硅橡胶用纳米二氧化硅表面有机修饰及补强机理研究进展

doi:10.11949/0438-1157.20241515

摘要/Abstract

摘要：

纳米二氧化硅作为补强剂分散在硅橡胶基体中，与硅橡胶基体相互连接，可以显著提高拉伸强度、模量、耐磨性等性能。但纳米二氧化硅表面富含羟基，易于团聚，直接应用效果差，需要在其表面接枝有机基团，提高其在硅橡胶中的分散性、相容性和功能性。针对改性二氧化硅颗粒与硅橡胶间的相互作用，综述了含可分散基团和可交联基团修饰剂对纳米二氧化硅颗粒表面有机修饰的研究进展，阐述了硅橡胶的分子结构特性，分析了修饰剂对颗粒表面的修饰效果以及颗粒表面与硅橡胶间的作用机制，总结了纳米二氧化硅补强硅橡胶机理研究进展，对合理选择修饰剂和设计修饰工艺，科学调控分散和交联提出了展望。

关键词: 二氧化硅, 表面, 修饰, 聚合物, 硅橡胶

Abstract:

Nano-silica serves as a reinforcing agent in silicone rubber matrices, forming an interconnected network that significantly increases properties such as tensile strength, modulus, and wear resistance. However, the surface of nano-silica is rich in hydroxyl groups, easy to agglomerate, and the direct application effect is poor. It is necessary to graft organic groups on its surface to improve its dispersibility, compatibility and functionality in silicone rubber. This review focused on the interactions between modified nano-silica particles and silicone rubber, summarized recent advances in surface organic modification using dispersible and cross-linkable functional groups. The molecular structure characteristics of silicone rubber are explained, the modification effect of modifiers on the particle surface and the mechanism of action between the particle surface and silicone rubber are analyzed, and the research progress of nano-silica reinforcement mechanism of silicone rubber is summarized. Perspectives are proposed for the rational selection of modifiers, the strategic design of modification processes, and the precise control of particle dispersion and cross-linking to optimize silicone rubber performance.

Key words: silicon dioxide, surface, modification, polymer, silicone rubber

中图分类号:

TB 332

赵美, 甘雨欣, 赵绍磊, 杨令, 王亭杰. 硅橡胶用纳米二氧化硅表面有机修饰及补强机理研究进展[J]. 化工学报, 2025, 76(7): 3125-3136.

Mei ZHAO, Yuxin GAN, Shaolei ZHAO, Ling YANG, Tingjie WANG. Research progress on organic modifications of silica nanoparticles and reinforcing mechanism in silicone rubber[J]. CIESC Journal, 2025, 76(7): 3125-3136.

图/表 14

参考文献 84

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分类方法	硅橡胶类型
单体类型	二甲基硅橡胶（MQ）甲基乙烯基硅橡胶（VMQ）甲基乙烯基苯基硅橡胶（PVMQ）甲基乙烯基三氟丙基硅橡胶（FVMQ）
硫化类型	高温硫化硅橡胶（HTV）单组分室温硫化硅橡胶（RTV1）双组分室温硫化硅橡胶（RTV2）液体硅橡胶（LSR）
硫化机理	缩合型硅橡胶加成型硅橡胶
应用领域	耐高温型硅橡胶低压缩永久变形型硅橡胶耐溶剂型硅橡胶阻燃型硅橡胶导电型硅橡胶

分类方法	硅橡胶类型
单体类型	二甲基硅橡胶（MQ）甲基乙烯基硅橡胶（VMQ）甲基乙烯基苯基硅橡胶（PVMQ）甲基乙烯基三氟丙基硅橡胶（FVMQ）
硫化类型	高温硫化硅橡胶（HTV）单组分室温硫化硅橡胶（RTV1）双组分室温硫化硅橡胶（RTV2）液体硅橡胶（LSR）
硫化机理	缩合型硅橡胶加成型硅橡胶
应用领域	耐高温型硅橡胶低压缩永久变形型硅橡胶耐溶剂型硅橡胶阻燃型硅橡胶导电型硅橡胶

