Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate–co–terephthalate)

Aboukeila, Hesham; Singh, Onkar; Klier, John; Huber, George W.; Grady, Brian P.

doi:10.1002/pen.26878

Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate–co–terephthalate)

Journal Article · Fri Jul 26 00:00:00 EDT 2024 · Polymer Engineering and Science

DOI:https://doi.org/10.1002/pen.26878· OSTI ID:2407065

^[1]; Singh, Onkar ^[1]; Klier, John ^[1]; Huber, George W. ^[2]; ^[1]

University of Oklahoma, Norman, OK (United States)
University of Wisconsin–Madison, WI (United States)

Traditionally, most flexible food packaging is made of linear low-density polyethylene (LLDPE) which cannot easily be recycled, nor will it degrade in a reasonable timescale. In this work, a biobased biodegradable polyester alternative was investigated as a possible replacement for LLDPE. High molecular weight poly (pentylene adipate-co-terephthalate) with a 40/60 adipic acid/terephthalic acid mole ratio was synthesized using direct esterification and polycondensation. Glycerol and hexane-1,2,5,6-tetrol were added as branching agents to better match the structure of the LLDPE which in turn might help the ability of these materials in film-blowing. Thermal, mechanical, and rheological properties of the copolyesters were thoroughly investigated. All copolyesters had a weight-average molecular weight of over 140,000 g/mol, which is necessary for proper rheology, and were thermally stable up to 350°C. Here, the addition of branching agents led to a slight decrease in crystallinity, d-spacing, melting temperature, enthalpy of melting, stress at break, and elongation at break. However, an increase in Young's modulus and complex viscosity at high frequency were observed compared to PPeAT60 without branching agent added. Although the improved crystallinity and mechanical properties of the copolyesters made them viable for film-blowing, the slow crystallization rate creates a major challenge.

View Accepted Manuscript (DOE)

Research Organization:: University of Oklahoma, Norman, OK (United States); University of Wisconsin–Madison, WI (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: EE0009305

OSTI ID:: 2407065

Journal Information:: Polymer Engineering and Science, Journal Name: Polymer Engineering and Science Journal Issue: 10 Vol. 64; ISSN 0032-3888

