Bon Stefan A F, Colver Patrick J
Centre for Interfaces and Materials, Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK.
Langmuir. 2007 Jul 31;23(16):8316-22. doi: 10.1021/la701150q. Epub 2007 Jun 29.
Solid-stabilized, or Pickering, miniemulsion polymerizations using Laponite clay discs as stabilizer are investigated. Free radical polymerizations are carried out using a variety of hydrophobic monomers (i.e., styrene, lauryl (meth)acrylate, butyl (meth)acrylate, octyl acrylate, and 2-ethyl hexyl acrylate). Armored latexes, of which the surfaces of the particles are covered with clay discs, are obtained, as confirmed by scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Overall polymerization kinetics of the Pickering miniemulsion polymerizations of styrene were investigated via gravimetry. Comparison with the bulk polymerization analogue clearly shows compartmentalization. Moreover, retardation effects up to intermediate monomer conversions are observed; they are more prominent for the smaller particles and are ascribed to the Laponite clay. A model is presented that allows for the prediction of the average particle size of the latexes produced as a function of the amounts of monomer and Pickering stabilizers used. It shows that under specific generic conditions the number of clay discs used correlates in a linear fashion with the total surface area of the latex particles. This is a direct result of the reversibility of the Laponite clay disc adhesion process under the emulsification conditions (i.e., sonication) used.
研究了使用锂皂石粘土盘作为稳定剂的固体稳定或皮克林细乳液聚合反应。使用多种疏水性单体(即苯乙烯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸丁酯、丙烯酸辛酯和丙烯酸2-乙基己酯)进行自由基聚合反应。通过扫描电子显微镜(FE-SEM)和原子力显微镜(AFM)证实,获得了颗粒表面覆盖有粘土盘的铠装胶乳。通过重量法研究了苯乙烯的皮克林细乳液聚合反应的整体聚合动力学。与本体聚合类似物的比较清楚地显示了分区化。此外,观察到直至中间单体转化率的阻滞效应;它们在较小颗粒中更为突出,并归因于锂皂石粘土。提出了一个模型,该模型可以预测所制备胶乳的平均粒径与所用单体和皮克林稳定剂用量的函数关系。结果表明,在特定的一般条件下,所用粘土盘的数量与胶乳颗粒的总表面积呈线性相关。这是在所用乳化条件(即超声处理)下锂皂石粘土盘粘附过程可逆性的直接结果。