Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Applying machine learning and quantum chemistry to predict the glass transition temperatures of polymers

Journal Article · · Computational Materials Science
Glass transition temperature (Tg) is important for understanding the physical and mechanical properties of a polymer material because it relates to the thermal energy required to transition between a hard glassy state and a soft rubbery one. Over the years, various models have been developed for predicting this thermal property from molecular structure to aid in designing novel polymers in selected classes. This work builds on those efforts by utilizing both machine learning (ML) and quantum chemistry (QC) techniques to develop models that can predict Tg values from the molecular structure under different data availability scenarios and for a wide variety of polymer types. For the ML model, a graph convolutional network (GCN) was used to map topological polymer features; this model was trained against a dataset of more than 7500 Tg values and resulted in a root mean square error (RMSE) of 38.1 °C. The QC-based regression model was trained on 83 Tg values and produced an RMSE of 34.5 °C. In conclusion, this work demonstrated that while both model techniques produce accurate predictions and are suitable for different data availability scenarios, the QC-based regression model offered a more interpretable model framework with significantly less training data.
Research Organization:
Argonne National Laboratory (ANL); IL (United States)
Sponsoring Organization:
USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2328569
Alternate ID(s):
OSTI ID: 2369661
Journal Information:
Computational Materials Science, Journal Name: Computational Materials Science Vol. 238; ISSN 0927-0256
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (95)

The relationship between glass temperature, molar cohesion, and polymer structure journal May 1961
Correlation and prediction of polyamide glass transitions journal December 1965
Physical properties of molecular crystals, liquids and glasses. Arnold, Bondi, Wiley, New York, 1968, 502 pp. $18.50 journal August 1969
Contribution of the methylene group to the glass transition temperatures of polymers journal January 1968
Prediction of the glass transition temperature of polymers journal February 1970
Degradation of Natural Rubber and Synthetic Elastomers book January 2017
A simulation study of the number of events per variable in logistic regression analysis journal December 1996
Prediction of the thermal decomposition property of polymers using quantum chemical descriptors journal March 2007
Prediction of the glass transition temperatures of styrenic copolymers using a QSPR based on the DFT method journal August 2006
Revealing Structural Changes at Glass Transition via Radial Distribution Functions journal March 2020
Dramatic Behavioral Differences of the Copolymerization Reactions of 1,4-Cyclohexadiene and 1,3-Cyclohexadiene Oxides with Carbon Dioxide journal March 2015
New Aspects for the Hierarchical Cooperative Motions in Photoalignment Process of Liquid Crystalline Block Copolymer Films journal March 2015
Epicyanohydrin: Polymerization by Monomer Activation Gives Access to Nitrile-, Amino-, and Carboxyl-Functional Poly(ethylene glycol) journal October 2015
Chain Collapse and Interfacial Slip of Polystyrene Films in Good/Nonsolvent Vapor Mixtures journal February 2016
Effect of Compatibilization on Interfacial Polarization and Intrinsic Length Scales in Biphasic Polymer Blends of PαMSAN and PMMA: A Combined Experimental and Modeling Dielectric Study journal February 2016
Major Impact of Cyclic Chain Topology on the T g -Confinement Effect of Supported Thin Films of Polystyrene journal December 2015
High Temperature Thermoplastic Elastomers Synthesized by Living Anionic Polymerization in Hydrocarbon Solvent at Room Temperature journal March 2016
Enhancing the Electrospinnability of Low Molecular Weight Polymers Using Small Effective Cross-Linkers journal January 2016
Prediction and Interpretation of Polymer Properties Using the Graph Convolutional Network journal January 2022
Chemical Name to Structure: OPSIN, an Open Source Solution journal February 2011
Universal Solvation Model Based on the Generalized Born Approximation with Asymmetric Descreening journal August 2009
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Counterion Effect on the Rheology and Morphology of Tailored Poly(dimethylsiloxane) Ionomers journal February 2006
