Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

作者: Viet Hildebrand , André Laschewsky , Michael Päch , Peter Müller-Buschbaum , Christine M. Papadakis

DOI: 10.1039/C6PY01220E

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摘要: A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents zwitterionic group. Radical polymerisation via RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and well controlled, yielding polymers with predictable molar masses. Molar mass analysis control end-group fidelity were facilitated labeling a fluorescent dye. The showed distinct thermo-responsive behaviour UCST (upper critical solution temperature) type an aqueous solution, which could not be simply correlated to their molecular structure incremental hydrophilic hydrophobic elements incorporated within them. Increasing spacer length separating ammonium sulfonate groups zwitterion moiety from three four carbons increased phase transition temperatures markedly, whereas increasing group carboxylate ester on backbone two provoked opposite effect. Moreover, analogous polyzwitterions decreased order dimethylammonio > morpholinio piperidinio alkanesulfonates. In addition basic effect polymers’ precise structure, concentration dependence studied. Furthermore, we investigated influence added low salts aqueous-phase for sodium chloride bromide as sulfate. strong effects evolved complex way salt concentration. strength these depended nature anion added, sulfate < bromide, thus following empirical Hofmeister series. contrast, no significant differences observed when changing cation, i.e. adding or

参考文章(78)
Sarkyt Kudaibergenov, Werner Jaeger, Andre Laschewsky, Polymeric Betaines: Synthesis, Characterization, and Application Advances in Polymer Science. ,vol. 201, pp. 157- 224 ,(2006) , 10.1007/12_078
Peter Anton, André Laschewsky, POLYSOAPS VIA ALTERNATING OLEFIN/SO2 COPOLYMERS Die Makromolekulare Chemie, Rapid Communications. ,vol. 12, pp. 189- 196 ,(1991) , 10.1002/MARC.1991.030120307
Peter Köberle, André Laschewsky, Terence D. Lomax, Interactions of a zwitterionic polysoap and its cationic analog with inorganic salts Die Makromolekulare Chemie, Rapid Communications. ,vol. 12, pp. 427- 433 ,(1991) , 10.1002/MARC.1991.030120709
Malcolm B. Huglin, Mostafa A. Radwan, Properties of poly[N‐2‐(methyacryloyloxy)ethyl‐N,N‐dimethyl‐N‐3‐sulfopropylammonium betaine] in dilute solution Macromolecular Chemistry and Physics. ,vol. 192, pp. 2433- 2445 ,(1991) , 10.1002/MACP.1991.021921021
Hongbo Du, Xianghong Qian, The hydration properties of carboxybetaine zwitterion brushes Journal of Computational Chemistry. ,vol. 37, pp. 877- 885 ,(2016) , 10.1002/JCC.24234
Fei Wang, Jingfa Yang, Jiang Zhao, Understanding anti‐polyelectrolyte behavior of a well‐defined polyzwitterion at the single‐chain level Polymer International. ,vol. 64, pp. 999- 1005 ,(2015) , 10.1002/PI.4907
Tao Ye, Yihu Song, Qiang Zheng, Salt response and rheological behavior of acrylamide-sulfobetaine copolymer Colloid and Polymer Science. ,vol. 294, pp. 389- 397 ,(2016) , 10.1007/S00396-015-3790-6
Domenic Kratzer, Leonie Barner, Christian Friedmann, Stefan Bräse, Joerg Lahann, A Synthetic Route to Sulfobetaine Methacrylates with Varying Charge Distance European Journal of Organic Chemistry. ,vol. 2014, pp. 8064- 8071 ,(2014) , 10.1002/EJOC.201402734
V.M. Monroy Soto, J.C. Galin, Poly(sulphopropylbetaines): 1. Synthesis and characterization Polymer. ,vol. 25, pp. 121- 128 ,(1984) , 10.1016/0032-3861(84)90276-3
Michel Arotçaréna, Bettina Heise, Sultana Ishaya, André Laschewsky, Switching the Inside and the Outside of Aggregates of Water-Soluble Block Copolymers with Double Thermoresponsivity Journal of the American Chemical Society. ,vol. 124, pp. 3787- 3793 ,(2002) , 10.1021/JA012167D