Precision Polyelectrolytes with Phenylsulfonic Acid Branches at Every Five Carbons

Kendrick, Aaron; Neary, William J.; Delgado, Jose D.; Bohlmann, Michele; Kennemur, Justin G.

doi:10.1002/marc.201800145

Cited by 14 publications

(44 citation statements)

References 28 publications

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“…1,3,12 All of these are important factors we must consider when designing new polymeric PEMs. 13 This study focuses on a novel linear polyethylene with an atactic phenylsulfonic acid pendant group precisely spaced on every 5 th carbon, p5PhSA, Figure 1. This polymer was previously synthesized through ring-opening metathesis polymerization (ROMP) of 4phenylcyclopentene (4PCP), followed by mild hydrogenation of the backbone olefins (> 99%), and sulfonation of the phenyl rings (95%).…”

Section: Introductionmentioning

confidence: 99%

Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

et al. 2021

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Designing polymers with controlled nanoscale morphologies and scalable synthesis is of great interest in the development of fluorine-free materials for proton exchange membranes in fuel cells. This study focuses on a precision polyethylene with phenylsulfonic acid branches at every 5 th carbon, p5PhSA, with a high ion-exchange capacity (4.2 mmol/g). The polymers selfassemble into hydrophilic and hydrophobic co-continuous nanoscale domains. In the hydrated state, the hydrophilic domain, comprised of the polar sulfonic acid moieties and water, serves as a pathway for efficient mesoscopic proton conductivity. The morphology and proton transport of p5PhSA are evaluated under hydrated conditions using in situ X-ray scattering and electrochemical impedance spectroscopy techniques. At 40 °C and 95% relative humidity, the proton conductivity of p5PhSA is 0.28 S/cm, which is four times greater than Nafion™ 117 under the same conditions. Atomistic molecular dynamics (MD) simulations are also used to elucidate the interplay between the structure and the water dynamics. The MD simulations show strong nanophase separation between the percolated hydrophilic and hydrophobic domains over a wide range of water contents. The percolated hydrophilic nanoscale domain facilitates the rapid proton transport in p5PhSA and demonstrates the potential of precise hydrocarbon-based polymers as processible and effective proton exchange membranes.

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Section: Introductionmentioning

confidence: 99%

Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

et al. 2021

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“…Details of the synthesis of p 5PhS‐Li have been previously reported. [ 21 ] For the specific material reported herein, the parent polymer, p 5Ph, was determined to have a number averaged molar mass ( M n ) of 17 kg mol −1 and a dispersity ( Đ ) of 1.67 via size exclusion chromatography. Full synthesis and characterization details are provided in the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

“…In prior work, it was shown that the sulfonation and neutralization procedure is not deleterious to the molar mass and dispersity of the parent polymer. [ 21 ]…”

Section: Methodsmentioning

confidence: 99%

“…[ 20 ] Soon after, p 5Ph was successfully sulfonated (95% of repeating units) and neutralized with a variety of counter cations to produce a unique set of precision polyelectrolytes that feature the 5‐carbon charge spacing. [ 21 ] We envisioned that the increase in segmental mobility of these SICs, supplied by the lower T g of p 5Ph, would lead to an increase in ionic conductivity when compared to their PS counterparts.…”

Section: Introductionmentioning

confidence: 99%

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Ionic Transport and Thermodynamic Interaction in Precision Polymer Blend Electrolytes for Lithium Batteries

Kim

Nguyen

Marxsen

et al. 2021

Macro Chemistry & Physics

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Single-ion conducting polymer electrolytes are of interest for use with advanced battery electrodes such as lithium metal, but achieving sufficiently high conductivity has been challenging. In this work, a model system containing charged sites that are precisely spaced along the polymer backbone is explored. Precision sulfonated poly(4-phenylcyclopentene) lithium salt (p5PhS-Li) with a high degree of sulfonation (> 90%) is synthesized and blended with poly(ethylene oxide) (PEO) to investigate the thermodynamic and transport properties. Melting point depression is measured via differential scanning calorimetry, ionic conductivity, 𝜿, is determined using electrochemical impedance spectroscopy, and the fraction of current carried by Li + is estimated based on steady-state current measurements. In conjunction with a density measurement, melting point depression is used to find an effective Flory-Huggins interaction parameter, 𝝌 eff = − 0.21, suggesting miscibility of the blend. 𝜿 spans a large range from 2 × 10 −11 to 2 × 10 −7 S cm −1 over the composition and temperature range investigated. The fraction of charge carried by lithium ions also spans a significant range from 0.12 in majority PEO blend to 0.98 in majority p5PhS-Li blend. This study addresses several limitations of sulfonated polystyrene and opens up the possibility of precisely controlling the spacing of other anion types.

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“…Post-polymerization functionalization represents one approach to introduce charged moieties, ranging from statistical 16 to periodic 17 arrangements. Alternatively, statistical copolymerization of distinct charged and uncharged monomers remains a facile strategy to construct sequencepolydisperse designer polyelectrolytes.…”

Section: Introductionmentioning

confidence: 99%

Patterning Polyelectrolyte Complexes with Alternating Monomer Sequence Distributions

Herzog‐Arbeitman¹,

Ting

Meng³

et al. 2019

Preprint

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Charge-driven complexation of polyelectrolytes in water is a fundamental phase separation phenomenon that is prevalent in nature and across the high-value technology landscape.Condensed ionic biopolymers often rely on multiple non-covalent driving forces in patterned sequences to carefully preserve hierarchical structure and direct emerging function, and while synthetic polyelectrolyte complex (PEC) assemblies have sought to emulate and recapitulate such associative capabilities into applications, molecular engineering design strategies to precisely modulate monomeric building blocks remain vastly limited. Here we describe an experimentally convenient and versatile approach to construct patterned PECs, comprising well-defined charged macromolecules with both ionic styrene and neutral maleimide units alternating in the chain sequence. The controlled chemical structure of the alternating polyelectrolytes directly impacted the physical properties of bulk complex assemblies, demonstrated by elevated salt resistance and differences in viscoelastic relaxation and stiffness. Analogously, by engineering alternating diblock polyelectrolyte architectures for micelle self-assembly, the kinetic formation and stability pathways of PEC micelles were tailored without modifying nanoparticle size, attributed to the reduction in charge density and increased core hydrophobicity. We conclude by showing how multiple segments of donor/acceptor styrene-maleimide blocks can be incorporated into model polyelectrolyte chains in semi-batch reactions, enabling avenues to further explore sequencecontrolled polymers that regulate placement of N-substituted maleimides in polymer encryption endeavors. This unique copolymerization approach integrates appealing aspects of precision polymer synthesis with programmable self-assembly for advancing new directions in chemistry, physics, and engineering related to the complexation of oppositely-charged designer polymers.

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Precision Polyelectrolytes with Phenylsulfonic Acid Branches at Every Five Carbons

Cited by 14 publications

References 28 publications

Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

Fluorine-Free Precise Polymer Electrolyte for Efficient Proton Transport: Experiments and Simulations

Ionic Transport and Thermodynamic Interaction in Precision Polymer Blend Electrolytes for Lithium Batteries

Patterning Polyelectrolyte Complexes with Alternating Monomer Sequence Distributions

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