skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Abstract

Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (T g up to 184°C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest T g values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Cornell Univ., Ithaca, NY (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of Southern Mississippi, Hattiesburg, MS (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543746
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology; Other Topics

Citation Formats

Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., and DiStasio, Jr., Robert A. Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05269-3.
Copy to clipboard
Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., & DiStasio, Jr., Robert A. Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters. United States. doi:10.1038/s41467-018-05269-3.
Copy to clipboard
Yu, Xiaopeng, Jia, Junteng, Xu, Shu, Lao, Ka Un, Sanford, Maria J., Ramakrishnan, Ramesh K., Nazarenko, Sergei I., Hoye, Thomas R., Coates, Geoffrey W., and DiStasio, Jr., Robert A. Mon . "Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters". United States. doi:10.1038/s41467-018-05269-3. https://www.osti.gov/servlets/purl/1543746.
Copy to clipboard
@article{osti_1543746,
title = {Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters},
author = {Yu, Xiaopeng and Jia, Junteng and Xu, Shu and Lao, Ka Un and Sanford, Maria J. and Ramakrishnan, Ramesh K. and Nazarenko, Sergei I. and Hoye, Thomas R. and Coates, Geoffrey W. and DiStasio, Jr., Robert A.},
abstractNote = {Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184°C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.},
doi = {10.1038/s41467-018-05269-3},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1038/s41467-018-05269-3
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Furfural-A Promising Platform for Lignocellulosic Biofuels
journal, December 2011

  • Lange, Jean-Paul; van der Heide, Evert; van Buijtenen, Jeroen
  • ChemSusChem, Vol. 5, Issue 1
  • DOI: 10.1002/cssc.201100648

Psi4 1.1: An Open-Source Electronic Structure Program Emphasizing Automation, Advanced Libraries, and Interoperability
journal, June 2017

  • Parrish, Robert M.; Burns, Lori A.; Smith, Daniel G. A.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 7
  • DOI: 10.1021/acs.jctc.7b00174

Substituted Phthalic Anhydrides from Biobased Furanics: A New Approach to Renewable Aromatics
journal, July 2015

  • Thiyagarajan, Shanmugam; Genuino, Homer C.; Śliwa, Michał
  • ChemSusChem, Vol. 8, Issue 18
  • DOI: 10.1002/cssc.201500511

Positronium Annihilation in Molecular Substances
journal, June 1972

  • Tao, S. J.
  • The Journal of Chemical Physics, Vol. 56, Issue 11
  • DOI: 10.1063/1.1677067

Algorithm 97: Shortest path
journal, June 1962

An infra-red study of conformational changes occurring during the drawing of PEMT, PET and PEMT/PET copolymer
journal, January 1992

Aliphatic Polyester Block Polymers: Renewable, Degradable, and Sustainable
journal, May 2014

  • Hillmyer, Marc A.; Tolman, William B.
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar500121d

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources
journal, February 2013

  • van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed
  • Chemical Reviews, Vol. 113, Issue 3
  • DOI: 10.1021/cr300182k

A density functional study of the simplest hydrogen abstraction reaction. Effect of self-interaction correction
journal, April 1994

Segmental Mobility of Polymers Near Their Glass Temperature
journal, October 1953

  • Bueche, F.
  • The Journal of Chemical Physics, Vol. 21, Issue 10
  • DOI: 10.1063/1.1698677

Di-magnesium and zinc catalysts for the copolymerization of phthalic anhydride and cyclohexene oxide
journal, January 2014

  • Saini, Prabhjot K.; Romain, Charles; Zhu, Yunqing
  • Polym. Chem., Vol. 5, Issue 20
  • DOI: 10.1039/C4PY00748D

Free volume, glass transition, and degree of branching in metallocene-based propylene/?-olefin copolymers: Positron lifetime, density, and differential scanning calorimetric studies
journal, January 2002

  • Dlubek, G.; Bamford, D.; Rodriguez-Gonzalez, A.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 5
  • DOI: 10.1002/polb.10108

Alternating Ring-Opening Polymerization of Cyclohexene Oxide and Anhydrides: Effect of Catalyst, Cocatalyst, and Anhydride Structure
journal, February 2012

  • Hosseini Nejad, Elham; van Melis, Carlo G. W.; Vermeer, Tim J.
  • Macromolecules, Vol. 45, Issue 4
  • DOI: 10.1021/ma2025804

Substituent Effects on the Reversibility of Furan–Maleimide Cycloadditions
journal, October 2011

  • Boutelle, Robert C.; Northrop, Brian H.
  • The Journal of Organic Chemistry, Vol. 76, Issue 19
  • DOI: 10.1021/jo201606z

Program system for analysing positron lifetime spectra and angular correlation curves
journal, July 1981

Assessing DFT-D3 Damping Functions Across Widely Used Density Functionals: Can We Do Better?
journal, April 2017

  • Witte, Jonathon; Mardirossian, Narbe; Neaton, Jeffrey B.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 5
  • DOI: 10.1021/acs.jctc.7b00176

The promise of plastics from plants
journal, November 2017

Free volume and intrinsic microporosity in polymers
journal, January 2005

  • Budd, Peter M.; McKeown, Neil B.; Fritsch, Detlev
  • Journal of Materials Chemistry, Vol. 15, Issue 20
  • DOI: 10.1039/b417402j

