Analysis of the Amorphous and Interphase Influence of Comononomer Loading on Polymer Properties toward Forwarding Bioadvantaged Copolyamides

Abdolmohammadi, Sanaz; Gansebom, Dustin; Goyal, Shailja; Lee, Ting-Han; Kuehl, Baker; Forrester, Michael J.; Lin, Fang-Yi; Hernández, Nacú; Shanks, Brent H.; Tessonnier, Jean-Philippe; Cochran, Eric W.

doi:10.1021/acs.macromol.1c00651

Analysis of the Amorphous and Interphase Influence of Comononomer Loading on Polymer Properties toward Forwarding Bioadvantaged Copolyamides

Journal Article · Tue Aug 17 00:00:00 EDT 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.1c00651· OSTI ID:1848819

Abdolmohammadi, Sanaz ^[1]; ^[2]; ^[3]; Lee, Ting-Han ^[3]; Kuehl, Baker ^[3]; ^[3]; Lin, Fang-Yi ^[3]; ^[3]; ^[2]; ^[2]; ^[3]

Iowa State University, Ames, IA (United States); Center for Biorenewable Chemicals (CBiRC), Ames, IA (United States); Iowa State University
Iowa State University, Ames, IA (United States); Center for Biorenewable Chemicals (CBiRC), Ames, IA (United States)
Iowa State University, Ames, IA (United States)

In this paper we present an approach for selectively modifying the properties of semicrystalline polymers by introducing “bioadvantaged” counits. With this approach, the unique functionality of biomass can be leveraged to tailor the properties of the amorphous phase of semicrystalline polymers with minimal impact on crystallinity and thermomechanical properties. As a model case, PA 6,6 copolyamides were produced using the bioadvantaged monomer trans-3-hexenedioic acid (t3HDA). The analogous structure of t3HDA to adipic acid, a PA 6,6 monomer, allows for seamless integration. Screening over the entire composition range identified the t3HDA loading (20 mol%) beyond which properties deviate appreciably from Nylon 6,6. Once identified, copolyamides of suitable compositions were upgraded to commercial quality and fully characterized to assess the influence of counit loading and polymer structure on thermal and mechanical properties. Samples were characterized using gel permeation chromatography (GPC), proton nuclear magnetic resonance spectroscopy (1H NMR), heteronuclear single quantum coherence spectroscopy (HSQC), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), tensile testing, flexural testing, and water absorption testing. t3HDA units were shown to hydrate during the harsh polycondensation to 3-hydroxyhexanedioic acid (3HHDA) and fully incorporate into the polymer backbone. Loading levels up to 20% were shown to have comparable thermal and mechanical properties in the dry state, yet moisture absorption—a known method for improving the toughness, yield strain, and elongation of polyamides—was enhanced by over 100% at 20% loading. This case study on bioadvantaged copolymers elucidates the governing structure-function principles that can be leveraged to forward value-added renewable polymers.

View Accepted Manuscript (DOE)

Research Organization:: Iowa State University, Ames, IA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008492

OSTI ID:: 1848819

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 17 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