pH-Responsive Diblock Copolymers Prepared by the Dual Initiator Strategy journal April 2006
Optically Active Poly(phenylacetylene) Film:  Simultaneous Change of Color and Helical Structure journal March 2006
Polymers for Photothermography:  Controlled Thermal Release of Color Photographic Developer from Substituted Polystyrene Derivatives journal July 2006
Microbeam X-ray Diffraction and Enzymatic Degradation of Poly[(R)-3-hydroxybutyrate] Fibers with Two Kinds of Molecular Conformations journal July 2006
Glass Transition Behavior of Clay Aerogel/Poly(vinyl alcohol) Composites journal August 2006
Synthesis and Characterization of Poly(vinylidene fluoride)- g -poly(styrene) Graft Polymers Obtained by Atom Transfer Radical Polymerization of Styrene journal November 2006
Structural Changes in Thermally Induced Phase Transitions of Uniaxially Oriented δe Form of Syndiotactic Polystyrene Investigated by Temperature-Dependent Measurements of X-ray Fiber Diagrams and Polarized Infrared Spectra journal October 2006
Chain Architecture Effects on the Diffusion of Cylinder-Forming Block Copolymers journal March 2007
Control of Mechanical Behavior in Polyolefin Composites:  Integration of Glassy, Rubbery, and Semicrystalline Components journal February 2007
Synthesis of Polymandelide:  A Degradable Polylactide Derivative with Polystyrene-like Properties journal July 2007
Preparation and Characterization of Nanocellular Poly(phenylquinoxaline) Foams. A New Approach to Nanoporous High-Performance Polymers journal March 2007
Zero Growth Temperature of Crystallizing Polyethylene journal March 2007
Mechanical Spectroscopy of PVCN with Increasing Cross-Linking Degree journal May 2007
Phase Behavior and Temperature-Responsive Molecular Filters Based on Self-Assembly of Polystyrene- block -poly( N -isopropylacrylamide)- bloc k -polystyrene journal July 2007
Enzymatic Synthesis and Solid-State Properties of Aliphatic Polyesteramides with Polydimethylsiloxane Blocks journal October 2007
Investigation of Dynamics of Poly(dimethylsilane) in the Mesophase by Solid-State 29Si NMR:  Evidence for Rotator Phase journal June 2007
Electrospinning and Solution Properties of Nafion and Poly(acrylic acid) journal January 2008
Unidirectional Dimerization and Stacking of Ureidopyrimidinone End Groups in Polycaprolactone Supramolecular Polymers journal November 2007
Living Anionic Polymerization of the Amphiphilic Monomer 2-(4-Vinylphenyl)pyridine journal November 2007
RAFT Homo- and Copolymerization of N-Acryloyl-morpholine, Piperidine, and Azocane and Their Self-Assembled Structures journal February 2008
Structural Correlation between Crystal Lattice and Lamellar Morphology in the Phase Transitions of Uniaxially Oriented Syndiotactic Polystyrene (δ and δe Forms) As Revealed by Simultaneous Measurements of Wide-Angle and Small-Angle X-ray Scatterings journal February 2008
Radical Copolymerization of α,β-Difluoroacrylic Acid with Vinylidene Fluoride. journal May 2010
Enthalpy Recovery of PMMA/Silica Nanocomposites journal August 2010
Double Reaction-induced Microphase Separation in Epoxy Resin Containing Polystyrene-block-poly(ε-caprolactone)-block-poly(n-butyl acrylate) ABC Triblock Copolymer journal December 2010
Miscible and Core−Sheath PS/PVME Fibers by Electrospinning journal March 2011
Phase Separation and Lamellae Assembly below UCST in Poly(l-lactic acid)/Poly(1,4-butylene adipate) Blend Induced by Crystallization journal March 2012
Hybrid Copolymerization of ε-Caprolactone and Methyl Methacrylate journal April 2012
First Example of a Universal and Cost-Effective Approach: Polymers with Tunable Upper Critical Solution Temperature in Water and Electrolyte Solution journal April 2012
Synthesis and Properties of Highly Cross-Linked Thermosetting Resins of Benzocyclobutene-Functionalized Benzoxazine journal May 2012
Comparison of Shell-Cross-Linked Micelles with Soft and Glassy Cores as a Drug Delivery Vehicle for Albendazole: Is There a Difference in Performance? journal June 2012
Synthesis of Novel Cyclic Olefin Copolymer (COC) with High Performance via Effective Copolymerization of Ethylene with Bulky Cyclic Olefin journal June 2012
Theoretical and Experimental Evaluation of Crystallite Moduli of Various Crystalline Forms of Poly(l-lactic acid) journal August 2012
Study of Strain-Induced Crystallization and Enzymatic Degradation of Drawn Poly(l-lactic acid) (PLLA) Films journal September 2012
Thermal Behavior, Stability, and Decomposition Mechanism of Poly(N-vinylimidazole) journal November 2012
Selective Molecular Permeability Induced by Glass Transition Dynamics of Semicrystalline Polymer Ultrathin Films journal December 2012
