Co-assembly of precision polyurethane ionomers reveals role of and interplay between individual components

Timmers, Elizabeth M.; Fransen, Peter; García, Álvaro González; Schoenmakers, Sandra M. C.; Magana, José Rodrigo; Peeters, Joris W.; Tennebroek, Ronald; Casteren, Ilse van der Hoeven‐van; Tuinier, Remco; Janssen, Henk M.; Voets, Ilja K.

doi:10.1039/d1py00079a

Cited by 5 publications

(2 citation statements)

References 24 publications

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“…[2,[24][25][26][27][28] The lack of control over PU molar mass and architecture renders difficult their precise study and comprehension of properties. [29][30][31] The alternative used so far to overcome these secondary reactions is to conduct the polymerization at low temperatures (≤60 °C) with anhydrous aprotic solvents. [10,23,26,[32][33][34][35][36][37] However, this strategy increases the environmental impact as well as the labor required for PU synthesis for advanced applications.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐Ð Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control

Fonseca

2022

Macro Chemistry & Physics

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Dynamic urea bond-mediated polymerization (DUBMP) has been employed for the synthesis of linear, branched, telechelic, and random-block polyurethanes (PUs) with low molar-mass dispersity relative to conventionally synthesized PUs (Ð < 1.5). However, the reason for the improved control of the molar mass and reduction in dispersity, promoted by DUBMP, has not been explained. In this paper, the DUBMP synthesis of linear PU based on low-molar-mass poly(ethylene glycol) (PEG) and isophorone diisocyanate is studied comprehensively. The lower viscosity of the PEG-based PU allows DUBMP to reach high conversions (≈0.97) for the first time, while molar mass and Ð vary substantially with reaction conditions, despite yielding similar/equal conversion values. Both molar mass and Ð increase with an increase in reaction temperature, or with a reduction of the amine/isocyanate molar ratio. Therefore, evidence suggests that DUBMP provides diffusion control due to the lower mobility of the longer chains associated with an isocyanate-deactivator-rich environment. An increase in the reaction temperature, and/or a decrease in the amine/isocyanate molar ratio, reduces the diffusion control, leading to higher Ð values and molar mass. Tuning of the reaction conditions allows obtaining PU of controlled molar mass (11 kDa ≤ M w ≤ 42 kDa) and 1.3 < Ð < 1.75.

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Section: Introductionmentioning

confidence: 99%

Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐Ð Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control

Fonseca

2022

Macro Chemistry & Physics

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“…For example, monodisperse (discrete) materials have been synthesized directly via stepwise iterative coupling and, recently, isolated in large quantities from disperse mixtures with automated column chromatography 4–12 . Utilizing these methods, many research groups have reported scalable and versatile control of polymer dispersity and molar mass distribution, yielding previously unknown length‐dependent properties and providing invaluable fundamental insights 9–19 . For example, Meijer and coworkers showed that discrete ABA‐type amphiphilic triblock co‐oligomers self‐assemble in water with higher structural regularity (nanofibers/2D sheets) and crystallinity than their disperse counterparts 16 .…”

Section: Introductionmentioning

confidence: 99%

Elucidating the impact of side chain dispersity on the assembly of bottlebrush polymers at the air‐water interface

Ogbonna

Dearman

Bharti

et al. 2021

Journal of Polymer Science

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The synthesis of bottlebrush polymers with discrete side chains, their surface pressure isotherm measurements, and thin film molecular dynamics simulations are reported. Our results show that monolayers of bottlebrushes with discrete side chains achieve higher packing densities and exhibit previously unknown, distinct phase transitions that are unseen in their disperse counterparts. The combination of experimental findings and simulation results show that shape‐defined bottlebrush polymers can advance structure–property relationship studies of branched polymers and the theoretical descriptions of polymer monolayer self‐assembly.

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From nano to the macro: tuning hierarchical aggregation of thermoresponsive PEG/PCL-based polyurethanes via molar mass/composition control

Fonseca

2023

Macromol. Res.

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Amphiphilic hyperbranched polyurethanes (HPUs) based on PEG and PCL are promising for several biomedical applications. However, the lack of control over the molar mass and composition hinders a deep understanding of the aqueous self-assembly of HPUs. In this paper, the control over the HPU molar mass and composition was provided by dynamic urea bond-mediated polymerization (DUBMP), enabling a careful evaluation of their aqueous self-assembly by 1H NMR, DLS, and Cryo-TEM. HPUs containing a single PCL block per chain self-assemble into nanoaggregates (Rh ≈ 10 nm) in water up to its cloud-point temperature (Tcp) of 34 °C. On the other hand, HPUs with more than one PCL block per chain self-assemble into nanoaggregates and their clusters below Tcp. In this case, the solution behavior can be tuned by the HPU molar mass. Increasing $$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ from 4 to 19 kDa, HPUs of similar composition can form colloidally stable cluster suspensions ($$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 4 kDa) and phase separate into a denser liquid aggregate–cluster phase ($$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 7 kDa) or into a highly viscous aggregate-network phase ($$\overline{{\mathrm{M} }_{\mathrm{w}}}$$ M w ¯ = 19 kDa). This type of control over the hierarchical aggregation of HPUs was reported for the first time and is interesting for biomedical applications. Graphical abstract

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Co-assembly of precision polyurethane ionomers reveals role of and interplay between individual components

Abstract: Industrial and household products, such as paints, inks and cosmetics usually consist of mixtures of macromolecules that are disperse in composition, in size and in monomer sequence. Identifying structure-function relationships...

Cited by 5 publications

References 24 publications

Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐Ð Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control

Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐Ð Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control

Elucidating the impact of side chain dispersity on the assembly of bottlebrush polymers at the air‐water interface

From nano to the macro: tuning hierarchical aggregation of thermoresponsive PEG/PCL-based polyurethanes via molar mass/composition control

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