Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

Yu-Tong Zhou; You-Fan Wu; Qian-Qian Yang; Hai-Bao Zhang; Ting Zhang; Hao-Yan Guo; Zhen-Jun Wang; Gang Li

doi:10.1007/s10118-026-3688-4

Your Location：

Home >

Browse articles >

Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber

RESEARCH ARTICLE | Updated：2026-08-31

- Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber
- Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber
- Chinese Journal of Polymer Science 2026年44卷第9期页码：3129-3141
- Affiliations：
  
  a.School of Materials Science and Engineering, Chang’an University, Xi’an 710061, China
  b.Shaanxi Union Research Center of University and Enterprise for Advanced Transportation Infrastructure Materials, Xi’an 710064, China
  c.College of Water Conservancy & Architectural Engineering, Shihezi University, Shihezi 832003, China
- Author bio：
  
  zhangting@chd.edu.cn (T.Z.)
  zjwang@chd.edu.cn (Z.J.W.)
- Funds：
  
  This work was financially supported by the Natural Science Support Program of Xinjiang Production and Construction Corps (XPCC), China (No. 2025YD005), Fundamental Research Funds for the Central Universities, Chang'an University (CHD) (No. 300102314901), Shaanxi Transportation Technology Project, China (No. 24-104K), Project funded by the China Postdoctoral Science Foundation (No. 2024M762772), Shaanxi Province Natural Science Basic Research Program Project (No. 2025JC-YBQN-499), and Young Talent Fund of Xi'an Association for Science and Technology (No. 0959202513004). The authors also thank the reviewers for their valuable comments and suggestions on our manuscript.;The authors declare no interest conflict.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3688-4
  中图分类号：
- 收稿：2025-12-11，
  
  录用：2026-03-27，
  
  网络首发：2026-06-10，
  
  纸质出版：2026-09-05
- Accepted：
Scan QR Code
Zhou, Y. T.; Wu, Y. F.; Yang, Q. Q.; Zhang, H. B.; Zhang, T.; Guo, H. Y.; Wang, Z. J.; Li, G. Improvements of hydrophobicity and toughness of epoxy coatings modified with hydroxyl-terminated fluororubber. Chinese J. Polym. Sci. 2026, 44, 3129–3141

Yu-Tong Zhou, You-Fan Wu, Qian-Qian Yang, et al. Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3129-3141.
Zhou, Y. T.; Wu, Y. F.; Yang, Q. Q.; Zhang, H. B.; Zhang, T.; Guo, H. Y.; Wang, Z. J.; Li, G. Improvements of hydrophobicity and toughness of epoxy coatings modified with hydroxyl-terminated fluororubber. Chinese J. Polym. Sci. 2026, 44, 3129–3141 DOI： 10.1007/s10118-026-3688-4.

Yu-Tong Zhou, You-Fan Wu, Qian-Qian Yang, et al. Improvements of Hydrophobicity and Toughness of Epoxy Coatings Modified with Hydroxyl-terminated Fluororubber[J]. Chinese Journal of Polymer Science, 2026, 44(9): 3129-3141. DOI： 10.1007/s10118-026-3688-4.

摘要

Flexible fluororubber grafting onto epoxy resin achieves high toughness (elongation at break: 46.40%) and hydrophobicity (contact angle: 110°) at 25% HTFR content

significantly enhancing cavitation erosion resistance.

Abstract

To address the brittleness of epoxy resin (EP) caused by high crosslinking density

the modification of epoxy resin with flexible rubber segments was proposed in this work. Bisphenol A-type epoxy resin (E51) was reacted with isocyanate-terminated groups

via

an addition reaction to prepare a prepolymer (E51-TDI). Subsequently

E51-TDI was grafted with hydroxyl-terminated fluororubber (HTFR) to synthesize a high-toughness fluorinated epoxy resin (E51-TDI-HTFR) with side chains. A mixture of E51-TDI-HTFR and curing agent (D230) was used to fabricate the coating. The chemical structure of the modified epoxy resin and the thermal

hydrophobic

mechanical

and cavitation erosion resistance of the coatings were investigated. When the HTFR concentration was 25%

the epoxy coating exhibited the best hydrophobicity

mechanical properties

and cavitation resistance. The contact angle of the modified epoxy resin was increased to 110°. Meanwhile

the elongation at break increased to 46.40%

which was approximately four times that of the unmodified coatings. The fracture surface gradually became rougher as the HTFR content increased

indicating a ductile fracture characteristic. Although the addition of HTFR slightly reduced the glass transition temperature

it maintained good thermal stability. In addition

the cavitation erosion resistance of the epoxy coatings was enhanced. This study provides theoretical support for the development of high-toughness and hydrophobic epoxy coatings.

