PNIPAM和PNIPAM-PEI微凝胶的合成、表征及作为皮克林乳液乳化剂的研究

李明昊, 王玲, 许远航, 张帅, 李可鑫, 李佳锡, 石山

PDF(2133 KB)
中国高校科技期刊信息汇聚平台
PDF(2133 KB)
塑料科技 ›› 2025, Vol. 53 ›› Issue (01) : 103-108. DOI: 10.15925/j.cnki.issn1005-3360.2025.01.019
助剂

PNIPAM和PNIPAM-PEI微凝胶的合成、表征及作为皮克林乳液乳化剂的研究

作者信息 +

Synthesis, Characterization and Application of PNIPAM and PNIPAM-PEI Microgels as Emulsifiers in Pickering Emulsions

Author information +
History +

摘要

通过无皂乳液聚合法制备聚N-异丙基丙烯酰胺（PNIPAM）微凝胶，再以PNIPAM微凝胶为种子，N-异丙基丙烯酰胺（NIPAM）和聚乙烯亚胺（PEI）为第二单体，叔丁基过氧化氢为引发剂，采用种子无皂乳液聚合法合成PNIPAM-PEI微凝胶。利用傅里叶红外光谱、核磁共振氢谱、透射电子显微镜和动态光散射等多种手段对所得微凝胶进行详细表征，探讨其作为乳化剂形成稳定的皮克林乳液的可行性。PNIPAM和PNIPAM-PEI微凝胶均为亚微米级球体，粒度分散均匀，具有良好的分散稳定性。两种微凝胶均表现出明显的温度响应性，体积相变温度分别为32.9、34.8 ℃。另外，PNIPAM-PEI微凝胶的流体粒径随着pH值的升高而减小，表现出显著的pH值响应性。以质量浓度为1%的PNIPAM和PNIPAM-PEI微凝胶水分散液为水相，甲苯为油相，两种微凝胶分别在油水体积比为8∶4和7∶5时形成均一稳定的O/W型皮克林乳液，且所形成的乳液表现出一定的环境响应性。

Abstract

Poly(N-isopropylacrylamide) (PNIPAM) microgels were prepared by soap-free emulsion polymerization. Then, PNIPAM-PEI microgels were synthesized by seed soap-free emulsion polymerization with PNIPAM microgels as seeds, N-isopropylacrylamide (NIPAM) and polyethyleneimine (PEI) as second monomers, and tert-butyl hydrogen peroxide as initiator. The obtained microgels were characterized in detail by Fourier transform infrared spectroscopy, nuclear magnetic resonance hydrogen spectrum, transmission electron microscopy and dynamic light scattering, and the feasibility of its use as an emulsifier to form stable pickling emulsions was discussed. PNIPAM and PNIPAM-PEI microgels were submicron spheres with uniform particle size distribution and good dispersion stability. Both microgels showed obvious temperature responsiveness, with volume phase transformation temperatures of 32.9, 34.8 ℃, respectively. In addition, the fluid particle size of PNIPAM-PEI microgels decreased with the increase of pH value, showing significant pH responsiveness. With 1% PNIPAM and PNIPAM-PEI microgel water dispersions as water phase and toluene as oil phase, the two microgels formed homogeneous and stable O/W pickling emulsions when the oil-water volume ratio was 8∶4 and 7∶5, respectively, and the emulsions formed showed certain environmental responsiveness.

关键词

聚N-异丙基丙烯酰胺 / 微凝胶 / 环境响应性 / 皮克林乳液 / 乳化剂

Key words

Poly-N-isopropylacrylamide / Microgel / Environmental responsiveness / Pickering emulsion / Emulsifier

中图分类号

TQ332

引用本文

EndNote

Ris (Procite)

Bibtex

导出引用
李明昊 , 王玲 , 许远航 , 等. PNIPAM和PNIPAM-PEI微凝胶的合成、表征及作为皮克林乳液乳化剂的研究. 塑料科技. 2025, 53(01): 103-108 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.01.019
LI Minghao, WANG Ling, XU Yuanhang, et al. Synthesis, Characterization and Application of PNIPAM and PNIPAM-PEI Microgels as Emulsifiers in Pickering Emulsions[J]. Plastics Science and Technology. 2025, 53(01): 103-108 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.01.019

