Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation

Goliath Beniah; William H. Heath; John M. Torkelson

doi:10.1002/pola.28722

Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation

Goliath Beniah, William H. Heath, John M. Torkelson^*

^*Corresponding author for this work

Chemical and Biological Engineering

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

17 Scopus citations

Abstract

The properties of segmented, nanophase-separated polyhydroxyurethane (PHUs) were investigated before and after hydroxyl group functionalization. Segmented PHU was synthesized using polytetramethylene oxide (PTMO)-based soft segment, divinylbenzene dicyclocarbonate (DVBDCC) as hard segment, and p-xylylene diamine as chain extender at 40 wt% hard-segment content. The pendant hydroxyl groups were subsequently functionalized with benzoyl chloride, and the properties of PHUs before and after functionalization were characterized with NMR spectroscopy, small-angle X-ray scattering (SAXS), and dynamic mechanical analysis (DMA). ¹H and ¹³C NMR spectra confirm the successful attachment of the benzoyl group to the hydroxyl group. The FTIR spectra of PHU-Bz in the carbonyl region also show a higher proportion of free carbonyl relative to hydrogen-bonded carbonyl, indicative of phase mixing. These results show that hydroxyl group functionalization with side groups as small as an acetyl group or as large as a benzoyl group provides similar, substantial steric hindrance to interurethane hydrogen bonding, leading to phase mixing in these segmented, functionalized PHUs. SAXS experiments were performed using a Rigaku S-MAX 3000 SAXS system emitting X-rays with a wavelength of 0.154 nm.

Original language	English (US)
Pages (from-to)	3347-3351
Number of pages	5
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	55
Issue number	20
DOIs	https://doi.org/10.1002/pola.28722
State	Published - Oct 15 2017

Funding

This work is supported by the University Partnership Initiative between Northwestern University and The Dow Chemical Company. This work made use of central facilities supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Northwestern University Materials Research Science and Engineering Center and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), as well as facilities supported by Northwestern University at the Integrated Molecular Structure Education and Research Center.

Keywords

nanophase separation
nonisocyanate polyurethane
polyhydroxyurethane

ASJC Scopus subject areas

Polymers and Plastics
Organic Chemistry
Materials Chemistry

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10.1002/pola.28722

Cite this

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title = "Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation",

abstract = "The properties of segmented, nanophase-separated polyhydroxyurethane (PHUs) were investigated before and after hydroxyl group functionalization. Segmented PHU was synthesized using polytetramethylene oxide (PTMO)-based soft segment, divinylbenzene dicyclocarbonate (DVBDCC) as hard segment, and p-xylylene diamine as chain extender at 40 wt% hard-segment content. The pendant hydroxyl groups were subsequently functionalized with benzoyl chloride, and the properties of PHUs before and after functionalization were characterized with NMR spectroscopy, small-angle X-ray scattering (SAXS), and dynamic mechanical analysis (DMA). 1H and 13C NMR spectra confirm the successful attachment of the benzoyl group to the hydroxyl group. The FTIR spectra of PHU-Bz in the carbonyl region also show a higher proportion of free carbonyl relative to hydrogen-bonded carbonyl, indicative of phase mixing. These results show that hydroxyl group functionalization with side groups as small as an acetyl group or as large as a benzoyl group provides similar, substantial steric hindrance to interurethane hydrogen bonding, leading to phase mixing in these segmented, functionalized PHUs. SAXS experiments were performed using a Rigaku S-MAX 3000 SAXS system emitting X-rays with a wavelength of 0.154 nm.",

keywords = "nanophase separation, nonisocyanate polyurethane, polyhydroxyurethane",

author = "Goliath Beniah and Heath, {William H.} and Torkelson, {John M.}",

note = "Funding Information: This work is supported by the University Partnership Initiative between Northwestern University and The Dow Chemical Company. This work made use of central facilities supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Northwestern University Materials Research Science and Engineering Center and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), as well as facilities supported by Northwestern University at the Integrated Molecular Structure Education and Research Center.",

year = "2017",

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doi = "10.1002/pola.28722",

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volume = "55",

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T1 - Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation

AU - Beniah, Goliath

AU - Heath, William H.

AU - Torkelson, John M.

N1 - Funding Information: This work is supported by the University Partnership Initiative between Northwestern University and The Dow Chemical Company. This work made use of central facilities supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Northwestern University Materials Research Science and Engineering Center and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), as well as facilities supported by Northwestern University at the Integrated Molecular Structure Education and Research Center.

PY - 2017/10/15

Y1 - 2017/10/15

N2 - The properties of segmented, nanophase-separated polyhydroxyurethane (PHUs) were investigated before and after hydroxyl group functionalization. Segmented PHU was synthesized using polytetramethylene oxide (PTMO)-based soft segment, divinylbenzene dicyclocarbonate (DVBDCC) as hard segment, and p-xylylene diamine as chain extender at 40 wt% hard-segment content. The pendant hydroxyl groups were subsequently functionalized with benzoyl chloride, and the properties of PHUs before and after functionalization were characterized with NMR spectroscopy, small-angle X-ray scattering (SAXS), and dynamic mechanical analysis (DMA). 1H and 13C NMR spectra confirm the successful attachment of the benzoyl group to the hydroxyl group. The FTIR spectra of PHU-Bz in the carbonyl region also show a higher proportion of free carbonyl relative to hydrogen-bonded carbonyl, indicative of phase mixing. These results show that hydroxyl group functionalization with side groups as small as an acetyl group or as large as a benzoyl group provides similar, substantial steric hindrance to interurethane hydrogen bonding, leading to phase mixing in these segmented, functionalized PHUs. SAXS experiments were performed using a Rigaku S-MAX 3000 SAXS system emitting X-rays with a wavelength of 0.154 nm.

AB - The properties of segmented, nanophase-separated polyhydroxyurethane (PHUs) were investigated before and after hydroxyl group functionalization. Segmented PHU was synthesized using polytetramethylene oxide (PTMO)-based soft segment, divinylbenzene dicyclocarbonate (DVBDCC) as hard segment, and p-xylylene diamine as chain extender at 40 wt% hard-segment content. The pendant hydroxyl groups were subsequently functionalized with benzoyl chloride, and the properties of PHUs before and after functionalization were characterized with NMR spectroscopy, small-angle X-ray scattering (SAXS), and dynamic mechanical analysis (DMA). 1H and 13C NMR spectra confirm the successful attachment of the benzoyl group to the hydroxyl group. The FTIR spectra of PHU-Bz in the carbonyl region also show a higher proportion of free carbonyl relative to hydrogen-bonded carbonyl, indicative of phase mixing. These results show that hydroxyl group functionalization with side groups as small as an acetyl group or as large as a benzoyl group provides similar, substantial steric hindrance to interurethane hydrogen bonding, leading to phase mixing in these segmented, functionalized PHUs. SAXS experiments were performed using a Rigaku S-MAX 3000 SAXS system emitting X-rays with a wavelength of 0.154 nm.

KW - nanophase separation

KW - nonisocyanate polyurethane

KW - polyhydroxyurethane

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

IS - 20

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Functionalization of hydroxyl groups in segmented polyhydroxyurethane eliminates nanophase separation

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