Institut de Química Avancada de Catalunya, CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain.
Langmuir. 2010 Jun 1;26(11):7717-24. doi: 10.1021/la904461a.
The seeded semicontinuous emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BuA) stabilized with a graft polymeric surfactant based on inulin, INUTEC SP1, as well as its mixture with sodium lauryl sulfate (SLS) is described. The mixture of SLS and Brij58 (alcohol ethoxylated) and the mixture of SLS and Pluronic P85 (block copolymer PEO-PPO-PEO) are also used as surfactant systems. The addition of methacrylic acid (MAA) or acrylic acid (AA) as comonomers is also studied. Previous results proved this inulin-derivative surfactant, INUTEC SP1, to be very effective on synthesizing latexes using a very low surfactant concentration. The kinetic features of the emulsion polymerization (instantaneous conversion and total conversion) were gravimetrically determined along the reactions. Latex dispersions were characterized by photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM) to obtain the average particle size, the particle size distributions (PSDs) as well as the polydispersity index (PdI). The stability was determined by turbidimetry measurements and expressed in terms of critical coagulation concentration. The results showed that the use of the graft polymeric surfactant allowed obtaining highly stable nanoparticles, at low surfactant concentrations and high solid contents (up to 37 wt %). This is an improvement with respect to previous works, in which a mixture of the graft polymeric surfactant with another surfactant was required to obtain stable nanoparticles with low polydispersity, at high solid content. In the present work, low polydispersity was achieved using INUTEC as the only emulsifier, which was related to the absence of secondary nucleations. When a mixture of INUTEC SP1 and SLS is used, a wider PSD is obtained due to secondary nucleations. Replacing INUTEC SP1 by other nonionic surfactants such as Brij58 or Pluronic P85 leads to an increase of average particle size and wider PSD.
甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BuA)的种 seeded 半连续乳液共聚反应,使用基于菊粉的接枝聚合物表面活性剂 INUTEC SP1 进行稳定,以及其与十二烷基硫酸钠(SLS)的混合物也被用作表面活性剂体系。还使用了 SLS 和 Brij58(醇乙氧基化物)的混合物以及 SLS 和 Pluronic P85(嵌段共聚物 PEO-PPO-PEO)的混合物作为表面活性剂体系。还研究了添加甲基丙烯酸(MAA)或丙烯酸(AA)作为共聚单体的情况。先前的结果证明,这种菊粉衍生的表面活性剂 INUTEC SP1 在使用非常低的表面活性剂浓度合成乳胶方面非常有效。通过反应过程中的重量法测定了乳液聚合的动力学特征(瞬时转化率和总转化率)。乳胶分散体通过光相关光谱(PCS)和透射电子显微镜(TEM)进行表征,以获得平均粒径、粒径分布(PSD)以及多分散指数(PdI)。通过浊度测量法确定稳定性,并以临界凝聚浓度表示。结果表明,使用接枝聚合物表面活性剂可以在低表面活性剂浓度和高固含量(高达 37wt%)下获得高度稳定的纳米颗粒。与以前的工作相比,这是一个改进,以前的工作需要使用接枝聚合物表面活性剂与另一种表面活性剂的混合物才能在高固含量下获得具有低多分散性的稳定纳米颗粒。在本工作中,使用 INUTEC 作为唯一的乳化剂即可实现低多分散性,这与不存在二次成核有关。当使用 INUTEC SP1 和 SLS 的混合物时,由于二次成核,得到的 PSD 更宽。用其他非离子表面活性剂如 Brij58 或 Pluronic P85 代替 INUTEC SP1 会导致平均粒径增加和 PSD 变宽。