DEAEMA-co-SVS聚合物的制备与CO_2开关性能
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摘要
以甲基丙烯酸二乙氨基乙酯(DEAEMA)和乙烯基磺酸钠(SVS)作为单体通过自由基聚合的方法合成了一种新型的CO_2开关的高分子表面活性剂:聚(甲基丙烯酸二乙氨基乙酯-co-乙烯基磺酸钠),命名为聚(DEAEMA-co-SVS).通过表面张力和界面张力的测量研究了该物质的表面活性及CO_2开关性能,并探究了该物质的CO_2开关机理.研究表明:该聚合物能有效的将水的表面张力降低至37.279 m N/m,将甲苯/水的界面张力降至4.9 m N/m;聚合物水溶液在通入CO_2时,叔胺基团在CO_2的作用下发生了质子化作用,形成了大量的季铵盐,溶液由乳白色变为澄清态,并且其表面张力明显升高(42.636 m N/m);在60℃下通入N2,叔胺基团失去质子化,溶液变回原始状态.将聚合物水溶液和甲苯混合能形成稳定的乳液,且该乳液能在通入或去除CO_2时实现破乳和再乳化;甲苯的量不同均可以形成稳定的乳液并在通入CO_2后破乳:聚合物水溶液浓度低于0.25 wt%时,形成的乳液不稳定.
A new CO_2-switchable polymer surfactant Poly( N,N-Diethylaminoethyl methacrylate-co-sodium vinylsulfonate)( abbreviated as Poly( DEAEMA-co-SVS)) was synthesized by N,N-Diethylaminoethyl methacrylate( DEAEMA) and sodium vinylsulfonate( SVS) via their free radical polymerization. The surface activity,CO_2 response and its mechanism of the material were assessed by evaluation of its surface tension and interfacial tension. The results show that the polymer effectively reduced the surface tension of water to37.279 m N/m,and reduced that of toluene/water to 4. 9 m N/m. Bubbling CO_2 to the milky polymer aqueous solution,the tertiary amine groups in it undergo protonation under the action of CO_2,forming a large amount of quaternary ammonium salts,resulting the clarified state and its surface tension significantly increased to 42. 636 m N/m. On the contrary,bubbling N2 at 60 ℃,The tertiary amine groups are deprotonated,and the polymer aqueous solution converted to its original state. Mixing the Poly( DEAEMA-co-SVS) aqueous solution with toluene,the mixture solution showed strong stability and CO_2 response. Bubbling CO_2 to or removing it from the mixture solution,its de-emulsification and re-emulsification process was observed,respectively. In addition,the mixture solution presented as a stable emulsion at varied concentration of toluene in it. However,the mixture solution showed poor stability when the concentration of Poly( DEAEMA-co-SVS) in it was lower than 0.25 wt%.
A new CO_2-switchable polymer surfactant Poly( N,N-Diethylaminoethyl methacrylate-co-sodium vinylsulfonate)( abbreviated as Poly( DEAEMA-co-SVS)) was synthesized by N,N-Diethylaminoethyl methacrylate( DEAEMA) and sodium vinylsulfonate( SVS) via their free radical polymerization. The surface activity,CO_2 response and its mechanism of the material were assessed by evaluation of its surface tension and interfacial tension. The results show that the polymer effectively reduced the surface tension of water to37.279 m N/m,and reduced that of toluene/water to 4. 9 m N/m. Bubbling CO_2 to the milky polymer aqueous solution,the tertiary amine groups in it undergo protonation under the action of CO_2,forming a large amount of quaternary ammonium salts,resulting the clarified state and its surface tension significantly increased to 42. 636 m N/m. On the contrary,bubbling N2 at 60 ℃,The tertiary amine groups are deprotonated,and the polymer aqueous solution converted to its original state. Mixing the Poly( DEAEMA-co-SVS) aqueous solution with toluene,the mixture solution showed strong stability and CO_2 response. Bubbling CO_2 to or removing it from the mixture solution,its de-emulsification and re-emulsification process was observed,respectively. In addition,the mixture solution presented as a stable emulsion at varied concentration of toluene in it. However,the mixture solution showed poor stability when the concentration of Poly( DEAEMA-co-SVS) in it was lower than 0.25 wt%.
