CO_2诱导的五嵌段非离子共聚物与阴离子氟碳表面活性剂的相互作用
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摘要
聚合物-表面活性剂复合物在诸多工业领域都具有重要的应用潜力,但利用CO_2气体调节复合物的相互作用及微观聚集体形貌鲜见报道。本文基于三嵌段共聚物普兰尼克F127制备了五嵌段共聚物聚甲基丙烯酸二乙氨基乙酯-block-聚氧化乙烯-block-聚氧化丙烯-block-聚氧化乙烯-block-聚甲基丙烯酸二乙氨基乙酯(PDEAEAM-b-F127-b-PDEAEMA)。通过聚合物溶液pH和电导率的变化研究了PDEAEAM-b-F127-b-PDEAEMA的CO_2刺激响应性,应用动态光散射和透射电子显微镜考察了PDEAEAM-b-F127-b-PDEAEMA与阴离子氟碳表面活性剂在CO_2刺激作用下的相互作用。结果表明,CO_2/N_2的交替通入可以使PDEAEAM-b-F127-b-PDEAEMA产生相应的质子化/去质子化过程,从而可逆地改变PDEAEAM-b-F127-b-PDEAEMA溶液的pH值和电导率;质子化/去质子化过程可以"开关"共聚物与阴离子氟碳表面活性剂之间的静电吸引作用,使体系中的聚集体在球形胶束与蠕虫状胶束之间发生可逆转变。CO_2可控的聚合物-表面活性剂复合物的形貌转变为构建气体响应的软材料提供了一种新的思路。
A polymer-surfactant complex is significant in understanding the interactions between amphiphilic molecules and has great potential for use in a vast number of industries. In addition, the stimuli-responsive polymersurfactant complex represents a hot research topic for the colloid community. However, the use of CO_2 gas to tune their interaction and the corresponding morphological change in the polymer-surfactant complex has been less documented. In this work, the commercially available triblock copolymer Pluronic F127 was used as a starting material and the macromolecular initiator Br-F127-Br was synthesized via esterification. Then, the pentablock copolymer poly(2-(diethylamino)ethyl methacrylate))-block-F127-block-poly(2-(diethylamino)ethyl methacrylate))(PDEAEAM-b-F127-b-PDEAEMA) was prepared via atom transfer radical polymerization(ATRP) of Br-F127-Br and the monomer 2-(diethylamino)ethyl methacrylate. Both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were characterized by FT-IR and 1 H NMR spectroscopies as well as gel permeation chromatography(GPC). The results indicated that both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were synthesized successfully. The CO_2-responsive behavior of the pentablock copolymer was examined by tracking the changes in pH and electrical conductivity of the polymer solution after alternatingly bubbling CO_2 and N_2. It was found that cyclic streaming of CO_2/N_2 could alter the pH of the polymer solution between 7.2 and 5.3, leading to the protonation degree of PDEAEAM-b-F127-b-PDEAEMA varying between 0.26 and 0.96; this in turn varied the electrical conductivity of the polymer solution between 19.4 μS·cm~(-1) and 70.6 μS·cm~(-1). The reversible changes in pH and electrical conductivity of the polymer solution indicate the good CO_2-stimuli responsiveness of PDEAEAM-b-F127-b-PDEAEMA. The interaction of PDEAEAM-b-F127-b-PDEAEMA with an anionic fluorocarbon surfactant potassium nonafluoro-1-butanesulfonate(C_4F_9SO_3K) with and without CO_2 was studied by ultraviolet-visible absorption spectrometry(UV-Vis), dynamic light scattering(DLS), and transmission electron microscopy(TEM). The transmittance of the mixed solution of PDEAEAM-b-F127-b-PDEAEMA and C_4F_9SO_3K could be varied between 84% and 52% in the absence and presence of CO_2, indicating the formation of aggregates with different sizes. The DLS results showed that the size of aggregates could be modified reversibly between tens of nanometers and several micrometers by bubbling CO_2 and replacing CO_2 by N_2. The TEM image revealed the reversible morphological transition of the aggregates from spherical to wormlike micelles after bubbling CO_2. The carbonic acid formed from CO_2 and water can protonate the PDEAEMA in the pentablock copolymer to form PDEAEMA·H~+, and thus the interaction between the pentablock copolymer and C_4F_9SO_3K becomes strong. When CO_2 is replaced by N_2, PDEAEMA·H~+ reverts to PDEAEMA, and the interaction becomes weak once again. It can therefore be concluded that the protonation/deprotonation process of the pentablock copolymer can be controlled by bubbling CO_2/N_2. The protonation/deprotonation process can "switch" the electrostatic attraction of PDEAEAM-b-F127-b-PDEAEMA to C_4F_9SO_3K, thereby tuning the hydrophilic-lipophilic balance(HLB) of the polymer-surfactant complex reversibly, leading to the reversible morphological transition of the aggregates. The strategy of CO_2-controllable morphological alteration of a polymer–surfactant complex opens a new avenue for preparing gas-sensitive soft materials.
