Synthesis and pH- and salinity-controlled self-assembly of novel amphiphilic block-gradient copolymers of styrene and acrylic acid

被引:80
作者
Borisova, O. [1 ,2 ]
Billon, L. [1 ]
Zaremski, M. [2 ]
Grassl, B. [1 ]
Bakaeva, Z. [3 ]
Lapp, A. [4 ]
Stepanek, P. [3 ]
Borisov, O. [1 ]
机构
[1] CNRS UMR 5254 IPREM Equipe Phys & Chim Polymeres, UPPA, Pau, France
[2] Moscow MV Lomonosov State Univ, Dept Polymer Sci, Moscow 119191, Russia
[3] Inst Macromol Chem AS CR, Vvi, CZ-16206 Prague 6, Czech Republic
[4] Lab Leon Brillouin LLB CNRS CEA, Saclay, France
关键词
NITROXIDE-MEDIATED POLYMERIZATION; DIBLOCK COPOLYMERS; POLYISOBUTYLENE-BLOCK-POLY(METHACRYLIC ACID); RADICAL COPOLYMERIZATION; POLYELECTROLYTE BRUSHES; RAFT POLYMERIZATION; POLY(ACRYLIC ACID); NEUTRON-SCATTERING; MICELLE STRUCTURE; BUTYL ACRYLATE;
D O I
10.1039/c2sm25625h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A novel type of amphiphilic ionic copolymer comprising a hydrophilic poly(acrylic acid) (PAA) block and an amphiphilic poly(acrylic acid)-grad-poly(styrene) (PAA-grad-PS) copolymer block was synthesized using a one step direct nitroxide-mediated polymerization (NMP). A strong influence of the macroinitiator on the values of the reactivity ratios of the co-monomers is confirmed by H-1 NMR. The aggregation behaviour of the copolymers in the aqueous medium was studied by small-angle neutron scattering (SANS) and dynamic light scattering (DLS) and by transmission electron microscopy (TEM) in a wide range of pHs and ionic strengths. It has been demonstrated that PAA-b-(PAA-grad-PS) copolymers are soluble in alkaline water at room temperature without the special experimental procedures (addition of co-solvent, heating, etc.) that are usually required for solubilisation of classical PAA-b-PS diblock copolymers. The self-assembly of the PAA-b-(PAA-grad-PS) copolymers into nanoscale aggregates at low/moderate pH and/or high ionic strength was demonstrated by SANS and DLS experiments. The SANS spectra for the copolymer solution exhibit a correlation peak pointing to the formation of micelles with repulsive coronae. TEM images indicate that the micelles have an approximately spherical shape and exhibit a wide size distribution. Our results prove, that in contrast to "frozen" aggregates formed by PAA-b-PS copolymers in aqueous media, the micelles of PAA-b-(PAA-grad-PS) amphiphilic copolymers exhibit "dynamic" pH-responsive properties, i.e. they can reversibly change their aggregation number upon a variation in the pH or salinity of the solution.
引用
收藏
页码:7649 / 7659
页数:11
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