Synthesis and self-assembly of temperature and anion double responsive ionic liquid block copolymers

doi:10.1007/s11706-015-0301-0

Front. Mater. Sci.

2015, Vol. 9

Issue (3) : 254-263 https://doi.org/10.1007/s11706-015-0301-0

RESEARCH ARTICLE

Synthesis and self-assembly of temperature and anion double responsive ionic liquid block copolymers

Ju LIANG¹,Wenlan WU²,Junbo LI^1,^*(

),Chen HAN¹,Shijie ZHANG¹,Jinwu GUO¹,Huiyun ZHOU¹

1. College of Chemical Engineering & Pharmaceutics, Henan University of Science & Technology, Luoyang 471023, China
2. Medical School, Henan University of Science & Technology, Luoyang 471003, China

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Abstract

In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly(N-isopropylacrylamide)-block-poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)] (PNIPAM-b-PMMPImB), were polymerized by two-step reversible addition-fragmentation chain transfer (RAFT) process. The?composition and molecular weight distributions of ILBCs were characterized using ¹HNMR and gel permeation chromatography (GPC). The self-assembly and temperature- and anion-responsive behaviors of ILBCs were investigated by UV-Vis spectroscopy, TEM and dynamic light scattering (DLS). With increasing the concentration of (CF₃SO₂)₂N^--, the micellization of self-assembling PNIPAM-b-PMMPImB was induced to form a core--shell structure containing the core with hydrophilic PMMPIm-(CF₃SO₂)₂N^-- surrounded by the shell of PNIPAM via the anion-responsive properties of ILBCs. However, upon temperature increasing, PNIPAM-b-PMMPImB formed the micelles composing of PNIPAM core and PMMPImB shell. The ionic liquid segment with strong hydrophilic property enhanced the hydrogen bonding interaction which expanded the temperature range of phase transition and increased the lower critical solution temperature (LCST) of the system. These results indicate that ILBCs prepared in this paper have excellent temperature and anion double responsive properties, and may be applied as a kind of potential environmental responsive polymer nanoparticles.

Keywords ionic liquid block copolymer (ILBC) self-assembly micelles stimulus-responsive polymer nanoparticle

Corresponding Author(s): Junbo LI

Online First Date: 11 June 2015 Issue Date: 23 July 2015

Cite this article:

Ju LIANG,Wenlan WU,Junbo LI, et al. Synthesis and self-assembly of temperature and anion double responsive ionic liquid block copolymers[J]. Front. Mater. Sci., 2015, 9(3): 254-263.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-015-0301-0
https://academic.hep.com.cn/foms/EN/Y2015/V9/I3/254

Fig.1 Scheme 1 Schematic representation for synthesis of PNIPAM-CTA and PNIPAM-b-PMMPImB.

Fig.2 ¹HNMR spectra of PNIPAM-CTA (A) in CDCl₃ and PNIPAM-b-PMMPImB (B) in DMSO.

Fig.3 GPC traces of PNIPAM in DMF (A) and PNIPAM-b-PMMPImB (B) in 8.5 g/L NaNO₃ aqueous solution at room temperature.

Fig.4 Scheme 2 Schematic illustration of temperature- and anion-responsive process of ILBCs.

Fig.5 The response of transmittance as a function of the concentration of (CF₃SO₂)₂N^-.

Fig.6 ¹HNMR spectra of the following: micelle of PNIPAM-b-PMMPImB by adding (CF₃SO₂)₂N^- (1/8 MR of (CF₃SO₂)₂N^- to MMPImB) in D₂O (A); micelle of PNIPAM-b-PMMPImB by adding (CF₃SO₂)₂N^- (1/4 MR of (CF₃SO₂)₂N^- to MMPImB) in D₂O (B); micelle of PNIPAM-b-PMMPImB by adding (CF₃SO₂)₂N^- (1/2 MR of (CF₃SO₂)₂N^- to MMPImB) in D₂O (C).

Fig.7 (a) DLS result and (b) TEM image of the hybrid micelles solution forming at the ratio of (CF₃SO₂)₂N^- to PMMPImB at 1/2, the inset indicating the local enlarged image of (b).

Fig.8 Temperature dependence of the transmittance at 500 nm in PNIPAM-CTA and PNIPAM-b-PMMPImB aqueous solutions.

Fig.9 DLS results of (a) PNIPAM-b-PMMPImB and (b) PNIPAM-CTA, and TEM images of (c) PNIPAM-b-PMMPImB and (d) PNIPAM-CTA at 45°C.

Fig.10 Response of transmittance with the change of temperature of PNIPAM-b-PMMPIm-(CF₃SO₂)₂N^- micelles.

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