymer microsphere profile control system based on multiple light scattering. Powder Technol. 2017 , 315 , 477−485..

Wang, K. L.; Li, G.; Zhang, B. W. Opposite results of emulsion stability evaluated by the TSI and the phase separation proportion. Colloid Surf. A 2018 , 558 , 402−409..

Mengual, O.; Meunier, G.; Cayré, I.; Puech, K.; Snabre, P. TURBISCAN MA 2000: multiple light scattering measurement for concentrated emulsion and suspension instability analysis. Talanta 1999 , 50 , 445−456..

Marhamati, M.; Ranjbar, G.; Rezaie, M. Effects of emulsifiers on the physicochemical stability of oil-in-water nanoemulsions: a critical review. J. Mol. Liq. 2021 , 340 , 117218..

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