关键词

Keywords

references

Toldy, A.; Szolnoki, B.; Marosi, G. Flame retardancy of fibre-reinforced epoxy resin composites for aerospace applications. Polym. Degrad. Stabil. 2011 , 96 , 371−376..

Radzuan, N.; Ismail, N.; Radzi, M.; Bin Razak, Z.; Tharizi, I.; Sulong, A.; Haron, C.; Muhamad, N. Kenaf composites for automotive components: enhancement in machinability and moldability. Polymers 2019 , 11 , 1707..

Xu, Y.; Shan, H.; Liu, Q.; Lin, Y.; Wu, L.; Xu, S.; Ji, J. Deicing performance improvement of single-component polyurethane pavement materials. J. Mater. Civ. Eng. 2025 , 37 , 04025389..

Yuan, D.; Jiang, W.; Sha, A.; Xiao, J.; Wu, W.; Wang, T. Technology method and functional characteristics of road thermoelectric generator system based on seebeck effect. Appl. ENERGY 2023 , 331 , 120459..

Jiang, W.; Yuan, D.; Shan, J.; Ye, W.; Lu, H.; Sha, A. Experimental study of the performance of porous ultra-thin asphalt overlay. Int. J. Pavement Eng. 2022 , 23 , 2049−2061..

Zhang, J.; Zhang, Z.; Huang, R.; Tan, L. Advances in toughening modification methods for epoxy resins: a comprehensive review. Polymers 2025 , 17 , 1288..

Turkben, M.; Kocaman, S.; Özmeral, N.; Soydal, U.; Cerit, A.; Ahmetli, G. Sustainable production of recycled rubber waste composites with various epoxy systems: a comparative study on mechanical and thermal properties. Ind. Crops Prod. 2023 , 195 , 116490..

Picu, C.; Krawczyk, K.; Wang, Z.; Pishvazadeh-Moghaddam, H.; Sieberer, M.; Lassnig, A.; Kern, W.; Hadar, A.; Constantinescu, D. Toughening in nanosilica-reinforced epoxy with tunable filler-matrix interface properties. Compos. Sci. Technol. 2019 , 183 , 107799..

Liu, W.; Ahmad, M.; Song, P.; Fang, Q.; Li, Q.; Huang, G.; Yang, C. In situ synthesis of organic polymer-inorganic nano zno core-shell structured sizing agents and their effect on carbon fiber interfaces and composite properties. Polymers 2025 , 17 , 773..

Yan, C.; Wang, H.; Song, L.; Zhou, G. Prepa ration, characterization, and performance of reactive phenolphthalein poly(aryl ether sulfone) tougheners highly compatible with epoxy resin. J. Appl. Polym. Sci. 2024 , 141 , e55480..

Chen, D.; Li, J.; Yuan, Y.; Gao, C.; Cui, Y.; Li, S.; Wang, H.; Peng, C.; Liu, X.; Wu, Z.; Ye, J. A new strategy to improve the toughness of epoxy thermosets by introducing the thermoplastic epoxy. Polymer 2022 , 240 , 124518..

Chai, M.; Liu, H.; Wu, Y.; Xue, K.; Zhang, P.; Liu, L.; Huang, Y. Flame retardant, toughened, reinforced, transparent and long shelf-life one-component epoxy resins via a p/n/si-containing hyperbranched polymer. Chem. Eng. J. 2024 , 493 , 152785..

Banan, A.; Mehdipour, H. Controlled degradation and functionalization of natural rubber by ozonolysis in organic solvent. J. Polym. Res. 2021 , 28 , 333..

