Hydrogels of Amphiphilic Triblock Copolymers with Independently Tunable pH and Temperature-Controlled Exchange Dynamics

Coudert, Noémie; Debrie, Clément; Harrisson, Simon; Rieger, Jutta; Nicolai, Taco; Colombani, Olivier

doi:10.1021/acs.macromol.3c01448

Cited by 3 publications

(3 citation statements)

References 50 publications

(116 reference statements)

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“…Indeed, a change in F AA , α and composition profile should alter the packing parameter, which may alter the morphology from a thermodynamic point of view. 28,47,48 Simultaneously, addition of AA units within hydrophobic blocks and variation of their ionization should alter the exchange rate of unimers, 31–33,49 which may favour morphological transitions from a kinetic point of view. At this stage, it is not possible to determine whether thermodynamics, kinetics or both explain our observations.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, we have previously demonstrated that P(MEA- co -AA) statistical copolymers are thermoresponsive and exhibit a LCST-type temperature transition that depends on pH. 20,49 We therefore studied post-polymerization the impact of α and temperature ( T ) on representative samples with different morphologies, molar content of AA ( F AA ) and DP n , B .…”

Section: Resultsmentioning

confidence: 99%

“…This quasi-reversible responsiveness might be understood by the fact that this sample has the shortest B block and the highest molar fraction of AA, which might lead to thermodynamically controlled assemblies. 33,34,49…”

Section: Resultsmentioning

confidence: 99%

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Single-Component Cellulose Acetate Sulfate Hydrogels for Direct Ink Writing 3D Printing

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Hydrogels, typically favored for 3D printing due to their viscoelasticity, are now trending toward ecofriendly alternatives amid growing environmental concerns. In this study, we crafted cellulose-based hydrogels, specifically employing cellulose acetate sulfate (CAS). By keeping the acetyl group substitution degree (DS acetyl = 1.8) and CAS molecular weight constant, we varied rheological properties by adjusting sulfate group substitution (DS sulfate = 0.4, 0.7, and 1.0) and CAS concentration (2−5 wt %). Rheological characterizations, including shear-thinning, yield stress, and thixotropy, were performed to identify optimal conditions for formulating CAS hydrogel ink in direct ink writing for 3D printing under selected experimental conditions. Based on rheological findings, CAS hydrogels with DS sulfate 0.7 and concentration of 4 wt % was used for 3D printing, with subsequent evaluation of printing metrics. Additionally, the effect of ionic cross-linking using Ca 2+ ions on the structural integrity of 3D-printed structures was evaluated, demonstrating effective preservation through reinforced polymer networks. The shrinking and swelling behaviors of the 3D-printed structures were also significantly affected by this ionic cross-linking. Building on these findings, this work could broaden the range of cellulose derivatives available for the preparation of cellulose-based hydrogels for 3D printing.

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Controlling the Composition Profile of Acrylic Acid Copolymers by Tuning the pH of Polymerization in Aqueous Dispersed Media

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et al. 2023

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In radical copolymerization, the intrinsic reactivity of acrylic acid (AA) with a comonomer is dependent on its degree of ionization (αAA). Furthermore, when monomers of different solubilities are copolymerized in a heterogeneous process, differences in partitioning between the continuous and discrete phases can result in apparent reactivity ratios that strongly differ from the intrinsic reactivity ratio observed in homogeneous solution. We demonstrate that this combination of chemical and physical contributions to the reactivity ratios of AA can be used to control the composition profile of acrylic acid copolymers in RAFT-controlled aqueous heterogeneous polymerization. Specifically, RAFT-mediated copolymerizations of acrylic acid (AA) with comonomers of varying hydrophobicity were performed in water at different αAA = 0 to 1 using a novel, water-soluble, sulfonate-functionalized trithiocarbonate chain transfer agent. A moderate decrease in the reactivity of AA with increasing αAA was observed under homogeneous conditions when AA was copolymerized with oligoethylene glycol acrylate (OEGA). A much greater change in apparent reactivity with increasing αAA was observed with the more hydrophobic comonomers 2-methoxyethyl acrylate (MEA) and methyl acrylate (MA). This was attributed to the partitioning of AA between the dispersed and continuous phases of these heterogeneous copolymerizations. Changing the pH of the reaction mixture thus allowed the synthesis of P(MEA-co-AA) and P(MA-co-AA) copolymers with very different composition profiles. In addition, when αAA was changed in situ, block-like copolymers with similar overall AA content but different composition profiles were obtained. These differences in composition profile strongly impacted their thermoresponsiveness in water.

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Hydrogels of Amphiphilic Triblock Copolymers with Independently Tunable pH and Temperature-Controlled Exchange Dynamics

Cited by 3 publications

References 50 publications

Effect of pH on the incorporation of acrylic acid units in the core of polymer nanoparticles prepared by PISA and on their morphology

Effect of pH on the incorporation of acrylic acid units in the core of polymer nanoparticles prepared by PISA and on their morphology

Single-Component Cellulose Acetate Sulfate Hydrogels for Direct Ink Writing 3D Printing

Controlling the Composition Profile of Acrylic Acid Copolymers by Tuning the pH of Polymerization in Aqueous Dispersed Media

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