Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane

Goliath Beniah; Xi Chen; Brice E. Uno; Kun Liu; Emily K. Leitsch; Junho Jeon; William H. Heath; Karl A. Scheidt; John M. Torkelson

doi:10.1021/acs.macromol.6b02513

Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane

Goliath Beniah, Xi Chen, Brice E. Uno, Kun Liu, Emily K. Leitsch, Junho Jeon, William H. Heath, Karl A. Scheidt, John M. Torkelson^*

^*Corresponding author for this work

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

51 Scopus citations

Abstract

The influence of hard-segment structure on the properties of segmented polyhydroxyurethane (PHU) was investigated using three bis-carbonate molecules: divinylbenzene dicyclocarbonate (DVBDCC), Bisphenol A dicarbonate (BPADC), and resorcinol bis-carbonate (RBC). These carbonates were formulated with poly(tetramethylene oxide) (PTMO)-based and polybutadiene-co-acrylonitrile (PBN)-based soft segments at 40 wt % hard-segment content, resulting in non-isocyanate polyurethanes (NIPUs). Small-angle X-ray scattering, dynamic mechanical analysis, and tensile testing reveal that hard-segment and soft-segment structures may cooperatively influence segmented PHU properties. With PTMO-based soft segment, BPADC yields phase-mixed PHU because of strong intersegmental hydrogen bonding from the hard-segment hydroxyl groups to the soft segment; in contrast, because of moderate intersegmental hydrogen bonding to the PTMO-based soft segment, DVBDCC and RBC lead to nanophase-separated PHUs with 15-17 nm interdomain spacings with substantial, broad interphase regions and low tensile strengths of ∼0.40 MPa for DVBDCC and ∼0.27 MPa for RBC. By suppressing intersegmental hydrogen bonding via the use of PBN-based soft segment, formulations with all three carbonate molecules lead to nanophase-separated PHUs with interdomain spacings of 11-16 nm, narrow interfaces, and improved tensile strengths ranging from 1.6 to 0.5 MPa in the order DVBDCC > BPADC > RBC. All PBN-based PHUs exhibit reversibility of extension with hysteresis similar to that found in thermoplastic polyurethane elastomers.

Original language	English (US)
Pages (from-to)	3193-3203
Number of pages	11
Journal	Macromolecules
Volume	50
Issue number	8
DOIs	https://doi.org/10.1021/acs.macromol.6b02513
State	Published - Apr 25 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 as well as facilities supported by Northwestern University at the Integrated Molecular Structure Education and Research Center. The authors thank Mr. Jeremy Pasatta from Emerald Performance Materials for supplying PBN-based soft segment and The Huntsman Corporation for supplying PTMO-based soft segment.

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1021/acs.macromol.6b02513

Cite this

@article{d7700ca7333a475daf7b0006fc81e588,

title = "Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane",

abstract = "The influence of hard-segment structure on the properties of segmented polyhydroxyurethane (PHU) was investigated using three bis-carbonate molecules: divinylbenzene dicyclocarbonate (DVBDCC), Bisphenol A dicarbonate (BPADC), and resorcinol bis-carbonate (RBC). These carbonates were formulated with poly(tetramethylene oxide) (PTMO)-based and polybutadiene-co-acrylonitrile (PBN)-based soft segments at 40 wt % hard-segment content, resulting in non-isocyanate polyurethanes (NIPUs). Small-angle X-ray scattering, dynamic mechanical analysis, and tensile testing reveal that hard-segment and soft-segment structures may cooperatively influence segmented PHU properties. With PTMO-based soft segment, BPADC yields phase-mixed PHU because of strong intersegmental hydrogen bonding from the hard-segment hydroxyl groups to the soft segment; in contrast, because of moderate intersegmental hydrogen bonding to the PTMO-based soft segment, DVBDCC and RBC lead to nanophase-separated PHUs with 15-17 nm interdomain spacings with substantial, broad interphase regions and low tensile strengths of ∼0.40 MPa for DVBDCC and ∼0.27 MPa for RBC. By suppressing intersegmental hydrogen bonding via the use of PBN-based soft segment, formulations with all three carbonate molecules lead to nanophase-separated PHUs with interdomain spacings of 11-16 nm, narrow interfaces, and improved tensile strengths ranging from 1.6 to 0.5 MPa in the order DVBDCC > BPADC > RBC. All PBN-based PHUs exhibit reversibility of extension with hysteresis similar to that found in thermoplastic polyurethane elastomers.",

author = "Goliath Beniah and Xi Chen and Uno, {Brice E.} and Kun Liu and Leitsch, {Emily K.} and Junho Jeon and Heath, {William H.} and Scheidt, {Karl A.} and Torkelson, {John M.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = apr,

day = "25",

doi = "10.1021/acs.macromol.6b02513",

language = "English (US)",

volume = "50",

pages = "3193--3203",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane

AU - Beniah, Goliath

AU - Chen, Xi

AU - Uno, Brice E.

