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研究论文

高强度含氟降冰片烯/PDMS双网络有机凝胶的制备及其防冰性能

范雯雯, 罗光增, 宫凯, 解竹柏, 谢春杰, 雷岚*, 李辉*   

  1. 济南大学化学化工学院,山东省耐极端环境特种化学品重点实验室,济南,250022
  • 投稿日期:2025-10-22
  • 基金资助:
    山东省自然科学基金 (ZR2022QB170); 济南大学新引进人才科研项目(XBS2418)

Preparation of High-Strength Fluorinated Norbornene /PDMS Dual-Network Organogel and Its Anti-Icing Performance

Wen-wen Fan, Guang-zeng Luo, Kai Gong, Zhu-bai Xie, Chun-jie Xie, Lan Lei*, Hui Li*   

  1. School of Chemistry and Chemical Engineering, University of Jinan, Shandong Provincial Key Laboratory of Special Chemicals for Extreme Environments Jinan, 250022, China
  • Received:2025-10-22
  • Contact: * E-mail: chm_leil@ujn.edu.cn; chm_lih1@ujn.edu.cn
  • Supported by:
    Project supported by the Natural Science Foundation of Shandong Province (ZR2022QB170); Research Project for Newly Introduced Talents of University of Jinan (XBS2418).

防冰材料在实际应用中长期面临耐久性不足、在复杂恶劣环境(如高湿度、超低温)下稳定性较差等挑战。因此,开发兼具高机械强度、良好耐久性和低冰粘附强度的新型材料具有重要意义。本文以降冰片烯基三氟乙酯(NTF)、降冰片烯基十二氟庚酯(NDF),二降冰片烯基乙二醇酯(NEG)分别为第一网络的单体和交联剂,Sylgard184 A和B组分为第二网络的单体,二甲基硅油为功能添加剂,通过开环易位聚合(ROMP)和硅氢加成反应成功制备了一系列二甲基硅油含量可调的含氟降冰片烯/PDMS双网络有机凝胶(NTDG/PDMS)。实验结果表明,硅油含量对材料的拉伸强度和冰剪切强度呈现较好的调控作用。随着硅油含量由0增加至80%,NTDG/PDMS凝胶的拉伸强度仍高于1.33 MPa,而冰剪切强度由211.59 kPa显著降低至9.96 kPa,结冰延迟时间也逐步延长至428 s。NTDG/PDMS-4在经历60次摩擦循环后,冰剪切强度由9.96 kPa增加至19.13 kPa,仅增加9.17 kPa,变化幅度较小,表现出优异的抗结冰性和机械耐久性。该类双网络有机凝胶兼具较高的机械强度、卓越的抗结冰性能及耐摩擦性能,在防冰领域显示出广阔的应用前景。

关键词: ROMP聚合, 降冰片烯/PDMS双网络, 高强度, 防冰, 耐摩擦

Ace-resistant materials have long been plagued by critical challenges in practical applications, including insufficient durability and compromised stability under complex harsh conditions (e.g., high humidity, ultra-low temperature) . Therefore, developing advanced materials that synergistically integrate high mechanical strength, superior durability, and low ice adhesion strength remains of paramount significance. Herein, we rationally designed target materials by leveraging the complementary merits of fluorinated norbornene polymers (low surface energy, high mechanical strength) and PDMS (low elastic modulus, low surface energy). Specifically, the first network (fluorinated norbornene polymer) was constructed via ring-opening metathesis polymerization (ROMP) using Grubbs 2nd generation catalyst, with norbornenyl trifluoroethyl ester (NTF) and norbornenyl dodecafluoroheptyl ester (NDF) as comonomers, and di-norbornenyl ethylene glycol ester (NEG) as the cross-linker. The second network was fabricated through hydrosilylation reaction, employing Sylgard 184 Components A and B as monomer precursors and dimethyl silicone oil as a functional additive. Through the sequential polymerization strategy, a series of fluorinated norbornene/PDMS double-network organogels (NTDG/PDMS) with tunable dimethyl silicone oil contents were successfully synthesized. The physicochemical and functional properties of the as-prepared double-network organogels were systematically characterized. Experimental results revealed that the dimethyl silicone oil content exerted a prominent regulatory effect on the tensile strength and ice shear strength (τ₁ce) of the materials . As the silicone oil content increased from 0 to 80%, the tensile strength of NTDG/PDMS gels retained above 1.33 MPa, while the ice shear strength underwent a significant reduction from 211.59 kPa to 9.96 kPa (well below the 100 kPa threshold for icephobic materials ), accompanied by a gradual extension of icing delay time to 428 s. Mechanical durability assessment demonstrated that after 60 friction cycles, the ice shear strength of NTDG/PDMS-4 only increased from 9.96 kPa to 19.13 kPa (a marginal increment of 9.17 kPa) with minimal variation, manifesting exceptional ice resistance and structural robustness. Collectively, this double-network organogel integrates high mechanical strength, outstanding ice-resistant performance, and favorable friction resistance, thereby holding broad application prospects in the field of ice protection.

Key words: ROMP Polymerization, Norbornene/PDMS Double Network, High Strength, Anti-icing, Abrasion Resistance