Hallett James E, Grillo Isabelle, Smith Gregory N
H. H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL, U.K.
Institut Laue-Langevin, 71 Avenue des Martyrs, 38042 Grenoble Cedex 9, France.
Langmuir. 2020 Mar 3;36(8):2071-2081. doi: 10.1021/acs.langmuir.9b03911. Epub 2020 Feb 18.
Hard-sphere particles in nonpolar solvents are an essential tool for colloid scientists. Sterically stabilized poly(methyl methacrylate) (PMMA) particles have long been used as the exemplary hard-sphere system. However, neither the particles themselves nor the poly(12-hydroxystearic acid) (PHSA) stabilizer necessary to prevent aggregation in nonpolar solvents are commercially available. To counter this, several alternatives have been proposed. In recent years, there has been an increased interest in poly(dimethylsiloxane) (PDMS) stabilizers as a commercially available alternative to PHSA, yet the structure of particles made in this way is not as well understood as those produced using PHSA. In this work, we employ small-angle neutron scattering to determine the internal structure of PDMS-stabilized PMMA particles, synthesized with and without an additional crosslinking agent. We report data consistent with a homogeneous PMMA core with a linearly decaying PDMS shell. The thickness of the shell was in excess of 50 nm, thicker than the PHSA layer typically used to stabilize PMMA but consistent with reports of the layer thickness for similar molecular weight PDMS at planar surfaces. We also show that the amount of the hydrogenous material in the particle core of the crosslinked particles notably exceeds the amount of added ethylene glycol dimethacrylate crosslinker, suggesting some entrapment of the PDMS stabilizer in the PMMA matrix.
非极性溶剂中的硬球颗粒是胶体科学家的重要工具。空间稳定的聚甲基丙烯酸甲酯(PMMA)颗粒长期以来一直被用作典型的硬球体系。然而,无论是颗粒本身还是在非极性溶剂中防止聚集所需的聚(12-羟基硬脂酸)(PHSA)稳定剂都没有商业供应。为了解决这个问题,人们提出了几种替代方案。近年来,聚二甲基硅氧烷(PDMS)稳定剂作为PHSA的商业可用替代品受到了越来越多的关注,但以这种方式制备的颗粒结构不如使用PHSA制备的颗粒那样为人所熟知。在这项工作中,我们利用小角中子散射来确定在有无额外交联剂的情况下合成的PDMS稳定的PMMA颗粒的内部结构。我们报告的数据与具有线性衰减PDMS壳层的均匀PMMA核一致。壳层厚度超过50nm,比通常用于稳定PMMA的PHSA层厚,但与平面表面上类似分子量PDMS的层厚报告一致。我们还表明,交联颗粒的颗粒核中含氢物质的量明显超过添加的乙二醇二甲基丙烯酸酯交联剂的量,这表明PMMA基质中截留了一些PDMS稳定剂。