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

Rheology of LLDPE, LDPE and LLDPE/LDPE blends and its relevance to the film blowing process Micic, Predrag; Bhattacharya, Sati N. Polymer International, Vol. 49, Issue 12 https://doi.org/10.1002/1097-0126(200012)49:12<1580::AID-PI547>3.0.CO;2-Q	journal	January 2000
Microbial Polyhydroxyalkanoates and Nonnatural Polyesters Choi, So Young; Cho, In Jin; Lee, Youngjoon Advanced Materials, Vol. 32, Issue 35 https://doi.org/10.1002/adma.201907138	journal	April 2020
Chemicals from Biomass: Combining Ring-Opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural Brentzel, Zachary J.; Barnett, Kevin J.; Huang, Kefeng ChemSusChem, Vol. 10, Issue 7 https://doi.org/10.1002/cssc.201700178	journal	March 2017
Microplastics in soils: a review of possible sources, analytical methods and ecological impacts Zhang, Bin; Yang, Xin; Chen, Liang Journal of Chemical Technology & Biotechnology, Vol. 95, Issue 8 https://doi.org/10.1002/jctb.6334	journal	February 2020
Film Blowing of Biodegradable Polymer Nanocomposites for Agricultural Applications Mistretta, Maria Chiara; Botta, Luigi; La Mantia, Francesco Paolo Macromolecular Materials and Engineering, Vol. 306, Issue 9 https://doi.org/10.1002/mame.202100177	journal	July 2021
Transient elongational viscosity of LLDPE/LDPE blends and its relevance to bubble stability in the film blowing process Micic, P.; Bhattacharya, S. N.; Field, G. Polymer Engineering & Science, Vol. 38, Issue 10 https://doi.org/10.1002/pen.10339	journal	October 1998
Tensile properties of linear low density polyethylene (LLDPE) blown films Krishnaswamy, Rajendra K.; Lamborn, Mark J. Polymer Engineering & Science, Vol. 40, Issue 11 https://doi.org/10.1002/pen.11370	journal	November 2000
Importance of elongational properties of polymer melts for film blowing and thermoforming Münstedt, Helmut; Kurzbeck, Stefan; Stange, Jens Polymer Engineering & Science, Vol. 46, Issue 9 https://doi.org/10.1002/pen.20588	journal	January 2006
Characterization and degradation behavior of poly(butylene adipate‐co‐terephthalate)s Herrera, Ricard; Franco, Lourdes; Rodríguez‐Galán, Alfonso Journal of Polymer Science Part A: Polymer Chemistry, Vol. 40, Issue 23 https://doi.org/10.1002/pola.10501	journal	October 2002
Isothermal crystallization kinetics of chain‐extended PET Sorrentino, L.; Iannace, S.; Di Maio, E. Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 15 https://doi.org/10.1002/polb.20480	journal	June 2005
Polyethylene Ronca, Sara Brydson's Plastics Materials https://doi.org/10.1016/B978-0-323-35824-8.00010-4	book	October 2016
Bio-based and sustainable food packaging systems: relevance, challenges, and prospects Donkor, Leticia; Kontoh, Gladys; Yaya, Abu Applied Food Research, Vol. 3, Issue 2 https://doi.org/10.1016/j.afres.2023.100356	journal	December 2023
Gas-phase dehydration of tetrahydrofurfuryl alcohol to dihydropyran over γ-Al2O3 Li, Ling; Barnett, Kevin J.; McClelland, Daniel J. Applied Catalysis B: Environmental, Vol. 245 https://doi.org/10.1016/j.apcatb.2018.12.039	journal	May 2019
Direct conversion of furfural to 1,5-pentanediol over a nickel–cobalt oxide–alumina trimetallic catalyst Kurniawan, Rizky Gilang; Karanwal, Neha; Park, Jaeyong Applied Catalysis B: Environmental, Vol. 320 https://doi.org/10.1016/j.apcatb.2022.121971	journal	January 2023
Improving economics of lignocellulosic biofuels: An integrated strategy for coproducing 1,5-pentanediol and ethanol Huang, Kefeng; Won, Wangyun; Barnett, Kevin J. Applied Energy, Vol. 213 https://doi.org/10.1016/j.apenergy.2017.11.002	journal	March 2018
Plastic in agricultural soils – A global risk for groundwater systems and drinking water supplies? – A review Wanner, Philipp Chemosphere, Vol. 264 https://doi.org/10.1016/j.chemosphere.2020.128453	journal	February 2021
Hazardous contaminants in plastics contained in compost and agricultural soil Scopetani, Costanza; Chelazzi, David; Cincinelli, Alessandra Chemosphere, Vol. 293 https://doi.org/10.1016/j.chemosphere.2022.133645	journal	April 2022