Ibrahim, S.; Daik, R.; Abdullah, I. Functionalization of liquid natural rubber via oxidative degradation of natural rubber. Polymers 2014 , 6 , 2928−2941..

Kim, D.; Ahn, B.; Kim, K.; Lee, J.; Kim, I.; Kim, W. Effects of molecular weight of functionalized liquid butadiene rubber as a processing aid on the properties of ssbr/silica compounds. Polymers 2021 , 13 , 850..

Thomas, R.; Durix, S.; Sinturel, C.; Omonov, T.; Goossens, S.; Groeninckx, G.; Moldenaers, P.; Thomas, S. Cure kinetics, morphology and miscibility of modified DGEBA-based epoxy resin–effects of a liquid rubber inclusion. Polymer 2007 , 48 , 1695−1710..

Arcos-Casarrubias, J.; Vázquez-Torres, H.; Granados-Olvera, J.; Cedeño, A.; Cervantes-Uc, J. Vscoelastic behavior and toughness of the DGEBA epoxy resin with 1,2-diaminocyclohexane: effect of functionalized poly(dimethylsiloxane), diglycidyl ether, PDMS-DGE, pre-reacted with 1,2-diaminocyclohexane. Polym. Bull. 2022 , 79 , 2871−2901..

Dou, H.; Tian, B.; Huang, Y.; Quan, Y.; Chen, Q.; Yin, G. Improved mechanical properties of ATBN-toughened epoxy networks by controlling the phase separation scale. J. Adhes. Sci. Technol. 2016 , 30 , 642−652..

Chen, S.; Wang, T. Hydroxy-terminated liquid nitrile rubber modified castor oil based polyurethane/epoxy ipn composites: damping, thermal and mechanical properties. Polym. Test. 2011 , 30 , 726−731..

Ge, Z.; Zhang, W.; Huang, C.; Luo, Y. Study on epoxy resin toughened by epoxidized hydroxy-terminated polybutadiene. Materials 2018 , 11 , 932..

Lou, C.; Zhang, X.; Wang, Y.; Chen, Z.; Li, H. Toughening epoxy resin with blocked isocyanate containing soft chain. J. Appl. Polym. Sci. 2015 , 132 , 41345..

Tang, W.; Zeng, T.; Hu, J.; Li, J.; Yang, R. Investigation on the thermal decomposition of the elastomer containing fluoroolefin segment by DSC-TG-MS-FTIR. Polym. Adv. Technol. 2021 , 32 , 4880−4890..

Zhang, X. F.; Cao, T.; Zhao, T. H.; Ma, C.; Liu, P. Y. Preparation and properties of a new type of flexible epoxy resin based on a molecular network structure. Express Polym. Lett. 2021 , 15 , 1032−1040..

Zhang, X.; Li, P.; Huang, D.; Shi, X.; Shi, Y.; Qu, C.; Tan, Q. Study on a novel epoxy-terminated dendritic modifier as an active toughening agent for epoxy resin. J. Appl. Polym. Sci. 2024 , 141 , e55717..

Kim, H.-C.; Moon, S.-J.; Kwon, Y.-R.; Moon, S.; Kim, D.; Kim, D.-H. Novelglycidyl carbamate functional epoxy resin using hydroxyl-terminated polybutadiene. Polymers 2024 , 16 , 3107..

Wu, P.; Li, S.; Guo, H.; Zhang, H.; He, R. Research on electromagnetic and rheological performance of microwave-sensitive emulsified asphalt containing SiC and Fe 3 O 4 . Materials 2025 , 18 , 4283..

Fedorov, Y.; Shadrinov, N.; Vasil’ev, S.; Savvina, A. Influence of thermoplastic elastomer filler on impact viscosity of epoxy resin at low temperatures. Inorg. Mater.-Appl. Res. 2023 , 14 , 1007−1012..

Wu, Y.; Yang, Q.; Zhang, H.; Zhou, Y.; Guo, H.; Wang, Z.; Li, G. Enhancing hydrophobicity and corrosion resistance of epoxy resin coatings using KH570-ZrO 2 nanoparticles. Polym. Test. 2026 , 154 , 109070.