Crystallization kinetics of poly(L-lactide-co-meso-lactide) Kolstad, Jeffrey J. Journal of Applied Polymer Science, Vol. 62, Issue 7 https://doi.org/10.1002/(SICI)1097-4628(19961114)62:7<1079::AID-APP14>3.0.CO;2-1	journal	November 1996
Thermal degradation of nylon polymers Holland, Barry J.; Hay, James N. Polymer International, Vol. 49, Issue 9 https://doi.org/10.1002/1097-0126(200009)49:9<943::AID-PI400>3.0.CO;2-5	journal	January 2000
Biodegradable Xylitol-Based Polymers Bruggeman, Joost P.; Bettinger, Christopher J.; Nijst, Christiaan L. E. Advanced Materials, Vol. 20, Issue 10 https://doi.org/10.1002/adma.200702377	journal	May 2008
4-Dialkylaminopyridines as Highly Active Acylation Catalysts. [New synthetic method (25)] Höfle, Gerhard; Steglich, Wolfgang; Vorbrüggen, Helmut Angewandte Chemie International Edition in English, Vol. 17, Issue 8 https://doi.org/10.1002/anie.197805691	journal	August 1978
Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar Suastegui, Miguel; Matthiesen, John E.; Carraher, Jack M. Angewandte Chemie International Edition, Vol. 55, Issue 7 https://doi.org/10.1002/anie.201509653	journal	January 2016
Biorenewable blends of polyamide‐4,10 and polyamide‐6,10 Moran, Christopher S.; Barthelon, Agathe; Pearsall, Andrew Journal of Applied Polymer Science, Vol. 133, Issue 45 https://doi.org/10.1002/app.43626	journal	April 2016
Synthesis and properties of polyamides from 2,5-furandicarboxylic acid: Research Article Cousin, Thibault; Galy, Jocelyne; Rousseau, Alain Journal of Applied Polymer Science, Vol. 135, Issue 8 https://doi.org/10.1002/app.45901	journal	October 2017
Synthesis and characterization of poly (1,6-hexamethylene oxamide-co-m-xylene oxamide) copolymers Yang, Tingting; Mutua, Fredrick Nzioka; Gao, Yuanbo Polymers for Advanced Technologies, Vol. 29, Issue 12 https://doi.org/10.1002/pat.4414	journal	July 2018
Crystallization-induced formation of rigid amorphous fraction Di Lorenzo, Maria Laura; Righetti, Maria Cristina Polymer Crystallization, Vol. 1, Issue 2 https://doi.org/10.1002/pcr2.10023	journal	August 2018
Influence of molecular weight and molecular weight distribution on mechanical properties of polymers Nunes, Ronald W.; Martin, John R.; Johnson, Julian F. Polymer Engineering and Science, Vol. 22, Issue 4 https://doi.org/10.1002/pen.760220402	journal	March 1982
The microstructure of injection-molded semicrystalline polymers: A review Katti, S. S.; Schultz, M. Polymer Engineering and Science, Vol. 22, Issue 16 https://doi.org/10.1002/pen.760221602	journal	November 1982
Influence of molecular weight and degree of crosslinking on the specific volume and glass temperature of polymers Fox, T. G.; Loshaek, S. Journal of Polymer Science, Vol. 15, Issue 80 https://doi.org/10.1002/pol.1955.120158006	journal	February 1955
Effect of crystallinity on the properties of nylons Starkweather, Howard W.; Moore, George E.; Hansen, John E. Journal of Polymer Science, Vol. 21, Issue 98 https://doi.org/10.1002/pol.1956.120219803	journal	August 1956
Crystalline transitions in powders of nylon 66 crystallized from solution Starkweather, Howard W.; Jones, Glover A. Journal of Polymer Science: Polymer Physics Edition, Vol. 19, Issue 3 https://doi.org/10.1002/pol.1981.180190307	journal	March 1981
The structure of copolymer crystals formed from dilute solution and in bulk Domszy, R. C.; Alamo, R.; Mathieu, P. J. M. Journal of Polymer Science: Polymer Physics Edition, Vol. 22, Issue 10 https://doi.org/10.1002/pol.1984.180221003	journal	October 1984
Spherulite growth rate and fold surface free energy of the form II mesophase in isotactic polybutene-1 and random butene-1/ethylene copolymers Stolte, Isabell; Androsch, René; Di Lorenzo, Maria Laura Colloid and Polymer Science, Vol. 292, Issue 6 https://doi.org/10.1007/s00396-014-3221-0	journal	April 2014
