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Title: Biomass-derived monomers for performance-differentiated fiber reinforced polymer composites

Nearly all polymer resins used to manufacture critically important fiber reinforced polymer (FRP) composites are petroleum sourced. In particular, unsaturated polyesters (UPEs) are widely used as matrix materials and are often based on maleic anhydride, a four-carbon, unsaturated diacid. Typically, maleic anhydride is added as a reactant in a conventional step-growth polymerization to incorporate unsaturation throughout the backbone of the UPE, which is then dissolved in a reactive diluent (styrene is widely used) infused into a fiber mat and cross-linked. Despite widespread historical use, styrene has come under scrutiny due to environmental and health concerns; in addition, many conceivable UPEs are not soluble in styrene. In this study, we demonstrate that renewably-sourced monomers offer the ability to overcome these issues and improve overall composite performance. The properties of poly(butylene succinate)-based UPEs incorporating maleic anhydride are used as a baseline for comparison against UPEs derived from fumaric acid, cis, cis-muconate, and trans, trans-muconate, all of which can be obtained biologically. The resulting biobased UPEs are combined with styrene, methacrylic acid, or a mixture of methacrylic acid and cinnaminic acid, infused into woven fiberglass and cross-linked with the addition of a free-radical initiator and heat. This process produces a series of partiallymore » or fully bio-derived composites. Overall, the muconate-containing UPE systems exhibit a more favorable property suite than the maleic anhydride and fumaric acid counterparts. In all cases at the same olefinic monomer loading, the trans, trans-muconate polymers exhibit the highest shear modulus, storage modulus, and glass transition temperature indicating stronger and more thermally resistant materials. They also exhibit the lowest loss modulus indicating a greater adhesion to the glass fibers. The use of a mixture of methacrylic and cinnaminic acid as the reactive diluent results in a FRP composite with properties that can be matched to reinforced composites prepared with styrene. Significantly, at one-third the monomer loading (corresponding to two-thirds the number of double bonds), trans, trans-muconate produces approximately the same storage modulus and glass transition temperature as maleic anhydride, while exhibiting a superior loss modulus. Altogether, this work demonstrates the novel synthesis of performance-differentiated FRP composites using renewably-sourced monomers.« less
Authors:
 [1] ;  [1] ;  [2] ;  [1] ; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. Michigan State Univ., East Lansing, MI (United States)
Publication Date:
Report Number(s):
NREL/JA-5100-68265
Journal ID: ISSN 1463-9262; GRCHFJ
Grant/Contract Number:
AC36-08GO28308
Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 19; Journal Issue: 12; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), NREL Laboratory Directed Research and Development (LDRD); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; monomers; composite performance; unsaturated polyesters; UPEs; fiber reinforced polymer; FRP
OSTI Identifier:
1369120

Rorrer, Nicholas A., Vardon, Derek R., Dorgan, John R., Gjersing, Erica J., and Beckham, Gregg T.. Biomass-derived monomers for performance-differentiated fiber reinforced polymer composites. United States: N. p., Web. doi:10.1039/C7GC00320J.
Rorrer, Nicholas A., Vardon, Derek R., Dorgan, John R., Gjersing, Erica J., & Beckham, Gregg T.. Biomass-derived monomers for performance-differentiated fiber reinforced polymer composites. United States. doi:10.1039/C7GC00320J.
Rorrer, Nicholas A., Vardon, Derek R., Dorgan, John R., Gjersing, Erica J., and Beckham, Gregg T.. 2017. "Biomass-derived monomers for performance-differentiated fiber reinforced polymer composites". United States. doi:10.1039/C7GC00320J. https://www.osti.gov/servlets/purl/1369120.
@article{osti_1369120,
title = {Biomass-derived monomers for performance-differentiated fiber reinforced polymer composites},
author = {Rorrer, Nicholas A. and Vardon, Derek R. and Dorgan, John R. and Gjersing, Erica J. and Beckham, Gregg T.},
abstractNote = {Nearly all polymer resins used to manufacture critically important fiber reinforced polymer (FRP) composites are petroleum sourced. In particular, unsaturated polyesters (UPEs) are widely used as matrix materials and are often based on maleic anhydride, a four-carbon, unsaturated diacid. Typically, maleic anhydride is added as a reactant in a conventional step-growth polymerization to incorporate unsaturation throughout the backbone of the UPE, which is then dissolved in a reactive diluent (styrene is widely used) infused into a fiber mat and cross-linked. Despite widespread historical use, styrene has come under scrutiny due to environmental and health concerns; in addition, many conceivable UPEs are not soluble in styrene. In this study, we demonstrate that renewably-sourced monomers offer the ability to overcome these issues and improve overall composite performance. The properties of poly(butylene succinate)-based UPEs incorporating maleic anhydride are used as a baseline for comparison against UPEs derived from fumaric acid, cis,cis-muconate, and trans,trans-muconate, all of which can be obtained biologically. The resulting biobased UPEs are combined with styrene, methacrylic acid, or a mixture of methacrylic acid and cinnaminic acid, infused into woven fiberglass and cross-linked with the addition of a free-radical initiator and heat. This process produces a series of partially or fully bio-derived composites. Overall, the muconate-containing UPE systems exhibit a more favorable property suite than the maleic anhydride and fumaric acid counterparts. In all cases at the same olefinic monomer loading, the trans,trans-muconate polymers exhibit the highest shear modulus, storage modulus, and glass transition temperature indicating stronger and more thermally resistant materials. They also exhibit the lowest loss modulus indicating a greater adhesion to the glass fibers. The use of a mixture of methacrylic and cinnaminic acid as the reactive diluent results in a FRP composite with properties that can be matched to reinforced composites prepared with styrene. Significantly, at one-third the monomer loading (corresponding to two-thirds the number of double bonds), trans,trans-muconate produces approximately the same storage modulus and glass transition temperature as maleic anhydride, while exhibiting a superior loss modulus. Altogether, this work demonstrates the novel synthesis of performance-differentiated FRP composites using renewably-sourced monomers.},
doi = {10.1039/C7GC00320J},
journal = {Green Chemistry},
number = 12,
volume = 19,
place = {United States},
year = {2017},
month = {3}
}

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