Preparation and research of Diatomite@PNIPAm-stabilized Pickering emulsion with temperature responsiveness
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摘要: 针对由表面活性剂所稳定的乳液具有毒性且不环保的缺点，对硅藻土颗粒(Diatomite，DE)进行改性，并对其所制备的具有温度响应性的Pickering乳液进行了研究。由于硅藻土颗粒具有生物相容性好的优势，在化妆品和制药领域具有应用潜力。先通过硅烷偶联剂(MPS)疏水改性DE得到Diatomite@MPS，再接枝温敏型聚合物聚N-异丙基丙烯酰胺(PNIPAm)，成功合成了具有温度响应性的改性硅藻土颗粒(Diatomite@PNIPAm)。由TGA结果表明制备Diatomite@PNIPAm的最佳MPS与NIPAm摩尔比为1∶1。随后，将Diatomite@PNIPAm作为乳化剂分别在不同浓度的条件下制备了水包油(O/W)型Pickering乳液，确定了3.0 wt%为最佳浓度。此外，确定Diatomite@PNIPAm浓度后，分别从1∶9到9∶1的不同油水体积比制备乳液，结果表明油水体积比为7∶3时最佳。通过差示扫描量热仪(DSC)测定所制备的Pickering乳液的低临界溶解温度(LCST)为40℃，且乳液至少可以进行6次破乳-再乳化循环，具备良好的破乳-再乳化循环性能。
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关键词:
- 温度响应性 /
- Pickering乳液 /
- 硅藻土 /
- 低临界溶解温度 /
- 破乳-再乳化循环性能
Abstract: Aiming at the shortcomings of the emulsion stabilized by surfactant due to toxicity and non-environmental protection, modified diatomite particles (DE), the temperature-responsive Pickering emulsion was studied. Due to the advantages of superior biocompatibility, DE have application potential in the field of cosmetics and pharmaceuticals. First, the Diatomite@MPS was obtained by silane coupling agent (MPS) hydrophobic modified DE. Then, modified DE (Diatomite@PNIPAm) with temperature responsiveness was synthesized successfully by grafting the temperature-responsive polymer poly N-isopropylacrylamide (PNIPAm). According to the characterization results of FT-IR testing and water contact angle testing, the diatomaceous earth was modified successfully. The TGA results showed that the optimal molar ratio of the Diatomite@PNIPAm prepared from MPS to NIPAm was 1∶1. Subsequently, oil-in-water (O/W) Pickering emulsions were prepared with Diatomite@PNIPAm as an emulsifier at different concentrations, and 3.0 wt% was determined as the optimal concentration. In addition, the emulsion was prepared with different oil-water volume ratios from 1∶9 to 9∶1 after determining the Diatomite@PNIPAm concentration, and the results showed that the oil-water volume ratio was 7∶3 as the best. The characterization results of Differential scanning calorimeter (DSC) testing showed that the lower critical solution temperature (LCST) of the Pickering emulsion was 40℃. The emulsion can undergo at least 6 demulsification-reemulsification cycles, and possesses excellent demulsification-reemulsification cycle performance. -
图 1 Diatomite@聚N-异丙基丙烯酰胺(PNIPAm)的合成路线图和破乳-再乳化循环示意图
Figure 1. Synthesis route of Diatomite@ poly N-isopropylacrylamide (PNIPAm) and demulsification-reemulsification cycle
图 2 硅藻土颗粒(DE)与Diatomite@PNIPAm的FTIR光谱图
Figure 2. FTIR spectra of diatomite (DE) and Diatomite@PNIPAm
图 3 不同硅藻土的水接触角图像
Figure 3. Image of water contact angle of different diatomaceous earths
图 6 由不同MPS与NIPAm摩尔比合成的Diatomite@PNIPAm稳定的Pickering乳液的图像和光学显微镜图
Figure 6. Digital photographs and optical microscope images of Pickering emulsions stabilized by different MPS to NIPAm ratios of Diatomite@PNIPAm
图 7 不同条件下制备的Pickering乳液
Figure 7. Pickering emulsions prepared under different conditions
图 8 不同Pickering乳液在稳定24小时和2个月后的对比图和光学显微镜图像
Figure 8. Comparison of different Pickering emulsions after 24 h and 2 months of stabilization and optical microscope images
图 9 Pickering乳液的DSC曲线图、直径图、光学显微镜图
Figure 9. DSC plots, diameter plots, and optical microscope plots of Pickering emulsions
图 10 Diatomite@PNIPAm浓度为3.0wt%和4.0wt%制备的Pickering乳液的破乳-再乳化循环图
Figure 10. Demulsification-reemulsification cycle diagram of Pickering emulsion prepared at 3.0wt% and 4.0wt% content Diatomite@PNIPAm
图 11 不同循环次数的Pickering乳液的光学显微镜和平均直径对比图
Figure 11. Optical microscope images and average diameter comparison plots of Pickering emulsions with different number of cycles
表 1 不同配方制备的改性硅藻土颗粒
Table 1. Modified diatomite particles prepared with different formulations
Sample Diatomite/g MPS/g NIPAm/g MPS:NIPAm/mol Grafting rate η/% Sample 1 4.0 10 3.19 1:0.7 10.05 Sample 2 4.0 10 4.56 1:1 15.02 Sample 3 4.0 10 9.12 1:2 13.46 Note: MPS—Silane coupling agent. 
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