Studies on the crystallization and melting of nylon-6,6: 1. The dependence of the Brill transition on the crystallization temperature Ramesh, C.; Keller, A.; Eltink, S. J. E. A. Polymer, Vol. 35, Issue 12 https://doi.org/10.1016/0032-3861(94)90367-0	journal	June 1994
Biorefining of biomass to liquid fuels and organic chemicals Levy, P. F.; Sanderson, J. E.; Kispert, R. G. Enzyme and Microbial Technology, Vol. 3, Issue 3 https://doi.org/10.1016/0141-0229(81)90087-9	journal	July 1981
Economics of biofuels: Market potential of furfural and its derivatives Dalvand, Kaveh; Rubin, Jonathan; Gunukula, Sampath Biomass and Bioenergy, Vol. 115 https://doi.org/10.1016/j.biombioe.2018.04.005	journal	August 2018
Biotechnological production of muconic acid: current status and future prospects Xie, Neng-Zhong; Liang, Hong; Huang, Ri-Bo Biotechnology Advances, Vol. 32, Issue 3 https://doi.org/10.1016/j.biotechadv.2014.04.001	journal	May 2014
Laboratory investigation of using acrylated epoxidized soybean oil (AESO) for asphalt modification Chen, Conglin; Podolsky, Joseph H.; Williams, R. Christopher Construction and Building Materials, Vol. 187 https://doi.org/10.1016/j.conbuildmat.2018.07.204	journal	October 2018
Evaluation of kinetics parameters for poly(l-lactic acid) hydrolysis under high-pressure steam Mohd-Adnan, Ahmad-Faris; Nishida, Haruo; Shirai, Yoshihito Polymer Degradation and Stability, Vol. 93, Issue 6 https://doi.org/10.1016/j.polymdegradstab.2008.03.022	journal	June 2008
The suppression of strain induced crystallization in PET through sub micron TiO2 particle incorporation Taniguchi, Atsushi; Cakmak, Miko Polymer, Vol. 45, Issue 19 https://doi.org/10.1016/j.polymer.2004.06.056	journal	September 2004
Transcrystallinity in aramid and carbon fiber reinforced nylon 66: determining the lamellar orientation by synchrotron X-ray micro diffraction Feldman, Alexander Y.; Fernanda Gonzalez, M.; Wachtel, Ellen Polymer, Vol. 45, Issue 21 https://doi.org/10.1016/j.polymer.2004.08.027	journal	September 2004
Tailoring the rigid amorphous fraction of isotactic polybutene-1 by ethylene chain defects Di Lorenzo, Maria Laura; Androsch, René; Stolte, Isabell Polymer, Vol. 55, Issue 23 https://doi.org/10.1016/j.polymer.2014.09.040	journal	November 2014
Production costs of the chemical industry in the EU and other countries: Ammonia, methanol and light olefins Boulamanti, Aikaterini; Moya, Jose A. Renewable and Sustainable Energy Reviews, Vol. 68 https://doi.org/10.1016/j.rser.2016.02.021	journal	February 2017
Multilevel engineering of the upstream module of aromatic amino acid biosynthesis in Saccharomyces cerevisiae for high production of polymer and drug precursors Suástegui, Miguel; Yu Ng, Chiam; Chowdhury, Anupam Metabolic Engineering, Vol. 42 https://doi.org/10.1016/j.ymben.2017.06.008	journal	July 2017
Engineering glucose metabolism for enhanced muconic acid production in Pseudomonas putida KT2440 Bentley, Gayle J.; Narayanan, Niju; Jha, Ramesh K. Metabolic Engineering, Vol. 59 https://doi.org/10.1016/j.ymben.2020.01.001	journal	May 2020
Self-Assembly of Poly(styrene- block -acrylated epoxidized soybean oil) Star-Brush-Like Block Copolymers Lin, Fang-Yi; Hohmann, Austin D.; Hernández, Nacú Macromolecules, Vol. 53, Issue 18 https://doi.org/10.1021/acs.macromol.0c00441	journal	August 2020
Insights into the Role of Hydrogen Bonds on the Mechanical Properties of Polymer Networks Huang, Xin; Nakagawa, Shintaro; Houjou, Hirohiko Macromolecules, Vol. 54, Issue 9 https://doi.org/10.1021/acs.macromol.1c00120	journal	April 2021