Fate and occurrence of micro(nano)plastics in soils: Knowledge gaps and possible risks Hurley, Rachel R.; Nizzetto, Luca Current Opinion in Environmental Science & Health, Vol. 1 https://doi.org/10.1016/j.coesh.2017.10.006	journal	February 2018
Policy considerations for limiting unintended residual plastic in agricultural soils Brodhagen, Marion; Goldberger, Jessica R.; Hayes, Douglas G. Environmental Science & Policy, Vol. 69 https://doi.org/10.1016/j.envsci.2016.12.014	journal	March 2017
Different structure transitions and tensile property of LLDPE film deformed at slow and very fast speeds Du, Wenjie; Ren, Yi; Tang, Yujing European Polymer Journal, Vol. 103 https://doi.org/10.1016/j.eurpolymj.2018.04.003	journal	June 2018
Selective and efficient production of 1,5-pentanediol from tetrahydrofurfuryl alcohol using Ni-La(OH)3 catalysts Zhao, Wenqi; Bai, Xiaowei; Lin, Xiangrui Fuel, Vol. 354 https://doi.org/10.1016/j.fuel.2023.129312	journal	December 2023
Processing of poly(lactic acid): Characterization of chemical structure, thermal stability and mechanical properties Carrasco, F.; Pagès, P.; Gámez-Pérez, J. Polymer Degradation and Stability, Vol. 95, Issue 2 https://doi.org/10.1016/j.polymdegradstab.2009.11.045	journal	February 2010
Synthesis and properties of long chain polyesters from biobased 1,5-pentanediol and aliphatic α,ω-diacids with 10-16 carbon atoms Zhou, Lizhong; Wu, Linbo; Qin, Pengkai Polymer Degradation and Stability, Vol. 187 https://doi.org/10.1016/j.polymdegradstab.2021.109546	journal	May 2021
Plastics in soil: Analytical methods and possible sources Bläsing, Melanie; Amelung, Wulf Science of The Total Environment, Vol. 612 https://doi.org/10.1016/j.scitotenv.2017.08.086	journal	January 2018
Effect of (bio)plastics on soil environment: A review Liwarska-Bizukojc, Ewa Science of The Total Environment, Vol. 795 https://doi.org/10.1016/j.scitotenv.2021.148889	journal	November 2021
Non-isothermal crystallization behavior of PLA/LLDPE/nanoclay hybrid: Synergistic role of LLDPE and clay As’habi, Ladan; Jafari, Seyed Hassan; Khonakdar, Hossein Ali Thermochimica Acta, Vol. 565 https://doi.org/10.1016/j.tca.2013.04.016	journal	August 2013
Application of bioplastics for food packaging Peelman, Nanou; Ragaert, Peter; De Meulenaer, Bruno Trends in Food Science & Technology, Vol. 32, Issue 2 https://doi.org/10.1016/j.tifs.2013.06.003	journal	August 2013
Are Agricultural Soils Dumps for Microplastics of Urban Origin? Nizzetto, Luca; Futter, Martyn; Langaas, Sindre Environmental Science & Technology, Vol. 50, Issue 20 https://doi.org/10.1021/acs.est.6b04140	journal	September 2016
Even–Odd Effect in Aliphatic Polycarbonates with Different Chain Lengths: from Poly (Hexamethylene Carbonate) to Poly (Dodecamethylene Carbonate) Pérez-Camargo, Ricardo A.; Meabe, Leire; Liu, Guoming Macromolecules, Vol. 54, Issue 1 https://doi.org/10.1021/acs.macromol.0c02374	journal	December 2020
Plastic Pollution: A Material Problem? Millican, Jonathan M.; Agarwal, Seema Macromolecules, Vol. 54, Issue 10 https://doi.org/10.1021/acs.macromol.0c02814	journal	April 2021
Perfectly Alternating Copolymerization of CO and Epoxides to Aliphatic Polyester Oligomers via Cooperative Organoboron–Cobalt Complexes Zhang, Yao-Yao; Yang, Li; Xie, Rui Macromolecules, Vol. 54, Issue 20 https://doi.org/10.1021/acs.macromol.1c01324	journal	October 2021
Bio-Based Poly(butylene furandicarboxylate-co-glycolate) Copolyesters: Synthesis, Properties, and Hydrolysis in Different Aquatic Environments for Water Degradation Application Ding, Yue; Huang, Dan; Ai, Tianhao ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 3 https://doi.org/10.1021/acssuschemeng.0c07351	journal	January 2021
Production of Hexane-1,2,5,6-tetrol from Biorenewable Levoglucosanol over Pt-WO_x/TiO₂ Cuello-Penaloza, Paolo; Krishna, Siddarth H.; De bruyn, Mario ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 48 https://doi.org/10.1021/acssuschemeng.1c04759	journal	November 2021