Huang, B.; Ai, S.; Tan, J.; Zhou, B.; Pan, Y.; Zheng, Z.; Ding, X.; Deng, J. Enhancing tensile strength, hydrophobicity, and flame retardancy of epoxy resin: π-π stacking and hydrogen bonds, fluorine, and phosphorus- fluorine synergy. ACS Appl. Eng. Mater. 2025 , 3 , 2176−2189..

Wang, X.; Liao, X.; Tian, J.; Zou, H.; Liu, P. Fluorine-containing main-chain type active esters as curing agents for epoxy resins to achieve superior dielectric and thermal performances. Prog. Org. Coat. 2024 , 197 , 108806..

[Chai, W.; Wang, C.; Liu, H.; Gao, Y.; Zhang, S.; Xin, M.; Wang, R.; Liu, Z.; Wang, H. Novel amphiphilic crosslinked architecture in coatings for enhanced high-voltage corrosion resistance. Surf. Interfaces 2025 , 107338..

Shi, E.; Liu, B.; Zhao, B.; Jiang, C.; Zhou, W. Preparation and anti-icing characteristics of durable superhydrophobic composite coatings of nano-silica / fluorocarbon resin. China Surf. Eng. 2025 , 38 , 244−254..

Wang, C.; Yun, T.; You, W.; Ding, Y.; Fan, Z.; Liu, G.; Yu, W.; Yan, X. Mechanical-bond-toughened epoxy resins. Angew. Chem. Int. Ed. 2025 , 64 , e202516283..

Wang, Y.; Deng, J.; Zhao, J.; Ding, Y.; Yang, L.; Zhang, Z.; Yan, X. Bolster ing the mechanical robustness of supramolecular polymer network by mechanical bond. Chinese J. Polym. Sci. 2024 , 42 , 1536−1544..

Ji, X.; Wang, J.; Wang, Z.; Mao, B.; Cao, Y.; Xie, Y.; Yan, Y. Epoxy-poss toughened phenol-formaldehyde resin adhesive and its enhancement on the interfacial bonding strength of bamboo based composite. Polym. Compos. 2025 , 46 , 870−885..

Sim, K.; Back, J.; Han, G.; Kim, H. High-performance automotive adhesives with urethane-modified and nanophase-separated epoxy systems. Compos. Part Appl. Sci. Manuf. 2025 , 190 , 108652..

Chen, Z.; Li, Z.; Ran, Z.; Zhang, Y.; Lin, F.; Zhou, Y. Study on the performance of composite-modified epoxy resin potting adhesive for repairing oblique cracks. Materials 2025 , 18 , 3197..

Zhang, H.; Li, Y.; Huan, D.; Li, M.; Yang, L. Study on toughening modification of epoxy resin and its properties of T700 carbon fibre composites. J. Reinf. Plast. Compos. 2026 , 45 , 1503−1517..

Zhou, Y.; Zhao, Z.; Zeng, Y.; Tian, S.; Sun, F.; Cheng, Y.; Li, Y.; Fu, Z.; Fu, J. Ultra-robust and tough epoxy resin enabled by pulley mechanism-based curing agent for strong and reversible adhesion. Adv. Funct. Mater. 2025 , 35 , e17052..

Parameswaranpillai, J.; Sanjay, M.; Siengchin, S.; Sidhardhan, S.; Jose, S.; Salim, N.; Hameed, N. Intermolecular hydrogen bonding in developing nanostructured epoxy shape memory thermosets: effects on morphology, thermo-mechanical properties and surface wetting. Polym. Test. 2020 , 81 , 106279..

Li, D.; Yu, L.; Ning, S.; Li, P.; Chen, C.; Zhao, D.; Liao, M.; Meng, Q.; Zhang, S.; Fang, Q.; Kang, H.; Li, L.; Yang, J. Upcycling of waste fluororubber to photocurable high-performance vinyl-terminated liquid fluororubber by multifield coupling one-pot stepwise reactions. Adv. Sci. 2025 , 12 , e01460..

Karami, M.; Kalaee, M.; Khajavi, R.; Moradi, O.; Zaarei, D. Thermal degradation kinetics of epoxy resin modified with elastomeric nanoparticles. Adv. Compos. Hybrid Mater. 2022 , 5 , 390−401..

