由具有热响应接枝聚合物刷的纳米粒子稳定的 Pickering 乳液。
Pickering emulsions stabilized by nanoparticles with thermally responsive grafted polymer brushes.
机构信息
Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213-3890, USA.
出版信息
Langmuir. 2010 Oct 5;26(19):15200-9. doi: 10.1021/la1027898.
A study is presented of emulsification by silica nanoparticles with poly(2-(dimethylamino)ethyl methacrylate) brushes grafted from their surfaces (SiO(2)-PDMAEMA) by atom-transfer radical polymerization (ATRP). The grafted nanoparticles were used to stabilize xylene-in-water and cyclohexane-in-water Pickering emulsions. PDMAEMA is a water-soluble weak polyelectrolyte with a pH-dependent lower critical solution temperature (LCST). Accordingly, SiO(2)-PDMAEMA nanoparticles were thermally responsive, as shown by the fact that they displayed a critical flocculation temperature (CFT) when heated. ATRP provides a high degree of control over the brush grafting density and degree of polymerization, two of the principal variables examined in this study. The effects of the solvent quality of the "oil" for the PDMAEMA brush were studied in addition to the effects of aqueous pH, ionic strength, and temperature relative to the CFT. The preferred emulsion type was oil in water in all cases. The lowest grafting density particles (0.077 chains/nm(2)) proved to be the most efficient and robust emulsifiers, producing stable emulsions using as little as 0.05 wt % particles in the aqueous phase and successfully emulsifying over a broader range of solution conditions than for the higher grafting density particles (0.36 and 1.27 chain/nm(2)). Both good (xylene) and poor (cyclohexane) solvents could be emulsified, but the poor solvent could be emulsified over a broader range of conditions than the good solvent. Emulsions have been stable for over 13 months, and some have dispersed as much as 83 vol % oil in the emulsion phase. Thermally responsive emulsions were created with the SiO(2)-PDMAEMA particles such that stable emulsions prepared at low temperature were rapidly broken by increasing the temperature above the CFT.
研究了通过原子转移自由基聚合(ATRP)从表面接枝聚(2-二甲氨基乙基甲基丙烯酸酯)刷的二氧化硅纳米粒子(SiO 2 -PDMAEMA)进行乳液乳化。接枝的纳米粒子用于稳定二甲苯在水中和环己烷在水中的 Pickering 乳液。PDMAEMA 是一种水溶性的弱聚电解质,具有 pH 依赖性的较低临界溶液温度(LCST)。因此,SiO 2 -PDMAEMA 纳米粒子具有热响应性,这可以从加热时它们显示临界絮凝温度(CFT)这一事实中看出。ATRP 可以高度控制刷接枝密度和聚合度,这是本研究中检查的两个主要变量之一。除了考察水溶液的 pH、离子强度以及相对于 CFT 的温度对 PDMAEMA 刷的“油”的溶剂质量的影响外,还研究了这些影响。在所有情况下,首选的乳液类型都是油包水型。证明具有最低接枝密度的粒子(0.077 链/nm 2 )是最有效和最稳定的乳化剂,在水相中的用量低至 0.05wt%的粒子即可产生稳定的乳液,并且比高接枝密度的粒子(0.36 和 1.27 链/nm 2 )更能成功地乳化更广泛的溶液条件。既可以乳化良好的溶剂(二甲苯),也可以乳化较差的溶剂(环己烷),但较差的溶剂可以在比良好的溶剂更广泛的条件下乳化。乳液已经稳定了超过 13 个月,并且一些乳液已经分散了多达 83vol%的油在乳液相中。通过将温度升高到 CFT 以上,可以使 SiO 2 -PDMAEMA 粒子形成热响应性乳液,从而迅速破坏在低温下制备的稳定乳液。