Assembly of miscible supramolecular network blends using DDA·AAD hydrogen-bonding interactions of pendent side-chains

Coubrough, Heather M.; Reynolds, Matthew; Goodchild, James A.; Connell, Simon D.; Mattsson, Johan; Wilson, Andrew J.

doi:10.1039/c9py01913h

Cited by 4 publications

(2 citation statements)

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“…62 Furthermore, in hydrogenbonded polymer blends, the strength of H-bonding dictated by polymer chemistries also affects the blend miscibility, structure, and properties. For example, Wilson and co-workers showed that copolymer blends consisting of poly(methyl methacrylate) (PMMA) and polystyrene (PS) functionalized with high-affinity H-bonding motifs ureidoimidazole (UIM) and amidoisocytosine (AIC), respectively, 63 formed miscible supramolecular networks at a lower molar ratio of functionalized comonomers compared to PMMA and PS blends functionalized with low-affinity H-bonding motifs phenylureidopyrimidine (PUPY) and diamidopyridine (DAP), respectively. 64 Similarly, previous work focused on binary blends with the same hydrogen-bond-accepting polymer chemistry (poly(N-acryloyl piperidine) (PAP)) but different hydrogen-bond-donating polymers, namely, (poly(acrylic acid) (PAA), poly(vinyl alcohol) (PVA), or poly(4-vinyl phenol) (PVPh)), showed that the linker group chemistry dictated the donating strength of the −OH donor group and the distribution of hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Impact of Composition and Placement of Hydrogen-Bonding Groups along Polymer Chains on Blend Phase Behavior: Coarse-Grained Molecular Dynamics Simulation Study

2022

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In this paper, we study symmetric polymer blends comprised of two polymer chemistries, one containing hydrogenbonding (H-bonding) acceptor groups and another containing Hbonding donor groups to predict the blend morphology (i.e., twophase, ordered/lamellar, disordered, disordered microphase-separated, and bicontinuous microemulsion or BμE) for varying compositions (i.e., fraction of monomers containing hydrogenbonding groups along the polymer chain) and placements of hydrogen-bonding groups along the polymer chains. We use molecular dynamics (MD) simulations with a previously developed coarse-grained (CG) model that captures relevant macromolecular length and time scales and both the attractive directional interactions between H-bonding acceptor and donor groups and isotropic polymer−polymer interactions. We first validate our CG MD simulation approach by reproducing the published theoretical phase diagram for end-associating polymer chains at varying Hbonding strengths vs polymer segregation strengths. We also show that with increasing H-bonding strength, end-associating blends with short-chain lengths transition from two-phase to BμE or from disordered blends to BμE depending on the polymer segregation strength and finally to disordered microphase morphologies. End-associating blends with longer-chain lengths transition from twophase to ordered lamellar phase at high polymer segregation strengths and from two-phase to disordered microphase-separated state at low polymer segregation strengths. Next, we study blends with the center placement of a single H-bonding group in each polymer chain as well as random and regular placements of multiple H-bonding groups per polymer chain. Regardless of the number and placement of H-bonding groups, with increasing H-bonding strength, the fraction of associated H-bonding groups increases with the system transitioning from blends of unassociated polymers to a mixture of associated copolymers and unassociated polymers and finally to a melt of fully associated supramolecular copolymers. At intermediate strengths of H-bonding, we observe BμE morphologies in all systems with end, center, random, and regular placements of H-bonding group(s). At high strengths of Hbonding, the blend morphology is disordered microphase-separated with domain sizes being smallest for the center placement, followed by the end, regular, and then random placements. We find that this variation in the placement of H-bonding groups leads to a greater change in domain sizes than with variation in the strength of the isotropic polymer−polymer interaction at constant Hbonding attraction. These trends in disordered microphase domain sizes with varying compositions and placements of H-bonding groups are linked to the supramolecular copolymer architecture formed upon the association of the two homopolymer chemistries. The polymers with the center placement of H-bonding groups form miktoarm star copolymers upon association, which show smaller domain sizes compared to diblock copolymers formed by polymers with end p...

