超亲水纤维素/环糊精基聚电解质刷复合气凝胶的制备及对乳化油分离研究
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摘要
现代工业生产中会出现大量油滴粒径微小、能够在水体中稳定且长期存在的乳化油,其难以被破乳分离,对土壤、水体有严重危害。本文通过反相悬浮法制备β-环糊精(β-CD)微球,利用原子转移自由基聚合(ATRP)的方法在β-环糊精微球上接枝阳离子聚合物刷聚[甲基丙烯酸(N,N-二甲氨基)乙酯](PDMAEMA),再将纤维素与环糊精基聚电解质刷进行复合制备具有超亲水性/水下超疏油的纤维素/环糊精基聚电解质刷(CE/β-CD-g-PDMAEMA)复合气凝胶。以水包油(O/W)型吐温80(Tween 80)和十二烷基苯磺酸钠(SDBS)乳化油为研究对象,考察了环糊精基聚电解质刷的添加量对乳化油分离效果的影响,实验结果表明:当环糊精基聚电解质刷添加量为5%时,对乳化油的分离效率高达98%,乳化油分离粒径由1μm降至50 nm以下。CE/β-CD-g-PDMAEMA复合气凝胶的制备工艺简单,分离效率高,对于乳化油的破乳分离具有潜在的工业应用价值。
In modem industrial production, large quantities of emulsion oil with small particle size,which can be stable and exist for a long time in water, are difficult to be separated by demulsification and have serious harm to soil and water.β-cyclodextrinspherical polymer particles were prepared by inverse suspension polymerization in this paper. Then we synthesized cyclodextrin spherical polymer particles with cationic polymer brush2-(dimethylamino)ethylmethacrylate(PDMAEMA) by atom transfer radical polymerization(ATRP). The cellulose/cyclodextrin poly electrolyte brushes(CE/β-CD-g-PDMAEMA) composite aerogel with superhydrophilic/underwater superhydrophobic properties was successfully prepared by compositing cellulose(CE) andβ-CD-g-PDMAEMA. The effect of adding amount of cyclodextrin based polyelectrolyte. brush on the separation of emulsified oil was investigated with water-wrapped oil(0/W) Tween 80 and SDBS emulsion oil. The experimental results showed that when the addition amount of polyelectrolyte brush particleswas 5%, the separation efficiency of emulsion oil reached over 98%, and the particle size of emulsion oil was reduced to below 50 nm to 1 μm. CE/β-CD-g-PDMAEMA composite aerogel preparation process is simple, with high separation efficiency. The results have industrial application value for emulsion breaking separation.
In modem industrial production, large quantities of emulsion oil with small particle size,which can be stable and exist for a long time in water, are difficult to be separated by demulsification and have serious harm to soil and water.β-cyclodextrinspherical polymer particles were prepared by inverse suspension polymerization in this paper. Then we synthesized cyclodextrin spherical polymer particles with cationic polymer brush2-(dimethylamino)ethylmethacrylate(PDMAEMA) by atom transfer radical polymerization(ATRP). The cellulose/cyclodextrin poly electrolyte brushes(CE/β-CD-g-PDMAEMA) composite aerogel with superhydrophilic/underwater superhydrophobic properties was successfully prepared by compositing cellulose(CE) andβ-CD-g-PDMAEMA. The effect of adding amount of cyclodextrin based polyelectrolyte. brush on the separation of emulsified oil was investigated with water-wrapped oil(0/W) Tween 80 and SDBS emulsion oil. The experimental results showed that when the addition amount of polyelectrolyte brush particleswas 5%, the separation efficiency of emulsion oil reached over 98%, and the particle size of emulsion oil was reduced to below 50 nm to 1 μm. CE/β-CD-g-PDMAEMA composite aerogel preparation process is simple, with high separation efficiency. The results have industrial application value for emulsion breaking separation.
引文
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[2] AndréR C,Alexey R,Thorsteinn L.Self-assembly ofα-cyclodextrin andβ-cyclodextrin:identification and development of analytical techniques[J].Journal of Pharmaceutical Sciences,2018,107(8):2208-2215.
[3] Cem V,Erem B.Development of implantable hydroxypropyl-β-cyclodextrin coated polycaprolactone nanoparticles for the controlled delivery of docetaxel to solid tumors[J].Journal of Inclusion Phenomena&Macrocyclic Chemistry,2014,80(1-2):9-15.
[4] Agnes W,Artjom D,Martin S,et al.Synthesis ofβ-cyclodextrin-based star block copolymers with thermoresponsive behavior[J].Polymers,2015,7(5):921-938.
[5] Alam A U,Qin Y H,Howlader M,etal.Electrochemicalsensing of acetaminophen using multi-walled carbon nanotube andβ-cyclodextrin[J].Sensors&Actuators B Chemical,2018,254:896-909.
[6] Ong W J,Tan L L,Ng Y H,etal.Graphiticcarbon nitride(g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation:are we a step closer to achieving sustainability[J].Chemical Reviews,2016,116(12):7159-7329.
[7] Muna A,Sreekrishnan T R.Aquatic toxicity from pulp and paper mill effluents:a review[J].Advances in Environmental Research,2001,5(2):175-196.
[8] Wu W,Wei G,Li J S.Star polymers:advances in biomedical applications[J].Progress in Polymer Science,2015,46:55-85.
[9] Zhang L H,Lin Y,Zhang Y J,etal.Fluorescent micelles based on star amphiphilic copolymer with a porphyrin core for bioimaging and drug delivery[J].Macromolecular Bioscience,2012,12(1):83–92.
[10] Peng Y B,Guo Z G.Recent advances in biomimetic thin membranes applied in emulsified oil/water separation[J].Journal of Materials Chemistry A,2016,4(41):15749-15770.
[11] Xu H Y,Jia W H,Ren S L,etal.Novel and recyclable demulsifier of expanded perlite grafted by magnetic nanoparticles for oil separation from emulsified oil wastewaters[J].Chemical Engineering Journal,2018,337:10-18.
[12] Wang Q,Wu J N,Meng G H,etal.Preparation of novel cotton fabric composites with p H controlled switchable wettability for efficient water-in-oil and oil-in-water emulsions separation[J].Applied Physics A Materials Science&Processing,2018,124(6):422.
[13] Zhao L Y,Li L,Wang Y X,etal.Preparation and characterization of thermo and p H dual-responsive 3D cellulosebased aerogel for oil/water separation[J].Applied Physics A,2018,124(1):9.
[14] Chen Q C,Zhang R,Wang J,etal.Spherical particles ofα-,β-andγ-cyclodextrin polymers and their capability for phenol removal[J].Materials Letters,2012,79:156-158.
[15] Wang Q,Meng G H,Wu J N,etal.Novel robust cellulosebased foam with p H and light dual-response for oil recovery[J].Frontiers of Materials Science,2018,12(2):1-11.
[16] Peng H L,Wu J N,Wang Y X,etal.A facile approach for preparation of underwater superoleophobicity cellulose/chitosan composite aerogel for oil/water separation[J].Applied Physics A,2016,122(5):516.
[17] Meng G H,Peng H L,Wu J N,etal.Fabrication of superhydrophobic cellulose/chitosan composite aerogel for oil/water separation[J].Fibers&Polymers,2017,18(4):706-712.