ABC Supramolecular Triblock Copolymer by ROMP and ATRP

Diane S. Lye; Yan Xia; Madeleine Z. Wong; Yufeng Wang; Mu Ping Nieh; Marcus Weck

doi:10.1021/acs.macromol.7b00169

ABC Supramolecular Triblock Copolymer by ROMP and ATRP

Diane S. Lye, Yan Xia, Madeleine Z. Wong, Yufeng Wang, Mu Ping Nieh, Marcus Weck

Chemistry

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

Abstract

We report the controlled polymerization of three heterotelechelic polymers from supramolecular motif-bearing initiators, their assembly into supramolecular A/B/C triblock copolymers, the morphology of the resulting block copolymers, and their disassembly. The individual blocks are synthesized in a controlled or living fashion via ring-opening metathesis polymerization (ROMP) of norbornenes (block B) or atom-transfer radical polymerization (ATRP) of styrenes (block A) and methacrylates (block C). The building blocks are assembled via metal-coordination between blocks A and B using a palladated SCS pincer complex and pyridine, and hydrogen bonding between blocks B and C using Hamilton Wedge and barbituric acid derivatives. Scanning-transmission electron microscopy and small-angle X-ray scattering reveal lamellar domains of approximately 23, 15, and 21 nm for bulk samples of the A/B and B/C diblock copolymers and A/B/C triblock copolymers, with 1:1 and 1:1:1 block feed ratios, respectively. Nanoscale features are destroyed when the materials are exposed to dimethylformamide and/or triphenylphospine, removing noncovalent linkages between individual blocks.

Original language	English (US)
Pages (from-to)	4244-4255
Number of pages	12
Journal	Macromolecules
Volume	50
Issue number	11
DOIs	https://doi.org/10.1021/acs.macromol.7b00169
State	Published - Jun 13 2017

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.7b00169

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@article{a964f47e069c4345ac99e52e90917f7b,

title = "ABC Supramolecular Triblock Copolymer by ROMP and ATRP",

abstract = "We report the controlled polymerization of three heterotelechelic polymers from supramolecular motif-bearing initiators, their assembly into supramolecular A/B/C triblock copolymers, the morphology of the resulting block copolymers, and their disassembly. The individual blocks are synthesized in a controlled or living fashion via ring-opening metathesis polymerization (ROMP) of norbornenes (block B) or atom-transfer radical polymerization (ATRP) of styrenes (block A) and methacrylates (block C). The building blocks are assembled via metal-coordination between blocks A and B using a palladated SCS pincer complex and pyridine, and hydrogen bonding between blocks B and C using Hamilton Wedge and barbituric acid derivatives. Scanning-transmission electron microscopy and small-angle X-ray scattering reveal lamellar domains of approximately 23, 15, and 21 nm for bulk samples of the A/B and B/C diblock copolymers and A/B/C triblock copolymers, with 1:1 and 1:1:1 block feed ratios, respectively. Nanoscale features are destroyed when the materials are exposed to dimethylformamide and/or triphenylphospine, removing noncovalent linkages between individual blocks.",

author = "Lye, {Diane S.} and Yan Xia and Wong, {Madeleine Z.} and Yufeng Wang and Nieh, {Mu Ping} and Marcus Weck",

note = "Funding Information: This work was supported by the National Science Foundation under award number CHE-1506890. The authors thank Chris Petzold at the NYU Langone School of Medicine Microscopy Core for cryo- and room-temperature sample-sectioning, and Andrew D. Hollingsworth in NYU Department of Physics for assistance with the STEM instrument. The Bruker Avance 400, 500, and 600 MHz NMR spectrometers were acquired through support of the National Science Foundation (NSF, CHE- 01162222). Support from the Major Research Instrumentation (MRI) program of the National Science Foundation under Award No. DMR-0923251 enabled the purchase of the Zeiss field emission SEM. The Bruker NanoStar SAXS instrument was acquired through a NSF-MRI grant under Award No. NSFDMR 1228817. Y.X. is supported by NSF CBET-1510468. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = jun,

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doi = "10.1021/acs.macromol.7b00169",

language = "English (US)",

volume = "50",

pages = "4244--4255",

journal = "Macromolecules",

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T1 - ABC Supramolecular Triblock Copolymer by ROMP and ATRP

AU - Lye, Diane S.

AU - Xia, Yan

AU - Wong, Madeleine Z.

AU - Wang, Yufeng

AU - Nieh, Mu Ping

AU - Weck, Marcus

N1 - Funding Information: This work was supported by the National Science Foundation under award number CHE-1506890. The authors thank Chris Petzold at the NYU Langone School of Medicine Microscopy Core for cryo- and room-temperature sample-sectioning, and Andrew D. Hollingsworth in NYU Department of Physics for assistance with the STEM instrument. The Bruker Avance 400, 500, and 600 MHz NMR spectrometers were acquired through support of the National Science Foundation (NSF, CHE- 01162222). Support from the Major Research Instrumentation (MRI) program of the National Science Foundation under Award No. DMR-0923251 enabled the purchase of the Zeiss field emission SEM. The Bruker NanoStar SAXS instrument was acquired through a NSF-MRI grant under Award No. NSFDMR 1228817. Y.X. is supported by NSF CBET-1510468. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/6/13

Y1 - 2017/6/13

N2 - We report the controlled polymerization of three heterotelechelic polymers from supramolecular motif-bearing initiators, their assembly into supramolecular A/B/C triblock copolymers, the morphology of the resulting block copolymers, and their disassembly. The individual blocks are synthesized in a controlled or living fashion via ring-opening metathesis polymerization (ROMP) of norbornenes (block B) or atom-transfer radical polymerization (ATRP) of styrenes (block A) and methacrylates (block C). The building blocks are assembled via metal-coordination between blocks A and B using a palladated SCS pincer complex and pyridine, and hydrogen bonding between blocks B and C using Hamilton Wedge and barbituric acid derivatives. Scanning-transmission electron microscopy and small-angle X-ray scattering reveal lamellar domains of approximately 23, 15, and 21 nm for bulk samples of the A/B and B/C diblock copolymers and A/B/C triblock copolymers, with 1:1 and 1:1:1 block feed ratios, respectively. Nanoscale features are destroyed when the materials are exposed to dimethylformamide and/or triphenylphospine, removing noncovalent linkages between individual blocks.

AB - We report the controlled polymerization of three heterotelechelic polymers from supramolecular motif-bearing initiators, their assembly into supramolecular A/B/C triblock copolymers, the morphology of the resulting block copolymers, and their disassembly. The individual blocks are synthesized in a controlled or living fashion via ring-opening metathesis polymerization (ROMP) of norbornenes (block B) or atom-transfer radical polymerization (ATRP) of styrenes (block A) and methacrylates (block C). The building blocks are assembled via metal-coordination between blocks A and B using a palladated SCS pincer complex and pyridine, and hydrogen bonding between blocks B and C using Hamilton Wedge and barbituric acid derivatives. Scanning-transmission electron microscopy and small-angle X-ray scattering reveal lamellar domains of approximately 23, 15, and 21 nm for bulk samples of the A/B and B/C diblock copolymers and A/B/C triblock copolymers, with 1:1 and 1:1:1 block feed ratios, respectively. Nanoscale features are destroyed when the materials are exposed to dimethylformamide and/or triphenylphospine, removing noncovalent linkages between individual blocks.

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JO - Macromolecules

JF - Macromolecules

IS - 11

ER -

ABC Supramolecular Triblock Copolymer by ROMP and ATRP

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