AU - Liu, Kun

AU - Leitsch, Emily K.

AU - Jeon, Junho

AU - Heath, William H.

AU - Scheidt, Karl A.

AU - Torkelson, John M.

PY - 2017/4/25

Y1 - 2017/4/25

N2 - The influence of hard-segment structure on the properties of segmented polyhydroxyurethane (PHU) was investigated using three bis-carbonate molecules: divinylbenzene dicyclocarbonate (DVBDCC), Bisphenol A dicarbonate (BPADC), and resorcinol bis-carbonate (RBC). These carbonates were formulated with poly(tetramethylene oxide) (PTMO)-based and polybutadiene-co-acrylonitrile (PBN)-based soft segments at 40 wt % hard-segment content, resulting in non-isocyanate polyurethanes (NIPUs). Small-angle X-ray scattering, dynamic mechanical analysis, and tensile testing reveal that hard-segment and soft-segment structures may cooperatively influence segmented PHU properties. With PTMO-based soft segment, BPADC yields phase-mixed PHU because of strong intersegmental hydrogen bonding from the hard-segment hydroxyl groups to the soft segment; in contrast, because of moderate intersegmental hydrogen bonding to the PTMO-based soft segment, DVBDCC and RBC lead to nanophase-separated PHUs with 15-17 nm interdomain spacings with substantial, broad interphase regions and low tensile strengths of ∼0.40 MPa for DVBDCC and ∼0.27 MPa for RBC. By suppressing intersegmental hydrogen bonding via the use of PBN-based soft segment, formulations with all three carbonate molecules lead to nanophase-separated PHUs with interdomain spacings of 11-16 nm, narrow interfaces, and improved tensile strengths ranging from 1.6 to 0.5 MPa in the order DVBDCC > BPADC > RBC. All PBN-based PHUs exhibit reversibility of extension with hysteresis similar to that found in thermoplastic polyurethane elastomers.

AB - The influence of hard-segment structure on the properties of segmented polyhydroxyurethane (PHU) was investigated using three bis-carbonate molecules: divinylbenzene dicyclocarbonate (DVBDCC), Bisphenol A dicarbonate (BPADC), and resorcinol bis-carbonate (RBC). These carbonates were formulated with poly(tetramethylene oxide) (PTMO)-based and polybutadiene-co-acrylonitrile (PBN)-based soft segments at 40 wt % hard-segment content, resulting in non-isocyanate polyurethanes (NIPUs). Small-angle X-ray scattering, dynamic mechanical analysis, and tensile testing reveal that hard-segment and soft-segment structures may cooperatively influence segmented PHU properties. With PTMO-based soft segment, BPADC yields phase-mixed PHU because of strong intersegmental hydrogen bonding from the hard-segment hydroxyl groups to the soft segment; in contrast, because of moderate intersegmental hydrogen bonding to the PTMO-based soft segment, DVBDCC and RBC lead to nanophase-separated PHUs with 15-17 nm interdomain spacings with substantial, broad interphase regions and low tensile strengths of ∼0.40 MPa for DVBDCC and ∼0.27 MPa for RBC. By suppressing intersegmental hydrogen bonding via the use of PBN-based soft segment, formulations with all three carbonate molecules lead to nanophase-separated PHUs with interdomain spacings of 11-16 nm, narrow interfaces, and improved tensile strengths ranging from 1.6 to 0.5 MPa in the order DVBDCC > BPADC > RBC. All PBN-based PHUs exhibit reversibility of extension with hysteresis similar to that found in thermoplastic polyurethane elastomers.

UR - http://www.scopus.com/inward/record.url?scp=85018627101&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85018627101&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.6b02513

DO - 10.1021/acs.macromol.6b02513

M3 - Article

AN - SCOPUS:85018627101

SN - 0024-9297

VL - 50

SP - 3193

EP - 3203

JO - Macromolecules

JF - Macromolecules

IS - 8

ER -

Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this