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Section: Introductionmentioning

confidence: 99%

Impact of Composition and Placement of Hydrogen-Bonding Groups along Polymer Chains on Blend Phase Behavior: Coarse-Grained Molecular Dynamics Simulation Study

2022

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“…Herein, the strongly dimerizing UPy groups complemented with lateral stacking of urea moieties , and high glass transition temperatures ( T g ) of polynorbornene ensured the formation of stable, intramolecularly crosslinked nanoparticles. Weak hydrogen bonding motifs, − in contrast, exhibit fast exchange dynamics, resulting in higher probabilities of intermolecular crosslinking, and are therefore less suitable for this processing approach . The solvent generally plays a crucial role in this process as strong hydrogen bonding complexes should be formed while at the same time interparticle aggregation should be prevented.…”

Section: Introductionmentioning

confidence: 99%

Controlling the Processability and Stability of Supramolecular Polymers Using the Interplay of Intra- and Intermolecular Interactions

et al. 2022

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Polymer networks crosslinked via non-covalent interactions afford interesting materials for a wide range of applications due to their self-healing capability, recyclability, and tunable material properties. However, when strong non-covalent binding motifs in combination with high crosslink density are used, processing of the materials becomes troublesome because of high viscosities and the formation of insoluble gels. Here, we present an approach to control the processability of grafted polymers containing strong non-covalent interactions by balancing the interplay of intra- and intermolecular hydrogen bonding. A library of copolymers with different degrees of polymerization and content of protected ureido-pyrimidinone-urea (UPy-urea) grafts was prepared. Photo-deprotection in a good solvent like tetrahydrofuran (THF) at low concentrations (≤1 mg mL –1 ) created intramolecularly assembled nanoparticles. Remarkably, the intrinsic viscosity of these nanoparticle solutions was an order of magnitude lower compared to solutions of the intermolecularly assembled analogues, highlighting the crucial role of intra- versus intermolecular interactions. Due to the strong hydrogen bonds between UPy dimers, the intramolecularly assembled structures were kinetically trapped. As a result, the polymer nanoparticles were readily processed into a bulk material, without causing major changes in the morphology as verified by atomic force microscopy. Subsequent intermolecular crosslinking of the nanoparticle film, by heating to temperatures where the hydrogen-bond exchange becomes fast, resulted in a crosslinked network. The reversibility of the hereby obtained polymer networks was shown by retrieving the intramolecularly assembled nanoparticles via redissolution and sonication of the intermolecularly crosslinked film in THF with a small amount of acid. Our results highlight that the stability and processability of highly supramolecularly crosslinked polymers can be controlled both in solution and in bulk by using the interplay of intra- and intermolecular non-covalent interactions in grafted polymers.

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Evaluation of degradation kinetic and photostability of immobilized TiO2/activated carbon bilayer photocatalyst for phenol removal

Bahrudin

2022

Applied Surface Science Advances

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Assembly of miscible supramolecular network blends using DDA·AAD hydrogen-bonding interactions of pendent side-chains

Abstract: Miscible blends of poly(methyl methacrylate) and polystyrene polymers are assembled through triple hydrogen bonding between complementary ureidoimidazole and amidoisocytosine heterodimers.

Cited by 4 publications

References 61 publications

Impact of Composition and Placement of Hydrogen-Bonding Groups along Polymer Chains on Blend Phase Behavior: Coarse-Grained Molecular Dynamics Simulation Study

Impact of Composition and Placement of Hydrogen-Bonding Groups along Polymer Chains on Blend Phase Behavior: Coarse-Grained Molecular Dynamics Simulation Study

Controlling the Processability and Stability of Supramolecular Polymers Using the Interplay of Intra- and Intermolecular Interactions

Evaluation of degradation kinetic and photostability of immobilized TiO2/activated carbon bilayer photocatalyst for phenol removal

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