The effect of macromolecular structure on the rheology and surface properties of amphiphilic random polystyrene-<i>r</i>-poly(meth)acrylate copolymers prepared by RDRP

Migliore, Nicola; Picchioni, Francesco; Raffa, Patrizio

doi:10.1039/d0sm00153h

Cited by 8 publications

(6 citation statements)

References 45 publications

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“…The random copolymer R is remarkably more surface active, as shown in Figure , displaying a decrease of the surface tension up to 42 mN/m already at low polymer concentration values. These results are in line with that reported in the literature about the effect of the polymer architecture (random vs block copolymers) on surface tension …”

Section: Resultssupporting

confidence: 93%

“…These results are in line with that reported in the literature about the effect of the polymer architecture (random vs block copolymers) on surface tension. 53 As anticipated, we also carried out preliminary tests aimed at evaluating how the prepared polymers behave as emulsion stabilizers with three oils with different polarities (paraffin oil, isopropyl palmitate oil, and sunflower oil). For this reason, equal volumes of oil and aqueous polymer solutions at 5 mg/mL were put in contact in a graduated test tube and shaken vigorously, and emulsion formation was observed.…”

Section: Acs Sustainablementioning

confidence: 99%

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Lactic Acid-Derived Copolymeric Surfactants with Monomer Distribution Profile-Dependent Solution and Thermoresponsive Properties

Migliore

Guzik

Stuart

et al. 2022

ACS Sustainable Chem. Eng.

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We report the synthesis and solution properties of novel biobased thermoresponsive amphiphilic copolymers prepared using N,N-dimethyl lactamide acrylate (DMLA) and ethyl lactate acrylate (ELA) as hydrophilic and hydrophobic monomers, respectively. Copolymers with similar overall molecular weight but different monomer distribution profiles, such as random, diblock, triblock, and random−blocks, were prepared using photoinduced electron/energy transfer-reversible addition−fragmentation chain transfer (PET-RAFT) polymerization activated by a Zn-based photoredox catalyst. The synthesized polymers show interesting self-assembly and thermoresponsive behavior in water, depending on the monomers distribution along the chain. Different critical solution temperatures, in the range of 13−70 °C, were observed by tuning the monomers molar ratio and distribution. The formation of aggregates of various types was proven by transmission electron microscopy (TEM). The prepared polymers also display different surface activity with the fully random copolymer being significantly more surface active than block systems. A study of emulsion stabilization was performed with oils of various polarity, showing promising results for applications of these novel polymers as biobased surfactants and water/oil (w/o) emulsion stabilizers.

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Section: Resultssupporting

confidence: 93%

Section: Acs Sustainablementioning

confidence: 99%

Lactic Acid-Derived Copolymeric Surfactants with Monomer Distribution Profile-Dependent Solution and Thermoresponsive Properties

Migliore

Guzik

Stuart

et al. 2022

ACS Sustainable Chem. Eng.

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“…As the hydrophobicity increases, coil-to-globule transition and aggregation will start occurring (Figure 1d), resulting in complex structures and solution behavior. Highly hydrophobic PE with well-defined polymer architectures have been mostly studied experimentally by DLS, microscopy, rheology and surface tension measurements [19][20][21].…”

Section: Models Of Pe In Solutionmentioning

confidence: 99%

Interactions between an Associative Amphiphilic Block Polyelectrolyte and Surfactants in Water: Effect of Charge Type on Solution Properties and Aggregation

Raffa

2021

Polymers

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The study of interactions between polyelectrolytes (PE) and surfactants is of great interest for both fundamental and applied research. These mixtures can represent, for example, models of self-assembly and molecular organization in biological systems, but they are also relevant in industrial applications. Amphiphilic block polyelectrolytes represent an interesting class of PE, but their interactions with surfactants have not been extensively explored so far, most studies being restricted to non-associating PE. In this work, interactions between an anionic amphiphilic triblock polyelectrolyte and different types of surfactants bearing respectively negative, positive and no charge, are investigated via surface tension and solution rheology measurements for the first time. It is evidenced that the surfactants have different effects on viscosity and surface tension, depending on their charge type. Micellization of the surfactant is affected by the presence of the polymer in all cases; shear viscosity of polymer solutions decreases in presence of the same charge or nonionic surfactants, while the opposite charge surfactant causes precipitation. This study highlights the importance of the charge type, and the role of the associating hydrophobic block in the PE structure, on the solution behavior of the mixtures. Moreover, a possible interaction model is proposed, based on the obtained data.

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“…Highly hydrophobic PE with well-defined polymer architectures have been mostly studied experimentally by DLS, microscopy, rheology and surface tension measurements. [19][20][21] The distribution of hydrophobic groups and charges on the PE also plays a fundamental role in their solution behavior. [22,23] When hydrophobic and charged groups are completely segregated in block structures, formation of supra-molecular micellar aggregates will occur in solution.…”

Section: Models Of Pe In Solutionmentioning

confidence: 99%

Interactions Between an Associative Amphiphilic Block Polyelectrolyte and Surfactants in Water: Effect of Charge Type on Solution Properties and Aggregation

Raffa¹

2021

Preprint

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The study of interactions between polyelectrolytes (PE) and surfactants is of great interest for both fundamental and applied research. These mixtures can represent, for example, models of self-assembly and molecular organization in biological systems, but they are also relevant in industrial applications. Amphiphilic block polyelectrolytes represent an interesting class of PE, but their interactions with surfactants have not been extensively explored so far, most studies being restricted to non-associating PE. In this work, interactions between an anionic amphiphilic triblock polyelectrolyte and different types of surfactants bearing respectively negative, positive and no charge, are investigated via surface tension and solution rheology measurements for the first time. It is evidenced that the surfactants have different effects on viscosity and surface tension, depending on their charge type. Micellization of the surfactant is affected by the presence of the polymer in all cases; shear viscosity of polymer solutions decreases in presence of same charge or nonionic surfactants, while the opposite charge surfactant cause precipitation. This study highlights the importance of the charge type, and the role of the associating hydrophobic block in the PE structure, on the solution behavior of the mixtures. Moreover, a possible interaction model is proposed, based on the obtained data.

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The effect of macromolecular structure on the rheology and surface properties of amphiphilic random polystyrene-r-poly(meth)acrylate copolymers prepared by RDRP

Abstract: A systematic study of solution properties and micellization in water of amphiphilic random copolymers is presented for the first time.

Cited by 8 publications

References 45 publications

Lactic Acid-Derived Copolymeric Surfactants with Monomer Distribution Profile-Dependent Solution and Thermoresponsive Properties

Lactic Acid-Derived Copolymeric Surfactants with Monomer Distribution Profile-Dependent Solution and Thermoresponsive Properties

Interactions between an Associative Amphiphilic Block Polyelectrolyte and Surfactants in Water: Effect of Charge Type on Solution Properties and Aggregation

Interactions Between an Associative Amphiphilic Block Polyelectrolyte and Surfactants in Water: Effect of Charge Type on Solution Properties and Aggregation

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