修饰剂	应用硅橡胶与研究目标	主要反应条件
六甲基二硅氮烷（HMDS）（CAS: 999-97-3）	室温硫化硅橡胶；降低黏度甲基乙烯基硅橡胶；优化电气性能、提升力学性能、提高介电常数甲基乙烯基苯基硅橡胶；提升力学性能	干法、100℃、2 h^[55] 乙醇、70℃、5 h^[57] 乙醇、25℃、24 h、超临界干燥^[41] 乙醇、原位改性、60℃、4 h^[52] 醇水溶液、25℃、2 h^[54]
二苯基二甲氧基硅烷（DDS）（CAS: 6843-66-9）	硅橡胶；提高热稳定性	水、酸性（定量盐酸）、60℃、2 h^[58]
硬脂酸（SA）（CAS: 57-11-4）	单组分室温硫化硅橡胶；优化力学、电气性能	乙酸乙酯、25℃、1 h^[59]
十六烷基三甲氧基硅烷（HDTMS）（CAS: 16415-12-6）	甲基乙烯基硅橡胶；优化力学性能	甲苯、110℃、6 h^[60]
3-氨丙基三乙氧基硅烷（APTES）（CAS: 919-30-2） γ-缩水甘油醚氧丙基三甲氧基硅烷（KH560）（CAS: 2530- 83-8）	室温硫化硅橡胶；提升热性能、电性能、力学性能	Step 1（APTES）：醇水溶液、100℃、15 min； Step 2（KH560）：甲苯、80℃、 4 h、N₂^[61]
十三氟辛基三乙氧基硅烷（PFTS）（CAS: 51851-37-7）	甲基乙烯基硅橡胶；提升低温抗性	醇水溶液、pH=3、70℃、4 h^[62]
四苯基苯三乙氧基硅烷（TPHHS）	高温硫化硅橡胶；提升耐辐射性、力学性能	甲苯、25℃、12 h^[63]

修饰剂	应用硅橡胶与研究目标	主要反应条件
六甲基二硅氮烷（HMDS）（CAS: 999-97-3）	室温硫化硅橡胶；降低黏度甲基乙烯基硅橡胶；优化电气性能、提升力学性能、提高介电常数甲基乙烯基苯基硅橡胶；提升力学性能	干法、100℃、2 h^[55] 乙醇、70℃、5 h^[57] 乙醇、25℃、24 h、超临界干燥^[41] 乙醇、原位改性、60℃、4 h^[52] 醇水溶液、25℃、2 h^[54]
二苯基二甲氧基硅烷（DDS）（CAS: 6843-66-9）	硅橡胶；提高热稳定性	水、酸性（定量盐酸）、60℃、2 h^[58]
硬脂酸（SA）（CAS: 57-11-4）	单组分室温硫化硅橡胶；优化力学、电气性能	乙酸乙酯、25℃、1 h^[59]
十六烷基三甲氧基硅烷（HDTMS）（CAS: 16415-12-6）	甲基乙烯基硅橡胶；优化力学性能	甲苯、110℃、6 h^[60]
3-氨丙基三乙氧基硅烷（APTES）（CAS: 919-30-2） γ-缩水甘油醚氧丙基三甲氧基硅烷（KH560）（CAS: 2530- 83-8）	室温硫化硅橡胶；提升热性能、电性能、力学性能	Step 1（APTES）：醇水溶液、100℃、15 min； Step 2（KH560）：甲苯、80℃、 4 h、N₂^[61]
十三氟辛基三乙氧基硅烷（PFTS）（CAS: 51851-37-7）	甲基乙烯基硅橡胶；提升低温抗性	醇水溶液、pH=3、70℃、4 h^[62]
四苯基苯三乙氧基硅烷（TPHHS）	高温硫化硅橡胶；提升耐辐射性、力学性能	甲苯、25℃、12 h^[63]

修饰剂	应用硅橡胶与研究目标	主要反应条件
乙烯基三甲氧基硅烷（VTMS）（CAS: 2768-02-7）	液体硅橡胶；调控液体硅橡胶与不同表面附着二甲基硅橡胶；提升热稳定性、刚度二甲基硅橡胶；提升橡胶膜的分离系数	醇水溶液30℃、24 h水解；25℃、5 min反应^[78] THF、邻苯二甲酸正丁酯催化、25℃、3 h^[79] 丙酮、50℃、3 h^[76]
四甲基二乙烯基二硅氧烷（TMDVS）（CAS: 2627-95-4）	二甲基乙烯基硅橡胶；提升热稳定性、电导率、力学强度	乙醇、氨水催化、80℃、2 h^[77]
γ-甲基丙烯酰氧丙基三甲氧基硅烷（MPS）（CAS: 2530-85-0）	加成型液体硅橡胶；提升机械强度加成型室温硫化硅橡胶；制备高疏水硅橡胶复合微球	醇水、25℃、5 h、氨水催化^[80] 乙醇∶水=6∶1、pH=4、70℃、2 h^[81]
乙烯基三(β-甲氧基乙氧基)硅烷（A172）（CAS: 1067-53-4）	室温硫化硅橡胶；提升介电常数	乙醇、160℃、6 h^[75]