引文
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[3]Feng X,Mussone P,Gao S,et al.Mechanistic Study on Demulsification of Water-in-Diluted Bitumen Emulsions by Ethylcellulose[J].Langmuir the Acs Journal of Surfaces&Colloids,2010,26(5):3050-3057.
[4]Pensini E,Harbottle D,Fan Y,et al.Demulsification Mechanism of Asphaltene-Stabilized Water-in-Oil Emulsions by a Polymeric Ethylene Oxide-Propylene Oxide Demulsifier[J].Energy&Fuels,2014,28(11):6760-6771.
[5]Feng Y,Chu Z.p H-Tunable wormlike micelles based on an ultra-long-chain"pseudo"gemini surfactant[J].Soft Matter,2015,11(23):4614.
[6]Morse A J,Armes S P,Thompson K L,et al.Novel Pickering emulsifiers based on p H-responsive poly(2-(diethylamino)ethyl methacrylate)latexes[J].Langmuir the Acs Journal of Surfaces&Colloids,2013,29(18):5466-5475.
[7]Jiang Z,Li X,Yang G,et al.p H-responsive surface activity and solubilization with novel pyrrolidone-based Gemini surfactants[J].Langmuir,2012,28(18):7174-7181.
[8]Karthaus O,Shimomura M,Hioki M,et al.Reversible Photomorphism in Surface Monolayers[J].Journal of American Chemical Society,1996,118(38):9174-9175.
[9]Takahashi Y,Fukuyasu K,Horiuchi T,et al.Photoinduced demulsification of emulsions using a photoresponsive gemini surfactant[J].Langmuir the Acs Journal of Surfaces&Colloids,2013,30(1):41-47.
[10]Tsuchiya K,Orihara Y,Kondo Y,et al.Control of Viscoelasticity Using Redox Reaction[J].Journal of the American Chemical Society,2004,126(39):12282-12283.
[11]Brown P,Khan A M,Armstrong J P K,et al.Magnetizing DNA and Proteins Using Responsive Surfactants[J].Advanced Materials,2012,24(46):6244-6247.
[12]Qian Y,Zhang Q,Qiu X,et al.CO2-responsive diethylaminoethyl-modified lignin nanoparticles and their application as surfactant for CO2/N2-switchable Pickering emulsions[J].Green Chemistry,2014,16(12):4963-4968.
[13]Liu Y,Jessop P G,Cunningham M,et al.Switchable surfactants[J].Science,2006,313(5789):958-960.
[14]Zhang Y,Zhang Y,Wang C,et al.CO2-Responsive microemulsion:reversible switching from an apparent single phase to near-complete phase separation[J].Green Chemistry,2015,18(2):392-396.
[15]Jessop P G,Mercer S M,Heldebrant D J.CO2-Triggered Switchable Solvents,Surfactants,and Other Materials[J].Energy&Environmental Science,2012,5(6):7240-7253.
[16]王九霞,苏鑫,冯玉军.CO2开关型溶剂、溶质及表面活性剂[J].化学进展,2010,22(11):2099-2105.
[17]冯岸超,闫强,袁金颖.CO2刺激响应聚合物[J].化学进展,2012,24(10):1995-2003.
[18]Alshamrani A K,Vanderveen J R,Jessop P G.A guide to the selection of switchable functional groups for CO2-switchable compounds[J].Physical Chemistry Chemical Physics,2016,18(28):19276-19288.
[19]Wetering P V D,Zuidam N J,Steenbergen M J V,et al.A mechanistic study of the hydrolytic stability of poly(2-(dimethylamino)ethyl methacrylate)[J].Macromolecules,1998,31(23):8063-8068.
[20]Lei Z,Qian J,Fan Y,et al.A facile CO2switchable nanocomposite with reversible transition from sol to self healable hydrogel[J].Rsc Advances,2015,5(76):62229-62234.
[21]Lu H,Zhou Z,Jiang J,et al.Carbon dioxide switchable polymer surfactant copolymerized with 2-(dimethylamino)ethyl methacrylate and butyl methacrylate as a heavy-oil emulsifier[J].Journal of Applied Polymer Science,2015,132(3):41307.