A polymer-surfactant complex is significant in understanding the interactions between amphiphilic molecules and has great potential for use in a vast number of industries. In addition, the stimuli-responsive polymersurfactant complex represents a hot research topic for the colloid community. However, the use of CO_2 gas to tune their interaction and the corresponding morphological change in the polymer-surfactant complex has been less documented. In this work, the commercially available triblock copolymer Pluronic F127 was used as a starting material and the macromolecular initiator Br-F127-Br was synthesized via esterification. Then, the pentablock copolymer poly(2-(diethylamino)ethyl methacrylate))-block-F127-block-poly(2-(diethylamino)ethyl methacrylate))(PDEAEAM-b-F127-b-PDEAEMA) was prepared via atom transfer radical polymerization(ATRP) of Br-F127-Br and the monomer 2-(diethylamino)ethyl methacrylate. Both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were characterized by FT-IR and 1 H NMR spectroscopies as well as gel permeation chromatography(GPC). The results indicated that both Br-F127-Br and PDEAEAM-b-F127-b-PDEAEMA were synthesized successfully. The CO_2-responsive behavior of the pentablock copolymer was examined by tracking the changes in pH and electrical conductivity of the polymer solution after alternatingly bubbling CO_2 and N_2. It was found that cyclic streaming of CO_2/N_2 could alter the pH of the polymer solution between 7.2 and 5.3, leading to the protonation degree of PDEAEAM-b-F127-b-PDEAEMA varying between 0.26 and 0.96; this in turn varied the electrical conductivity of the polymer solution between 19.4 μS·cm~(-1) and 70.6 μS·cm~(-1). The reversible changes in pH and electrical conductivity of the polymer solution indicate the good CO_2-stimuli responsiveness of PDEAEAM-b-F127-b-PDEAEMA. The interaction of PDEAEAM-b-F127-b-PDEAEMA with an anionic fluorocarbon surfactant potassium nonafluoro-1-butanesulfonate(C_4F_9SO_3K) with and without CO_2 was studied by ultraviolet-visible absorption spectrometry(UV-Vis), dynamic light scattering(DLS), and transmission electron microscopy(TEM). The transmittance of the mixed solution of PDEAEAM-b-F127-b-PDEAEMA and C_4F_9SO_3K could be varied between 84% and 52% in the absence and presence of CO_2, indicating the formation of aggregates with different sizes. The DLS results showed that the size of aggregates could be modified reversibly between tens of nanometers and several micrometers by bubbling CO_2 and replacing CO_2 by N_2. The TEM image revealed the reversible morphological transition of the aggregates from spherical to wormlike micelles after bubbling CO_2. The carbonic acid formed from CO_2 and water can protonate the PDEAEMA in the pentablock copolymer to form PDEAEMA·H~+, and thus the interaction between the pentablock copolymer and C_4F_9SO_3K becomes strong. When CO_2 is replaced by N_2, PDEAEMA·H~+ reverts to PDEAEMA, and the interaction becomes weak once again. It can therefore be concluded that the protonation/deprotonation process of the pentablock copolymer can be controlled by bubbling CO_2/N_2. The protonation/deprotonation process can "switch" the electrostatic attraction of PDEAEAM-b-F127-b-PDEAEMA to C_4F_9SO_3K, thereby tuning the hydrophilic-lipophilic balance(HLB) of the polymer-surfactant complex reversibly, leading to the reversible morphological transition of the aggregates. The strategy of CO_2-controllable morphological alteration of a polymer–surfactant complex opens a new avenue for preparing gas-sensitive soft materials.
