聚多巴胺修饰纳米SiO2颗粒

doi:10.16085/j.issn.1000-6613.2021-0229

摘要/Abstract

摘要：

纳米SiO₂颗粒粒径小、比表面积大，广泛用做填料、涂料、催化剂等。由于纳米SiO₂颗粒表面能高、亲水性强、易团聚、在聚合物基体中的分散性差，需要对其表面修饰改性。多巴胺（DA）分子具有类似贻贝分泌的黏附蛋白的结构单元儿茶酚和活性基团氨基，在碱性条件下，通过氧化自聚可在多种材料表面沉积，形成富含活性基团的聚多巴胺（PDA）包覆层，可进行二次修饰，是近期发展的一种新型表面修饰方法。本文针对纳米SiO₂颗粒表面的PDA功能化修饰，分析了该修饰方法的工艺特点及优势，阐述了SiO₂@PDA纳米颗粒及SiO₂/PDA共聚复合颗粒的制备路线及应用，总结了SiO₂@PDA颗粒表面二次功能化修饰的研究进展。分析表明，SiO₂@PDA表面易于接枝功能化聚合物分子，并可负载功能纳米颗粒，有利于拓展SiO₂纳米颗粒的多功能应用。关于多巴胺与SiO₂纳米颗粒的表面反应机制、沉积动力学、聚合机理等仍需进一步研究。

关键词: 聚多巴胺, 纳米SiO₂, 表面修饰, 功能化, 聚合物

Abstract:

Silica (SiO₂) nanoparticles with small particle size and large specific surface area are widely used as fillers, paints, catalyst etc. However, due to the high surface energy and poor interface compatibility with polymer matrix, modification for the SiO₂ nanoparticles is necessary to solve the problems of the pool dispersion and easy agglomeration in application. Dopamine (DA) molecules possess the similar structure unit and strong adhesion as those of adhesive proteins secreted by mussels, and it can form polydopamine (PDA) coated layer on the surface of SiO₂ substrate in alkaline solution expeditiously, which results in the improvement of the chemical versatility and strong adhesion performance to substrate. PDA modification is a new modification method developed recently for particle surface. This paper reviewed the preparation and application of SiO₂@PDA nanoparticles and nanocomposite, as well as the secondary modification of SiO₂@PDA and the application. The characteristics and advantages of the PDA modification were summarized. The analysis indicated that SiO₂@PDA particle surface can easily graft functional polymer molecules and load metal nanoparticles, which expanded the multifunctional application of SiO₂ nanoparticles. However, the surface reaction mechanism, deposition kinetics and polymerization mechanism of SiO₂@PDA nanoparticles still needed to be further studied.

Key words: polydopamine, silica, surface modification, functionalization, polymer

中图分类号:

TB33

马冠香, 杨令, 王亭杰. 聚多巴胺修饰纳米SiO₂颗粒[J]. 化工进展, 2021, 40(12): 6729-6737.

MA Guanxiang, YANG Ling, WANG Ting-jie. Surface modification of silica nanoparticles using polydopamine[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6729-6737.

图/表 5

图1 SiO2@PDA核壳纳米颗粒的制备

图2 SiO2@SiO2/PDA复合核壳颗粒设计[39](a)为以DA和TEOS分子为前体，原位St?ber模板合成空心介孔碳球（HMCS）；(b)、(c)为通过NaOCl刻蚀除去PDA后剩下SiO2组分的TEM图；(d)、(e)为除去SiO2模板，并经过高温碳化后获得HMCS的TEM图

图3 通过PDA表面包覆和迈克尔加成反应制备SiO2@PDA@poly(PEGMA)纳米复合材料[42]I—以聚（乙二醇）甲基丙烯酸酯（PEGMA）单体和过硫酸铵为引发剂，制备poly(PEGMA)；Ⅱ—SiO2@PDA与氨基封端的聚合物反应

图4 SiO2@PDA@PAPTCl的制备及电镜图[47]

图5 SiO2@PDA@Ag的合成及其表征图[49-50]

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聚多巴胺修饰纳米SiO₂颗粒

Surface modification of silica nanoparticles using polydopamine

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