参考文献

列表( 原文顺序 | 文献年度倒序 | 文中引用次数倒序 ) 可视化分析
1
CHEVALIER Y, BOLZINGER M A. Emulsions stabilized with solid nanoparticles: Pickering Emulsions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 439: 23-34.
本文引用 [1]
2
RAMSDEN W. Separation of solids in the surface-layers of solutions and "suspensions" (observations on surface-membranes, bubbles, emulsions, and mechanical coagulation)—Preliminary account[J]. Proceedings of the Royal Society of London, 1904, 72(477/486): 156-164.
3
PICKERING S U. CXCVI.-Emulsions[J]. Journal of the Chemical Society, Transactions, 1907, 91: 2001-2021.
4
TCHOLAKOVA S, DENKOV N D, LIPS A. Comparison of solid particles, globular proteins and surfactants as emulsifiers[J]. Physical Chemistry Chemical Physics, 2008, 10(12): 1608-1627.
本文引用 [1]
5
ZHAI K K, PEI X P, WANG C, et al. Water-in-oil pickering emulsion polymerization of N-isopropyl acrylamide using starch-based nanoparticles as emulsifier[J]. International Journal of Biological Macromolecules, 2019, 131: 1032-1037.
本文引用 [1]
6
FENG H, VERSTAPPEN N A L, KUEHNE A J C, et al. Well-defined temperaturesensitive surfactants for controlled emulsion coalescence[J]. Polymer Chemistry, 2013, 4(6): 1842-1847.
本文引用 [1]
7
NGO T N N, GREY C, ADLERCREUTZ P. Chemoenzymatic synthesis of the pH responsive surfactant octyl β-D-glucopyranoside uronic acid[J]. Applied Microbiology and Biotechnology, 2020, 104(3): 1055-1062.
本文引用 [1]
8
ZHANG J Y, XU Q Q, WANG F, et al. pH and redox dual-stimulated wormlike micelles based on cystamine and conventional anionic surfactant[J]. Langmuir, 2019, 35(47): 15242-15248.
9
QI L Q, SONG C, WANG T X, et al. Polymer-coated nanoparticles for reversible emulsification and recovery of heavy oil[J]. Langmuir, 2018, 34(22): 6522-6528.
10
TANAKA T, OKAYAMA M, MINAMI H, et al. Dual stimuli-responsive "Mushroom-like" Janus polymer particles as particulate surfactants[J]. Langmuir, 2010, 26(14): 11732-11736.
本文引用 [1]
11
张晓丽,袁金芳,姚莉,等.温度、pH及离子强度敏感性聚氨酯水凝胶的合成与性能研究[J].胶体与聚合物,2006(4):7-10.
本文引用 [1]
12
JASINSKI F, GUIMARES T R, DAVID S, et al. Reversible destabilization of UV-responsive polymer particles (latex) using a photoresponsive surfactant[J]. Macromolecular Rapid Communications, 2019, DOI: 10.1002/marc.201900355.
本文引用 [1]
13
LV M, WANG L, HUANG R, et al. Preparation of a magnetocaloric dual-response SiO2-based green nano-emulsifier by an SET-LRP method and evaluation of its properties[J]. European Polymer Journal, 2023, DOI: 10.1016/j.eurpolymj.2022.111697.
本文引用 [1]
14
曾海燕,曹光群.壳聚糖纳米粒子的制备及其稳定皮克林乳液的研究[D].无锡:江南大学,2015.
本文引用 [1]
15
TSUJI S, KAWAGUCHI H. Thermosensitive pickering emulsion stabilized by poly(N-isopropylacrylamide)-carrying particles[J]. Langmuir, 2008, 24: 3300-3305.
本文引用 [1]
16
TANAKA T. Collapse of gels and the critical endpoint[J]. Physical Review Letters, 1978, 40(12): 820-823.
本文引用 [1]
17
LI W X, HU L, ZHU J H, et al. Comparison of the responsivity of solution‐suspended and surface bound poly(N‐isopropylacrylamide)‐based microgels for sensing applications[J]. ACS Applied Materials & Interfaces Journal, 2017, 9: 26539-26548.