Biorenewable Tough Blends of Polylactide and Acrylated Epoxidized Soybean Oil Compatibilized by a Polylactide Star Polymer Mauck, Sheli C.; Wang, Shu; Ding, Wenyue Macromolecules, Vol. 49, Issue 5 https://doi.org/10.1021/acs.macromol.5b02613	journal	February 2016
Electrochemical Conversion of Muconic Acid to Biobased Diacid Monomers Matthiesen, John E.; Carraher, Jack M.; Vasiliu, Monica ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 6 https://doi.org/10.1021/acssuschemeng.6b00679	journal	May 2016
Electrochemical Conversion of Biologically Produced Muconic Acid: Key Considerations for Scale-Up and Corresponding Technoeconomic Analysis Matthiesen, John E.; Suástegui, Miguel; Wu, Yutong ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12 https://doi.org/10.1021/acssuschemeng.6b01981	journal	October 2016
Itaconic Acid as a Green Alternative to Acrylic Acid for Producing a Soybean Oil-Based Thermoset: Synthesis and Properties Li, Peng; Ma, Songqi; Dai, Jinyue ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 1 https://doi.org/10.1021/acssuschemeng.6b02654	journal	December 2016
Development of High Performance Polyurethane Elastomers Using Vanillin-Based Green Polyol Chain Extender Originating from Lignocellulosic Biomass Gang, Haemin; Lee, Daewoo; Choi, Kwon-Young ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 6 https://doi.org/10.1021/acssuschemeng.6b02960	journal	April 2017
Conversion of biomass into chemicals with high-temperature wet oxidation McGinnis, Gary D.; Wilson, Wilber W.; Prince, Shawn E. Industrial & Engineering Chemistry Product Research and Development, Vol. 22, Issue 4 https://doi.org/10.1021/i300012a022	journal	December 1983
The Furans: Fifteen Years of Progress Peters, Fredus N. Industrial & Engineering Chemistry, Vol. 28, Issue 7 https://doi.org/10.1021/ie50319a002	journal	July 1936
Industrial Development of Furfural Brownlee, Harold J.; Miner, Carl S. Industrial & Engineering Chemistry, Vol. 40, Issue 2 https://doi.org/10.1021/ie50458a005	journal	February 1948
Crystallization in High Polymers. VII. Heat of Fusion of Poly-(N,N'-sebacoylpiperazine) and its Interaction with Diluents ¹ Flory, Paul J.; Mandelkern, Leo; Hall, Henry K. Journal of the American Chemical Society, Vol. 73, Issue 6 https://doi.org/10.1021/ja01150a035	journal	June 1951
Crystallization in High Polymers. V. Dependence of Melting Temperatures of Polyesters and Polyamides on Composition and Molecular Weight ^1,2 Evans, Robert D.; Mighton, Harold R.; Flory, Paul J. Journal of the American Chemical Society, Vol. 72, Issue 5 https://doi.org/10.1021/ja01161a040	journal	May 1950
Highly Powerful and Practical Acylation of Alcohols with Acid Anhydride Catalyzed by Bi(OTf) ₃ Orita, Akihiro; Tanahashi, Chiaki; Kakuda, Atsushi The Journal of Organic Chemistry, Vol. 66, Issue 26 https://doi.org/10.1021/jo0107453	journal	November 2001
An Extremely Powerful Acylation Reaction of Alcohols with Acid Anhydrides Catalyzed by Trimethylsilyl Trifluoromethanesulfonate Procopiou, Panayiotis A.; Baugh, Simon P. D.; Flack, Stephen S. The Journal of Organic Chemistry, Vol. 63, Issue 7 https://doi.org/10.1021/jo980011z	journal	March 1998
Premelting crystalline relaxations and phase transitions in nylon 6 and 6,6 Murthy, N. S.; Curran, S. A.; Aharoni, S. M. Macromolecules, Vol. 24, Issue 11 https://doi.org/10.1021/ma00011a027	journal	May 1991
Dependence of the Brill Transition on the Crystal Size of Nylon 10 10 Yang, Xiaoniu; Tan, Susheng; Li, Gao Macromolecules, Vol. 34, Issue 17 https://doi.org/10.1021/ma002091q	journal	July 2001
The Brill Transition in Transcrystalline Nylon-66 Feldman, A. Y.; Wachtel, E.; Vaughan, G. B. M. Macromolecules, Vol. 39, Issue 13 https://doi.org/10.1021/ma060487h	journal	June 2006
The Role of the Rigid Amorphous Fraction on Cold Crystallization of Poly(3-hydroxybutyrate) Di Lorenzo, Maria Laura; Gazzano, Massimo; Righetti, Maria Cristina Macromolecules, Vol. 45, Issue 14 https://doi.org/10.1021/ma3010907	journal	July 2012
