a Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Polym. Chem. 2014, 5, 4115-4123
We report facile synthesis, sequence-tuned thermoresponsive behaviours and reaction-induced reorganization of ketone-based hydrophilic reactive polymers. The well-controlled and living RAFT polymerisation of commercially-available diacetone acrylamide (DAAM), in methanol media on irradiation with visible light at 25 °C, leads to well-defined keto-polymers over wide degrees of polymerisation from 50–1000 and a block copolymer with poly(N,N-dimethyl acrylamide) (PDMA). Statistical copolymerisation with DMA gives a gradient copolymer, P(DAAM-grad-DMA), whose aqueous solubility can be finely tuned. Binary copolymers that have the tailored structures of PDMA-b-P(DAAM-grad-DMA) can be achieved via a one-pot iterative process. Aqueous solutions of the P(DAAM-grad-DMA) copolymers exhibit typical thermoresponsive behaviours on heating, with cloud points that can be widely tuned from 16 °C to permanently water-soluble. Adjusting the sequence from gradient, “short-block”-gradient, “middle-block”-gradient, “long-block”-gradient to block structures can induce diversity in the dehydration, heating-triggered phase transition, assembly and reaction-induced dynamic reorganization. These water-soluble reactive keto-polymers are thus promising for emerging biological applications on demand in physiological aqueous solution.
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//pubs.rsc.org/en/content/articlelanding/2014/py/c4py00146j#!divAbstract