本文引用 [1]
18
PELTON R. Poly(N‐isopropylacrylamide) (PNIPAM) is never hydrophobic[J]. Journal of Colloid and Interface Science, 2010, 348: 673-674.
19
KIM Y K, KIM D, JANG G, et al. Fluorescent, stimuli‐responsive, crosslinked PNIPAM-based microgel[J]. Sensors and Actuators B: Chemical, 2015, 207: 623-630.
20
QIU Y, PARK K. Environment‐sensitive hydrogels for drug delivery[J]. Advanced Drug Delivery Reviews, 2012, 64: 49-60.
本文引用 [1]
21
TANAKA R, UEOKA I, TAKAKI Y, et al. High molecular weight linear polyethylenimine and poly(N-methylethylenimine)[J]. Macromolecules, 1983, 16(6): 849-853.
本文引用 [1]
22
TAUHARDT L, KEMPE K, KNOP K, et al. Linear polyethyleneimine: optimized synthesis and characterization-on the way to "pharmagrade" batches[J]. Macromolecular Chemistry and Physics, 2011, 212(17): 1918-1924.
23
STEWART I C, LEE C C, BERGMAN R G, et al. Living ring-opening polymerization of N-sulfonylaziridines: Synthesis of high molecular weight linear polyamines[J]. Journal of the American Chemistry Society, 2005, 127(50): 17616-17617.
本文引用 [1]
24
JIA J, WU A, LUAN S J. Spectrometry recognition of polyethyleneimine towards heavy metalions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014, 449: 1-7.
本文引用 [1]
25
SAMAL S K, DASH M, VLIERBERGHE SV, et al. Cationic polymers and their therapeutic potential[J]. Chemical Society Review, 2012, 41: 7147-7194.
26
VIRGEN‐ORTÍZ J J, SANTOS J C S, BERENGUER‐MURCIA A, et al. Polyethylenimine: A very useful ionic polymer in the design of immobilized enzyme biocatalysts[J]. Journal of Materials Chemistry B, 2017, 5: 7461-7490.
27
AMARA M, KERDJOUDJ H. Modification of cation-exchange membrane properties by electro adsorption of polyethyleneimine[J]. Desalination, 2003, 155: 79-87.
本文引用 [1]
28
ZHANG H Z, LI Q B, ZHANG Y Y, et al. A nanogel with passive targeting function and adjustable polyplex surface properties for efficient anti‐tumor gene therapy[J]. RSC Advances, 2016, 6: 84445-84456.
本文引用 [1]
29
DUBEY N C, TRIPATHI B P, MÜLLER M, et al. Enhanced activity of acetyl CoA synthetase adsorbed on smart microgel: An implication for precursor biosynthesis[J]. ACS Applied Materials Interfaces, 2015, 7: 1500-1507.
本文引用 [1]
30
DUBEY N C, TRIPATHI B P, MÜLLER M, et al. Bienzymatic sequential reaction on microgel particles and their cofactor dependent applications[J]. Biomacromolecules, 2016, 17: 1610-1620.
本文引用 [1]
31
TAN N P B, LEE C H, CHEN L H, et al. Facile synthesis of gold/polymer nanocomposite particles using polymeric amine-based particles as dual reductants and templates[J]. Polymer, 2015, 76: 271-279.
本文引用 [1]
32
XU J, ZENG F, WU S Z, et al. Gold nanoparticles bound on microgel particles and their application as an enzyme support[J]. Nanotechnology, 2007, DOI: 10.1088/0957-4484/18/26/265704.
本文引用 [1]

基金

辽宁省教育厅科学研究青年项目(LJKQ20222422)

评论

PDF(2133 KB)

Accesses

Citation

Detail
段落导航
相关文章
Copyright 中国高校科技期刊信息汇聚平台 2024-2025
技术支持：北京玛格泰克科技发展有限公司
京ICP备05021913号-19

/

〈 〉