期刊
REACTIVE & FUNCTIONAL POLYMERS
卷 73, 期 3, 页码 484-491出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/j.reactfunctpolym.2012.11.004
关键词
Poly(N-isopropylacrylamide); Aqueous ATRP; Kinetic study; Dilatometry; Diffusional limitations
资金
- European Commission and Region Wallonne FEDER Program (Materia Nova)
- OPTI2MAT program of excellence
- Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office [PAI 6/27]
- FNRS-FRFC
- Long Term Structural Methusalem
- Flemish Government
- European Commission [280813]
- FRIA
The controlled and fast atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAm) initiated by ethyl 2-chloropropionate (ECP) and catalyzed by copper chloride ligated with tris(2-dimethylarninoethyl)amine (CuCI.Me6TREN) is reported in water:DMF (1:1 volume based) for a broad range of polymerization conditions (targeted polymerization degree: 50-188; [NIPAm](0) = 0.5-2 M; T: 10-30 degrees C). For temperatures below 30 degrees C, a faster ATRP is obtained with decreasing temperature, which is explained by the exothermic formation of a pre-reactive complex during propagation. For sufficiently high initial deactivator concentrations (>= 20 mol%) a faster ATRP also results, which is proposed to be caused by Lewis acid-base interactions between the Cu(II) species and NIPAm. The kinetic study indicates a limited importance of cyclization reactions implying a limited loss of end-group fidelity. Moreover, for an initial NIPAm concentration of 2 M, catalyst disproportionation can be sufficiently suppressed. (C) 2012 Elsevier Ltd. All rights reserved.
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