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

Borisova, O. V.; Billon, Laurent; Zaremski, M.b.; Grassl, Bruno; Bakaeva, Z.; Lapp, Alain; Štěpánek, Petr; Borisov, Oleg

doi:10.1039/c2sm25625h

Cited by 76 publications

(67 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…38 the incorporation of a fraction of AA monomer units into associating PS blocks leads to specific association behavior of these amphiphilic copolymers in aqueous solution. Micelle-like aggregates with spherical S-rich cores decorated by PAA coronae 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 The EQCM-D enabled us to study also the electro-responsive properties of the PAA and PAAb-P(AA-grad-S) brushes grafted from gold-coated surfaces.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

pH- and Electro-Responsive Properties of Poly(acrylic acid) and Poly(acrylic acid)-block-poly(acrylic acid-grad-styrene) Brushes Studied by Quartz Crystal Microbalance with Dissipation Monitoring

et al. 2015

Self Cite

View full text Add to dashboard Cite

We report on the synthesis of novel pH- and electro-responsive polyelectrolyte brushes from a gold substrate by direct one-step nitroxide-mediated polymerization of acrylic acid (AA) or copolymerization of AA and styrene (S). In the latter case, amphiphilic brushes of block-gradient copolymers PAA-b-(PAA-grad-PS) comprising one PAA block and one block with the gradient sequence of AA and S were obtained. The block-gradient copolymers are initiated from the surface by the start of the PAA block. The brushes were characterized by XPS and ellipsometry. (1)H NMR confirmed the gradient sequence of the PAA-grad-PS copolymer block. The pH- and electro-responsive properties of the brushes were studied by quartz crystal microbalance with dissipation monitoring (QCM-D) in combination with electrochemistry. This method provides evidence of swelling of the PAA brushes proportional to the contour length of the chains at elevated pH, whereas the response functions of the block-gradient copolymers are more complex and point to intermolecular aggregation in the brush at low pH. Monitoring of the changes in resonance frequency and dissipation of the QCM-D also demonstrates that application of negative voltage to the substrate leads to swelling of the brush; application of a positive voltage provokes only a transient collapse of the brush in proportion to the applied voltage.

show abstract

Section: Discussionmentioning

confidence: 99%

“…25,38,39 for synthesis of similar (co)polymers in the solution. The synthesis was performed in dioxane at 120°C in the presence of an initiator-coated gold surface and free alkoxyamine (MAMA).…”

Section: Surface-initiated Polymerizationmentioning

confidence: 99%

pH- and Electro-Responsive Properties of Poly(acrylic acid) and Poly(acrylic acid)-block-poly(acrylic acid-grad-styrene) Brushes Studied by Quartz Crystal Microbalance with Dissipation Monitoring

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…This is the result of the osmotic pressure exerted by the counter ions trapped in the corona by Coulombic interaction [23]. The stability of the micelles is ensured while the strong hydrophobicity of the core-forming PS overcomes the electrostatic repulsion between the PMAA chains [4]. With an increase in the concentration, the micelles start to interact and the viscosity increases sharply.…”

Section: Rheologymentioning

confidence: 99%

“…The possibility exists to introduce responsive behavior to parameters such as pH [3][4][5], temperature [6,7] or UV irradiation [2]. The versatility in properties has resulted in an increased attention in the last decades for application in several fields including smart materials [6,7], micro emulsion stabilization [8] and polymerization [9,10], coatings [11], drug delivery [12][13][14] and enhanced oil recovery [2,3,15,16].…”

Section: Introductionmentioning

confidence: 99%

Triblock copolymers of styrene and sodium methacrylate as smart materials: synthesis and rheological characterization

Meijerink

Mastrigt

Franken³

et al. 2017

Pure and Applied Chemistry

View full text Add to dashboard Cite

Well-defined amphiphilic triblock poly(sodium methacrylate)-polystyrene-poly(sodium methacrylate) (PMAA-b-PS-b-PMAA) copolymers characterized by a different length of either the hydrophilic or the hydrophobic block have been synthesized by ATRP. In solution the micelle-like aggregates consist of a collapsed PS core surrounded by stretched charged PMAA chains. The micelles are kinetically 'frozen' and as a consequence the triblock copolymers do not show a significant surface activity. The hydrophilic block length has a major influence on the rheology, the shortest PMAA blocks yielding the strongest gels (at the same total weight concentration). The hydrophobic block length has only a minor influence until a certain threshold, below which the hydrophobic interactions are too weak resulting in weak gels. A mathematical model is used to describe the micelle radius and the results were in good agreement with the experimentally found radius in transmission electron microscopy. The influences of the ionic strength, pH and temperature on the rheology has also been investigated, showing the potential of these polymers as smart hydrogels. The change in conformation of the hydrophilic corona from the collapsed state to the stretched state by changing the pH was quantified with zeta-potential measurements. To the best of our knowledge, this is the first systematic investigation of this kind of triblock copolymers in terms of their rheological behavior in water.

show abstract

“…One way to render these systems dynamic is to incorporate hydrophilic units within the hydrophobic blocks [28][29][30][31][32][33][34][35]. We have studied the effect of incorporating acrylic acid (AA) within the poly(n-butyl acrylate) B block of the triblock P(nBA-stat-AA)-b-PAA-b-P(nBA-stat-AA) [36][37][38][39].…”

Section: Introductionmentioning

confidence: 99%

Slow dynamics in transient polyelectrolyte hydrogels formed by self-assembly of block copolymers

et al. 2013

View full text Add to dashboard Cite

Transient polyelectrolyte hydrogels were formed by self-assembly of triblock copolyelectrolytes with a central hydrophilic block, poly(acrylic acid) (PAA), and two hydrophobic end blocks, poly(n-butyl acrylate(50%)-stat-acrylic acid(50%)) [P(nBA(50%)-stat-AA(50%))]. The relaxation of the concentration fluctuations was investigated by dynamic light scattering as a function of the concentration, the pH, the temperature, and the ionic strength. A relatively fast mode was observed at all polymer concentrations caused by cooperative diffusion of the polymers. Above the critical percolation concentration a second slow relaxation mode was observed caused by a linear displacement of small heterogeneities in the network with constant velocity. The relative amplitude of the slow mode was determined by the strength of the electrostatic repulsion. The velocity of the displacement in the transient network is shown to be directly correlated to the terminal relaxation time of the shear modulus and has the same Arrhenius temperature dependence. Both the velocity of the displacement and the mechanical relaxation strongly slow down with decreasing degree of ionization below 0.7 and increasing ionic strength above 0.5 M. A ballistic relaxation process has been reported earlier for colloidal gels, and the present study shows that it can also occur in polymeric networks.

show abstract

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

Cited by 76 publications

References 57 publications

pH- and Electro-Responsive Properties of Poly(acrylic acid) and Poly(acrylic acid)-block-poly(acrylic acid-grad-styrene) Brushes Studied by Quartz Crystal Microbalance with Dissipation Monitoring

pH- and Electro-Responsive Properties of Poly(acrylic acid) and Poly(acrylic acid)-block-poly(acrylic acid-grad-styrene) Brushes Studied by Quartz Crystal Microbalance with Dissipation Monitoring

Triblock copolymers of styrene and sodium methacrylate as smart materials: synthesis and rheological characterization

Slow dynamics in transient polyelectrolyte hydrogels formed by self-assembly of block copolymers

Contact Info

Product

Resources

About