引文
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(2)Goddard,E.D.Colloids Surf.1986,19,255.doi:10.1016/0166-6622(86)80340-7
(3)Goddard,E.D.Colloids Surf.1986,19,301.doi:10.1016/0166-6622(86)80341-9
(4)Chen,H.;Li,E.X.;Ye,Z.B.;Han,L.J.;Luo,P.Y.Acta Phys.-Chim.Sin.2011,27(3),671.[陈洪,李二晓,叶仲斌,韩利娟,罗平亚.物理化学学报,2011,27(3),671.]doi:10.3866/PKU.WHXB20110306
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(6)Chen,H.;Wu,X.Y.;Ye,Z.B.;Han,L.J.;Luo,P.Y.Acta Phys.-Chim.Sin.2012,28(6),903.[陈洪,吴晓艳,叶仲斌,韩利娟,罗平亚.物理化学学报,2012,28(6),903.]doi:10.3866/PKU.WHXB201202171
(7)Theato,P.;Sumerlin,B.S.;O'Reilly,R.K.;Epps,T.H.,III.Chem.Soc.Rev.2013,42,7055.doi:10.1039/c3cs90057f
(8)Liu,H.B.;Lin,S.J.;Feng,Y.J.;Theato,P.Polym.Chem.2017,8,12.doi:10.1039/c6py01101b
(9)Jessop,P.G.;Mercer,S.M.;Heldebrant,D.J.Energy Environ.Sci.2012,5,7240.doi:10.1039/c2ee02912j
(10)Darabi,A.;Jessop,P.G.;Cunningham,M.F.Chem.Soc.Rev.2016,45,4391.doi:10.1039/c5cs00873e
(11)Sha,K.;Li,D.S.;Li,Y.P.;Zhang,B.;Wang,J.Y.Macromolecules2008,41,361.doi:10.1021/ma0707234
(12)Xiong,X.Y.;Tam,K.C.;Gan,L.H.Macromolecules 2003,36,9979.doi:10.1021/ma035292d
(13)Xiong,X.Y.;Tam,K.C.;Gan,L.H.Macromolecules 2004,37,3425.doi:10.1021/ma049662p
(14)Agarwal,A.;Unfer,R.;Mallapragada,S.K.J.Controlled Release2005,103,245.doi:10.1016/j.jconrel.2004.11.022
(15)Determan,M.D.;Cox,J.P.;Seifert,S.;Thiyagarajan,P.;Mallapragada,S.K.Polymer 2005,46,6933.doi:10.1016/j.polymer.2005.05.138
(16)Xiong,X.Y.;Tam,K.C.;Gan,L.H.J.Appl.Polym.Sci.2006,100,4163.doi:10.1002/app.23470
(17)He,J.L.;Ni,P.H.;Liu,C.C.J.Polym.Sci.,Part A:Polym.Chem.2008,46,3029.doi:10.1002/pola.22641
(18)Abe,M.Curr.Opin.Colloid Interface Sci.1999,4,354.doi:10.1016/s1359-0294(99)90017-1
(19)Esumi,K.;Takehana,K.;Nojima,T.;Meguro,K.Colloids Surf.1992,64,15.doi:10.1016/0166-6622(92)80157-w
(20)Zhou,F.;Xie,M.X.;Chen,D.Y.Macromolecules 2014,47,365.doi:10.1021/ma401589z
(21)Gr?schel,A.H.;Walther,A.;L?bling,T.I.;Schmelz,J.;Hanisch,A.;Schmalz,H.;Müller,A.H.E.J.Am.Chem.Soc.2012,134,13850.doi:10.1021/ja305903u
(22)Wei,H.B.;Zhang,J.L.;Shi,N.;Liu,Y.;Zhang,B.;Zhang,J.;Wan,X.H.Chem.Sci.2015,6,7201.doi:10.1039/c5sc02020d
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(24)Liu,H.B.;Guo,Z.R.;He,S.;Yin,H.Y.;Fei,C.H.;Feng,Y.J.Polym.Chem.2014,5,4756.doi:10.1039/c4py00258j
(25)Wang,W.;Liu,H.B.;Mu,M.;Yin,H.Y.;Feng,Y.J.Polym.Chem.2015,6,2900.doi:10.1039/c5py00053j
(26)Li,S.;He,J.L.;Zhang,M.Z.;Wang,H.R.;Ni,P.H.Polym.Chem.2016,7,1773.doi:10.1039/c5py02017d
(27)Mac Knight,W.J.;Ponomarenko,E.A.;Tirrell,D.A.Acc.Chem.Res.1998,31,781.doi:10.1021/ar960309g
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(29)Zhang,L.;Qian,J.S.;Miao,J.B.;Xia,R.;Chen,P.;Cheng,G.J.Mater.Rev.2015,29(12),79.[张雷,钱家盛,苗继斌,夏茹,陈鹏,程国君.材料导报,2015,29(12),79.]doi:10.11896/j.issn.1005-023X.2015.12.018
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(31)Li,L.Y.;Raghupathi,K.;Song,C.F.;Prasad,P.;Thayumanavan,S.Chem.Commun.2014,50,13417.doi:10.1039/c4cc03688c