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications
journal, March 2017

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes
journal, July 2015

Cooperative molecular dynamics and strong/fragile behavior of polymers
journal, August 1999

A Facile Solid-Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
journal, December 2015

  • Thiyagarajan, Shanmugam; Genuino, Homer C.; van der Waal, Jan C.
  • Angewandte Chemie International Edition, Vol. 55, Issue 4
  • DOI: 10.1002/anie.201509346

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014

Stereochemistry of reaction paths at carbonyl centres
journal, January 1974

Communication: Practical intramolecular symmetry adapted perturbation theory via Hartree-Fock embedding
journal, August 2015

  • Parrish, Robert M.; Gonthier, Jérôme F.; Corminbœuf, Clémence
  • The Journal of Chemical Physics, Vol. 143, Issue 5
  • DOI: 10.1063/1.4927575

Glass transition and chain flexibility of linear polymers
journal, April 1974

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Stereochemistry of polypeptide chain configurations
journal, July 1963

Semiaromatic Polyesters Derived from Renewable Terpene Oxides with High Glass Transitions
journal, July 2017

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab initio studies on the structure, conformation, and chain flexibility of halogenated poly(thionylphosphazenes)
journal, March 1995

  • Jaeger, R.; Lagowski, J. B.; Manners, I.
  • Macromolecules, Vol. 28, Issue 2
  • DOI: 10.1021/ma00106a019

Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides with Discrete Metal Complexes: Structure–Property Relationships
journal, December 2016

Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride
journal, January 2014

  • Mahmoud, Eyas; Watson, Donald A.; Lobo, Raul F.
  • Green Chem., Vol. 16, Issue 1
  • DOI: 10.1039/C3GC41655K

Ring-opening copolymerization (ROCOP): synthesis and properties of polyesters and polycarbonates
journal, January 2015

  • Paul, Shyeni; Zhu, Yunqing; Romain, Charles
  • Chemical Communications, Vol. 51, Issue 30
  • DOI: 10.1039/C4CC10113H

Addition-Type Polynorbornenes with Si(CH3)3 Side Groups:  Synthesis, Gas Permeability, and Free Volume
journal, October 2006

  • Finkelshtein, E. Sh.; Makovetskii, K. L.; Gringolts, M. L.
  • Macromolecules, Vol. 39, Issue 20, p. 7022-7029
  • DOI: 10.1021/ma061215h

Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007

  • Corma, Avelino; Iborra, Sara; Velty, Alexandra
  • Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
  • DOI: 10.1021/cr050989d

Polymer Free Volume and Its Connection to the Glass Transition
journal, May 2016

Intramolecular symmetry-adapted perturbation theory with a single-determinant wavefunction
journal, December 2015

  • Pastorczak, Ewa; Prlj, Antonio; Gonthier, Jérôme F.
  • The Journal of Chemical Physics, Vol. 143, Issue 22
  • DOI: 10.1063/1.4936830

Dependence of glass transition temperature on chain flexibility and intermolecular interactions in polymers
journal, September 1991

Sustainable polymers from renewable resources
journal, December 2016

  • Zhu, Yunqing; Romain, Charles; Williams, Charlotte K.
  • Nature, Vol. 540, Issue 7633
  • DOI: 10.1038/nature21001

Dispersion-Corrected Mean-Field Electronic Structure Methods
journal, April 2016

Electronic Effects of Aluminum Complexes in the Copolymerization of Propylene Oxide with Tricyclic Anhydrides: Access to Well-Defined, Functionalizable Aliphatic Polyesters
journal, February 2016

  • Van Zee, Nathan J.; Sanford, Maria J.; Coates, Geoffrey W.
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b12888

A Theorem on Boolean Matrices
journal, January 1962

A Preliminary Survey of the Peptoid Folding Landscape
journal, November 2009

  • Butterfoss, Glenn L.; Renfrew, P. Douglas; Kuhlman, Brian
  • Journal of the American Chemical Society, Vol. 131, Issue 46
  • DOI: 10.1021/ja905267k

Internal rotation barriers: ab initio calculations on substituted ethyl benzoates and benzoic acids as models for polyester flexibility
journal, June 1998

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

A quantum mechanical study on polymer flexibility: Extended model from monomer to tetramer of 2- and 4-bromostyrenes
journal, January 2009

Asymmetric Alternating Copolymerization of Meso-epoxides and Cyclic Anhydrides: Efficient Access to Enantiopure Polyesters
journal, August 2016

  • Li, Jie; Liu, Ye; Ren, Wei-Min
  • Journal of the American Chemical Society, Vol. 138, Issue 36
  • DOI: 10.1021/jacs.6b07520

Effect of chemical structure on the softening point of substituted polystyrenes and related materials
journal, June 1959

Chemical Assignment of Symmetry-Adapted Perturbation Theory Interaction Energy Components: The Functional-Group SAPT Partition
journal, September 2014

  • Parrish, Robert M.; Parker, Trent M.; Sherrill, C. David
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 10
  • DOI: 10.1021/ct500724p
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: