Synthesis of urea-containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties

Mingtao Chen; David L. Inglefield; Keren Zhang; Amanda G. Hudson; Samantha J. Talley; Robert B. Moore; Timothy E. Long

doi:10.1002/pola.29066

Synthesis of urea-containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties

Mingtao Chen, David L. Inglefield, Keren Zhang, Amanda G. Hudson, Samantha J. Talley, Robert B. Moore, Timothy E. Long

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

10 Scopus citations

Abstract

Reversible addition-fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2-(3-hexylureido)ethyl methacrylate-co-2-(3-phenylureido)ethyl methacrylate) (polyUrMA, 18-116 kg/mol). Copolymerization of 2-(3-hexylureido)ethyl methacrylate (HUrMA) and 2-(3-phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block T_g's from 69 to 134 °C. Tunable hard block T_g's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT-FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas.

Original language	English (US)
Pages (from-to)	1844-1852
Number of pages	9
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	56
Issue number	16
DOIs	https://doi.org/10.1002/pola.29066
State	Published - Aug 15 2018
Externally published	Yes

Keywords

block copolymers
hydrogen bonding dissociation
morphology
reversible addition-fragmentation chain transfer polymerization
urea

ASJC Scopus subject areas

Polymers and Plastics
Organic Chemistry
Materials Chemistry

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10.1002/pola.29066

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@article{da05a7b1f5054bb4a15a254d164cdfa8,

title = "Synthesis of urea-containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties",

abstract = "Reversible addition-fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2-(3-hexylureido)ethyl methacrylate-co-2-(3-phenylureido)ethyl methacrylate) (polyUrMA, 18-116 kg/mol). Copolymerization of 2-(3-hexylureido)ethyl methacrylate (HUrMA) and 2-(3-phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block Tg's from 69 to 134 °C. Tunable hard block Tg's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT-FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas.",

keywords = "block copolymers, hydrogen bonding dissociation, morphology, reversible addition-fragmentation chain transfer polymerization, urea",

author = "Mingtao Chen and Inglefield, {David L.} and Keren Zhang and Hudson, {Amanda G.} and Talley, {Samantha J.} and Moore, {Robert B.} and Long, {Timothy E.}",

note = "Funding Information: The authors acknowledge the Institute of Critical Technology and Applied Science (ICTAS) and ICTAS Nanoscale Characterization and Fabrication Laboratory (NCFL) at Virginia Tech for instrumental support (AFM and TEM). They also acknowledge Stephen McCartney and Christopher Winkler for training and performing AFM. They thank Dr Bruce Orler for help in the review of this manuscript. Publisher Copyright: {\textcopyright} 2018 Wiley Periodicals, Inc.",

year = "2018",

month = aug,

day = "15",

doi = "10.1002/pola.29066",

language = "English (US)",

volume = "56",

pages = "1844--1852",

journal = "Journal of Polymer Science, Part A: Polymer Chemistry",

issn = "0887-624X",

publisher = "John Wiley and Sons Inc.",

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T1 - Synthesis of urea-containing ABA triblock copolymers

T2 - Influence of pendant hydrogen bonding on morphology and thermomechanical properties

AU - Chen, Mingtao

AU - Inglefield, David L.

AU - Zhang, Keren

AU - Hudson, Amanda G.

AU - Talley, Samantha J.

AU - Moore, Robert B.

AU - Long, Timothy E.

N1 - Funding Information: The authors acknowledge the Institute of Critical Technology and Applied Science (ICTAS) and ICTAS Nanoscale Characterization and Fabrication Laboratory (NCFL) at Virginia Tech for instrumental support (AFM and TEM). They also acknowledge Stephen McCartney and Christopher Winkler for training and performing AFM. They thank Dr Bruce Orler for help in the review of this manuscript. Publisher Copyright: © 2018 Wiley Periodicals, Inc.

PY - 2018/8/15

Y1 - 2018/8/15

N2 - Reversible addition-fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2-(3-hexylureido)ethyl methacrylate-co-2-(3-phenylureido)ethyl methacrylate) (polyUrMA, 18-116 kg/mol). Copolymerization of 2-(3-hexylureido)ethyl methacrylate (HUrMA) and 2-(3-phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block Tg's from 69 to 134 °C. Tunable hard block Tg's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT-FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas.

AB - Reversible addition-fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2-(3-hexylureido)ethyl methacrylate-co-2-(3-phenylureido)ethyl methacrylate) (polyUrMA, 18-116 kg/mol). Copolymerization of 2-(3-hexylureido)ethyl methacrylate (HUrMA) and 2-(3-phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block Tg's from 69 to 134 °C. Tunable hard block Tg's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT-FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas.

KW - block copolymers

KW - hydrogen bonding dissociation

KW - morphology

KW - reversible addition-fragmentation chain transfer polymerization

KW - urea

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JO - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

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ER -

Synthesis of urea-containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties

Abstract

Keywords

ASJC Scopus subject areas

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