Simultaneous Determination of Critical Micelle Temperature and Micelle Core Glass Transition Temperature of Block Copolymer–Solvent Systems via Pyrene-Label Fluorescence journal May 2013
Controlling the Rate of Water-Induced Switching in Mechanically Dynamic Cellulose Nanocrystal Composites journal October 2013
Tensile Deformation of Oriented Poly(ε-caprolactone) and Its Miscible Blends with Poly(vinyl methyl ether) journal August 2013
Allyl Glycidyl Ether-Based Polymer Electrolytes for Room Temperature Lithium Batteries journal November 2013
Synthesis and Characteristics of a Biobased High-Tg Terpolyester of Isosorbide, Ethylene Glycol, and 1,4-Cyclohexane Dimethanol: Effect of Ethylene Glycol as a Chain Linker on Polymerization journal September 2013
Photoinduced In-Plane Motions of Azobenzene Mesogens Affected by the Flexibility of Underlying Amorphous Chains journal September 2013
New Insights into Lamellar Structure Development and SAXS/WAXD Sequence Appearance during Uniaxial Stretching of Amorphous Poly(ethylene terephthalate) above Glass Transition Temperature journal March 2008
Concerning the Determination of Conformational States in Polymers by Infrared Spectroscopy: A Study of Poly(methyl methacrylate) journal February 2008
Small-Angle X-ray Scattering Study on the Tensile Fracture Process of Poly(ethylene terephthalate) Fiber journal June 2008
Synthesis and Properties of New Thermoplastic Elastomers Containing Poly[4-(1-adamantyl)styrene] Hard Segments journal July 2008
Rheological Properties of Poly(methyl methacrylate)/Nanoclay Composites As Investigated by Creep Recovery in Shear journal November 2008
Miscible Blends of Cyclic Poly(oxyethylene) in Linear Polystyrene journal November 2008
Correlation of Silicone Incorporation into Hybrid Acrylic Coatings with the Resulting Hydrophobic and Thermal Properties journal October 2008
Control of Morphology and Crystallization in Polyelectrolyte/Polymer Blends journal July 2008
Inducing Pendant Group Interactions in Precision Polyolefins: Synthesis and Thermal Behavior journal June 2008
Thickness-Dependent Properties of Polyzwitterionic Brushes journal August 2008
Diblock Copolymers as Scaffolds for Efficient Functionalization via Click Chemistry journal June 2008
Microphase Separation and Shear Alignment of Gradient Copolymers: Melt Rheology and Small-Angle X-Ray Scattering Analysis journal August 2008
Structure Evolution in a Polyurea Segmented Block Copolymer Because of Mechanical Deformation journal October 2008
Homologous Poly(isobutylene)s: Poly(isobutylene)/High-Density Poly(ethylene) Hybrid Polymers journal November 2008
Left- or Right-Handed Lamellar Twists in Poly[( R )-3-hydroxyvalerate] Banded Spherulite: Dependence on Growth Axis journal February 2009
Role of Solvent Molecules as a Trigger for the Crystal Phase Transition of Syndiotactic Polystyrene/Solvent Complex journal November 2008
Linear Viscoelastic Rheology of Moderately Entangled Telechelic Polybutadiene Temporary Networks journal August 2009
N-Heterocyclic Carbenes for the Organocatalytic Ring-Opening Polymerization of ε-Caprolactone journal February 2009
Difluoroboron Dibenzoylmethane PCL-PLA Block Copolymers: Matrix Effects on Room Temperature Phosphorescence journal April 2009
One-Step Synthetic Route for Conducting Core−Shell Poly(styrene/pyrrole) Nanoparticles journal June 2009
Liquid Crystallinity and Other Properties in Complexes of Cationic Azo-Containing Surfactomesogens with Poly(styrenesulfonate) journal June 2009
Cutinase-Catalyzed Hydrolysis of Poly(ethylene terephthalate) journal July 2009
On the Composition of the Top Layer of Microphase Separated Thin PS-PEO Films journal July 2009
Thermosensitive Self-Assembly of Diblock Copolymers with Lower Critical Micellization Temperatures in an Ionic Liquid journal August 2009
Synthesis and Characterization of Functionalized Polysiloxane for the Stabilization of Catalytically Active Metal Nanoparticles journal July 2009
Synthesis and Degradation Behavior of Cyclic Poly(ε-caprolactone) journal August 2009
Molecular Origin of Solvent Resistance of Polyacrylonitrile journal August 2009
N,N ,N′,N′ - Tetraphenyl-1,4-phenylenediamine−Fluorene Alternating Conjugated Polymer: Synthesis, Characterization, and Electrochromic Application journal March 2010
A machine learning workflow for molecular analysis: application to melting points journal June 2020
Graph Rationalization with Environment-based Augmentations conference August 2022
Prediction of Polymer Properties book July 2002