Interactions between Crystalline and Amorphous Domains in Semicrystalline Polymers: Small-Angle X-ray Scattering Studies of the Brill Transition in Nylon 6,6 Murthy, N. Sanjeeva; Wang, Zhi-Gang; Hsiao, Benjamin S. Macromolecules, Vol. 32, Issue 17 https://doi.org/10.1021/ma990475e	journal	July 1999
Molecular morphology in semicrystalline polymers Flory, Paul J.; Yoon, Do Yeung Nature, Vol. 272, Issue 5650 https://doi.org/10.1038/272226a0	journal	March 1978
Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited Bozell, Joseph J.; Petersen, Gene R. Green Chemistry, Vol. 12, Issue 4, p. 539-554 https://doi.org/10.1039/B922014C	journal	January 2010
The battle for the “green” polymer. Different approaches for biopolymer synthesis: bioadvantaged vs. bioreplacement Hernández, Nacú; Williams, R. Christopher; Cochran, Eric W. Org. Biomol. Chem., Vol. 12, Issue 18 https://doi.org/10.1039/C3OB42339E	journal	January 2014
Adipic acid production from lignin Vardon, Derek R.; Franden, Mary Ann; Johnson, Christopher W. Energy & Environmental Science, Vol. 8, Issue 2 https://doi.org/10.1039/C4EE03230F	journal	January 2015
Catalytic routes towards acrylic acid, adipic acid and ε-caprolactam starting from biorenewables Beerthuis, Rolf; Rothenberg, Gadi; Shiju, N. Raveendran Green Chemistry, Vol. 17, Issue 3 https://doi.org/10.1039/C4GC02076F	journal	January 2015
Bioprivileged molecules: creating value from biomass Shanks, Brent H.; Keeling, Peter L. Green Chemistry, Vol. 19, Issue 14 https://doi.org/10.1039/C7GC00296C	journal	January 2017
A simple strategy toward the substitution of styrene by sobrerol-based monomers in unsaturated polyester resins Lima, Mafalda S.; Costa, Cátia S. M. F.; Coelho, Jorge F. J. Green Chemistry, Vol. 20, Issue 21 https://doi.org/10.1039/C8GC01214H	journal	January 2018
Renewable polyols for advanced polyurethane foams from diverse biomass resources Furtwengler, Pierre; Avérous, Luc Polymer Chemistry, Vol. 9, Issue 32 https://doi.org/10.1039/C8PY00827B	journal	January 2018
Theory of crystallization in copolymers Flory, Paul J. Transactions of the Faraday Society, Vol. 51 https://doi.org/10.1039/TF9555100848	journal	January 1955
Thermodynamics of Crystallization in High Polymers II. Simplified Derivation of Melting‐Point Relationships Flory, Paul J. The Journal of Chemical Physics, Vol. 15, Issue 9 https://doi.org/10.1063/1.1746627	journal	September 1947
Chemicals from Biomass: Petrochemical Substitution Options Lipinsky, E. S. Science, Vol. 212, Issue 4502 https://doi.org/10.1126/science.212.4502.1465	journal	June 1981
Biomass Ethanol: Technical Progress, Opportunities, and Commercial Challenges Wyman, Charles E. Annual Review of Energy and the Environment, Vol. 24, Issue 1, p. 189-226 https://doi.org/10.1146/annurev.energy.24.1.189	journal	November 1999
The Relation between Structure and Properties of Crystalline Polymers Mandelkern, Leo Polymer Journal, Vol. 17, Issue 1 https://doi.org/10.1295/polymj.17.337	journal	January 1985
Top Value Added Chemicals from Biomass: Volume I -- Results of Screening for Potential Candidates from Sugars and Synthesis Gas Werpy, T.; Petersen, G. https://doi.org/10.2172/15008859	report	August 2004
Amorphous and crystalline phase interaction during the Brill transition in nylon 66 Wolanov, Y.; Feldman, A. Y.; Harel, H. Express Polymer Letters, Vol. 3, Issue 7 https://doi.org/10.3144/expresspolymlett.2009.55	journal	January 2009
Review on the Impact of Polyols on the Properties of Bio-Based Polyesters Lang, Kening; Sánchez-Leija, Regina J.; Gross, Richard A. Polymers, Vol. 12, Issue 12 https://doi.org/10.3390/polym12122969	journal	December 2020