Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles

Shuo Lu; Dong-jie Yang; Yuan-yuan Li; Zhi-xian Li; Xue-qing Qiu

doi:10.11777/j.issn1000-3304.2018.18211

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Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles

Research Article | 更新时间：2021-01-26

- Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles
- Acta Polymerica Sinica Vol. 50, Issue 2, Pages: 160-169(2019)
- 作者机构：
  
  1.华南理工大学化学与化工学院制浆造纸工程国家重点实验室　广州 510640
  2.河南中医药大学药学院　郑州 450046
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2018.18211
  CLC：
- Published：2019-2，
  
  Published Online：27 November 2018，
  
  Received：5 October 2018，
  
  Revised：25 October 2018，
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Shuo Lu, Dong-jie Yang, Yuan-yuan Li, Zhi-xian Li, Xue-qing Qiu. Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles. [J]. Acta Polymerica Sinica 50(2):160-169(2019)
DOI：

Shuo Lu, Dong-jie Yang, Yuan-yuan Li, Zhi-xian Li, Xue-qing Qiu. Double pH-Responsive Pickering Emulsions Stabilized by Quaternized Lignin Combination with Titanium Dioxide Nanoparticles. [J]. Acta Polymerica Sinica 50(2):160-169(2019) DOI： 10.11777/j.issn1000-3304.2018.18211.

摘要

利用季铵化木质素与TiO

纳米颗粒复合作为乳化剂，以正癸烷为油相，制备具有pH响应性的O/W型Pickering乳液. 该乳液在6.0

7.0范围内稳定，在酸性和碱性条件下不稳定. 在中性溶液中，季铵化木质素带负电，TiO

带正电，两者通过静电吸附作用结合，季铵化木质素的疏水性苯丙烷骨架使TiO

的亲水性降低，提高颗粒的界面活性，形成稳定的乳液. 在酸性和碱性条件下，季铵化木质素和TiO

带同种电荷，两者之间存在强烈的静电斥力，而单独的TiO

纳米颗粒亲水性太高，无法稳定于油水界面形成稳定的乳液，故乳液破乳. 因此季铵化木质素与TiO

纳米颗粒之间的吸附特征赋予Pickering乳液双重pH响应特性，向体系中加入HCl溶液以及NaOH溶液改变水相的pH值，能使乳液体系在乳化与破乳状态之间循环多次，同时乳滴没有明显的变化，具有优异的耐盐性.

Abstract

pH-Responsive oil-in-water Pickering emulsions using

-decane as oil phase were prepared by mixing quaternized lignin (QAL) and titanium dioxide (TiO

) nanoparticles as emulsifiers. The emulsions stabilized by 0.5 wt% TiO

neat nanoparticles are extremely unstable due to the strong hydrophilic properties of the nanoparticles. However

when TiO

nanoparticles are dispersed in neutral solution containing 0.1 wt% QAL

all the emulsifier particles can be applied onto the

-decane/water interface

which greatly improves the stability of the emulsions and the droplet size ranges from 20 μm to 60 μm. Meanwhile

emulsions stabilized by QAL and TiO

nanoparticles show outstanding pH-responsive properties

which are stable in the range of 6.0

7.0 while unstable under the acidic and basic conditions. The synergistic stabilization mechanism of QAL and TiO

nanoparticles was studied with zeta potential

adsorption kinetics

and three-phase contact angle. QAL pertains to amphoteric surfactants whose isoelectric point is 7.5. When 6.0

7.0

QAL molecules are negatively charged

allowing them to combine with TiO

nanoparticles

via

electrostatic interactions. The hydrophobic phenylpropane skeleton of QAL molecule reduces the hydrophilicity of TiO

nanoparticles thereby enhances their surface activity to form stable emulsions. However

under the acidic and alkaline conditions

QAL molecules turn into the same charge with TiO

nanoparticles. Thus

QAL molecules significantly desorb from TiO

nanoparticles surface due to electrostatic repulsion. TiO

nanoparticles become intensely hydrophilic again and unable to stay on the oil/water interface

which makes the emulsions unstable as a result. Therefore

the adsorption behaviour between QAL and TiO

nanoparticles endows Pickering emulsions with double pH-responsive characteristics. With the alternative pH of aqueous phase by adding aqueous HCl and aqueous NaOH

the emulsion system can be recycled many times between emulsification and demulsification while the average droplet size has no obvious change due to its excellent salt tolerance.

关键词

季铵化木质素TiO2pH响应性Pickering乳液吸附

Keywords

Quaternized ligninTiO2pH ResponsivePickering emulsionsAdsorption

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