Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Philip J. Scott; Glenn A. Spiering; Yangyang Wang; Zach D. Seibers; Robert B. Moore; Rajeev Kumar; Bradley S. Lokitz; Timothy E. Long

doi:10.1021/acs.macromol.0c02166

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

Philip J. Scott, Glenn A. Spiering, Yangyang Wang, Zach D. Seibers, Robert B. Moore, Rajeev Kumar, Bradley S. Lokitz, Timothy E. Long

Molecular Sciences, School of (SMS)

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

This manuscript describes a synthetic strategy and structure-property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (Tg) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in Tg and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

Original language	English (US)
Pages (from-to)	11009-11018
Number of pages	10
Journal	Macromolecules
Volume	53
Issue number	24
DOIs	https://doi.org/10.1021/acs.macromol.0c02166
State	Published - Dec 22 2020

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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@article{363db6a46f51472da862d8526b6b5b75,

title = "Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties",

abstract = "This manuscript describes a synthetic strategy and structure-property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (Tg) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in Tg and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.",

author = "Scott, {Philip J.} and Spiering, {Glenn A.} and Yangyang Wang and Seibers, {Zach D.} and Moore, {Robert B.} and Rajeev Kumar and Lokitz, {Bradley S.} and Long, {Timothy E.}",

note = "Funding Information: A portion of this research related to synthesis, BDS, and data analysis was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility at Oak Ridge National Laboratory. This is also based upon work supported by the National Science Foundation under Grant No. DMR-1809291. The authors also thank Dr. Mingtao Chen for helpful discussions and his expertise with ionomers and polyionic liquids. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = dec,

day = "22",

doi = "10.1021/acs.macromol.0c02166",

language = "English (US)",

volume = "53",

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T2 - Influence of Ionic Structure and Association on Mechanical Properties

AU - Scott, Philip J.

AU - Spiering, Glenn A.

AU - Wang, Yangyang

AU - Seibers, Zach D.

AU - Moore, Robert B.

AU - Kumar, Rajeev

AU - Lokitz, Bradley S.

AU - Long, Timothy E.

N1 - Funding Information: A portion of this research related to synthesis, BDS, and data analysis was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility at Oak Ridge National Laboratory. This is also based upon work supported by the National Science Foundation under Grant No. DMR-1809291. The authors also thank Dr. Mingtao Chen for helpful discussions and his expertise with ionomers and polyionic liquids. Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/12/22

Y1 - 2020/12/22

N2 - This manuscript describes a synthetic strategy and structure-property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (Tg) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in Tg and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

AB - This manuscript describes a synthetic strategy and structure-property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (Tg) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in Tg and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

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ER -

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

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