Ruamcharoen P, Umaree S, Ruamcharoen J. Relationship between tensile properties and morphology of epoxy resin modified by epoxidised natural rubber. J. Mater. Sci. Eng. 2011 , 5 , 504−510..

Lou, C.; Liu, X. Functional dendritic curing agent for epoxy resin: processing, mechanical performance and curing/toughening mechanism. Compos. Part B Eng. 2018 , 136 , 20−27..

Tian, W.; Wang, S.; Wang, C.; Xu, H.; Zhao, Y.; Jin, H.; Tian, L. An epoxy-modified polyurethane composite coating with repetitive self-healing function for anti-cavitation, anticorrosion, and antifouling applications. Chem. Eng. J. 2023 , 477 , 146849..

Zhang, Z.; Hou, G.; Wan, H.; Ma, J.; Ye, Y.; Zhou, H.; Chen, J. Effect of epoxy resin modification on the cavitation erosion resistance of polyamide-imide coatings. China Surf. Eng. 2024 , 37 , 88−101..

Tian, W.; Guo, Z.; Wang, S.; Yu, H.; Wang, S.; Jin, H.; Tian, L. Hydrogen and DA bond-based self-healing epoxy-modified polyurea composite coating with anti-cavitation, anticorrosion, antifouling, and strong adhesion properties. J. Mater. Sci. Technol. 2024 , 187 , 1−14..

Ogawa, M.; Morimura, A.; Haba, I.; Yonezu, A. Coarse-grained molecular dynamics simulations of nano-deformat ion behavior of epoxy adhesives’ interface during atomic force microscopy (AFM) mechanical testing. Polymer 2025 , 320 , 128071..

Wu, Y.; Zhou, Y.; Zhang, H.; Yang, Q.; Zhang, T.; Guo, H.; Wang, Z. Mechanical properties and hydrophobicity improvement of epoxy coatings through synthesis of modified alicyclic amine. Polymer 2025 , 341 , 129298..

Din, I.; Bathusha, M.; Khan, K. Effects of liquid rubber-modified epoxy on the fracture toughness of rGO-Coated fabric piezoresistive composites. Compos. Commun. 2025 , 56 , 102368..

Zhou, H.; Shi, Z.; Zhou, X.; Li, X.; Wen, Y.; Xue, Z.; Wang, Y.; Xie, X. Reversible and ultrastrong epoxy-polyurethane adhesives with microphase separation. Adv. Funct. Mater. 2025 , 35 , 2506419..

Wang, S.; Yu, Z.; Sun, X.; Panahi-Sarmad, M.; Yang, P.; Zhu, P.; Zhu, Y.; Liu, H.; Jiang, F. A Universal strategy to mitigate microphase separation via cellulose nanocrystal hydration in fabricating strong, tough, and fatigue-resistant hydrogels. Adv. Mater. 2025 , 37 , 2416916..

Fernandez-Rico, C.; Schreiber, S.; Oudich, H.; Lorenz, C.; Sicher, A.; Sai, T.; Bauernfeind, V.; Heyden, S.; Carrara, P.; De Lorenzis, L.; Style, R.; Dufresne, E. Elastic microphase separation produces robust bicontinuous materials. Nat. Mater. 2024 , 23 , 124..

Carrara, A.; Rodrigues, V.; Dutra, R.; Dutra, J. Impact assessment of synthesis parameter stirring speed in final physicochemical properties of PU microcapsules incorporated into epoxy matrixes. An. Acad. Bras. Cienc. 2023 , 95 , e20201518..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Effects of Different Nucleating Agents, Annealing and Pre-stretching Process on the Crystallinity and Mechanical Properties of Poly(butylene carbonate)

Advancing the Thin-film Mechanics of Conjugated Polymers: Characterization, Modulation, and Innovation

Enhanced Mechanical Properties and Prolonged Recovery Onset Period of Timed Shape Memory Hydrogels via Hydrophobic Interaction

A Phosphorus/Nitrogen-containing Phosphaphenanthrene Derivative as Flame Retardant for Poly(lactic acid)

Manipulating Hierarchical Aggregation Structure via Film-forming Kinetics Enables Organic Photovoltaics over 20% Efficiency