Biodegradable High-Molecular-Weight Poly(pentylene adipate-co-terephthalate): Synthesis, Thermo-Mechanical Properties, Microstructures, and Biodegradation Zheng, Lei; Kim, Min Soo; Xu, Shu ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 38 https://doi.org/10.1021/acssuschemeng.3c01831	journal	September 2023
Conversion of Furfural to 1,5-Pentanediol: Process Synthesis and Analysis Huang, Kefeng; Brentzel, Zachary J.; Barnett, Kevin J. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 6 https://doi.org/10.1021/acssuschemeng.7b00059	journal	May 2017
Autocatalytic Hydration of Dihydropyran to 1,5-Pentanediol Precursors via in situ Formation of Liquid- and Solid-Phase Acids Barnett, Kevin J.; McClelland, Daniel J.; Huber, George W. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 11 https://doi.org/10.1021/acssuschemeng.7b02208	journal	October 2017
From Lactic Acid to Poly(lactic acid) (PLA): Characterization and Analysis of PLA and Its Precursors Inkinen, Saara; Hakkarainen, Minna; Albertsson, Ann-Christine Biomacromolecules, Vol. 12, Issue 3 https://doi.org/10.1021/bm101302t	journal	March 2011
High Molecular Weight Poly(butylene succinate-co-butylene furandicarboxylate) Copolyesters: From Catalyzed Polycondensation Reaction to Thermomechanical Properties Wu, Linbo; Mincheva, Rosica; Xu, Yutao Biomacromolecules, Vol. 13, Issue 9 https://doi.org/10.1021/bm301044f	journal	August 2012
Blends of Linear and Long-Chain Branched Poly(l-lactide)s with High Melt Strength and Fast Crystallization Rate Wang, Liangyan; Jing, Xiabin; Cheng, Haibo Industrial & Engineering Chemistry Research, Vol. 51, Issue 30 https://doi.org/10.1021/ie300526u	journal	July 2012
A Spectroscopic Analysis of Poly(lactic acid) Structure Kang, Shuhui; Hsu, Shaw Ling; Stidham, Howard D. Macromolecules, Vol. 34, Issue 13, p. 4542-4548 https://doi.org/10.1021/ma0016026	journal	May 2001
Shear-Induced Crystallization in Novel Long Chain Branched Polypropylenes by in Situ Rheo-SAXS and -WAXD Agarwal, Pawan K.; Somani, Rajesh H.; Weng, Weiqing Macromolecules, Vol. 36, Issue 14 https://doi.org/10.1021/ma034154l	journal	July 2003
Glycerol Copolyesters: Control of Branching and Molecular Weight Using a Lipase Catalyst Kulshrestha, Ankur S.; Gao, Wei; Gross, Richard A. Macromolecules, Vol. 38, Issue 8, p. 3193-3204 https://doi.org/10.1021/ma0480190	journal	March 2005
Effect of the Precise Branching of Polyethylene at Each 21st CH₂ Group on Its Phase Transitions, Crystal Structure, and Morphology Qiu, Wulin; Sworen, John; Pyda, Marek Macromolecules, Vol. 39, Issue 1 https://doi.org/10.1021/ma052010w	journal	November 2005
Biobased poly(ethylene furanoate-co-ethylene succinate) copolyesters: solid state structure, melting point depression and biodegradability Terzopoulou, Zoe; Tsanaktsis, Vasilios; Bikiaris, Dimitrios N. RSC Advances, Vol. 6, Issue 87 https://doi.org/10.1039/c6ra15994j	journal	January 2016
Biobased copolyesters: synthesis, crystallization behavior, thermal and mechanical properties of poly(ethylene glycol sebacate-co-ethylene glycol 2,5-furan dicarboxylate) Wang, Guoqiang; Jiang, Min; Zhang, Qiang RSC Advances, Vol. 7, Issue 23 https://doi.org/10.1039/c6ra27795k	journal	January 2017
The effect of MDI on the structure and mechanical properties of poly(lactic acid) and poly(butylene adipate-co-butylene terephthalate) blends Pan, Hongwei; Li, Zonglin; Yang, Jia RSC Advances, Vol. 8, Issue 9 https://doi.org/10.1039/c7ra10745e	journal	January 2018
Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity Krishna, Siddarth H.; De bruyn, Mario; Schmidt, Zachary R. Green Chemistry, Vol. 20, Issue 19 https://doi.org/10.1039/c8gc02455c	journal	January 2018
Poly(lactic acid) (PLA) and polyhydroxyalkanoates (PHAs), green alternatives to petroleum-based plastics: a review Naser, Ahmed Z.; Deiab, I.; Darras, Basil M. RSC Advances, Vol. 11, Issue 28 https://doi.org/10.1039/d1ra02390j	journal	January 2021
Organic fertilizer as a vehicle for the entry of microplastic into the environment Weithmann, Nicolas; Möller, Julia N.; Löder, Martin G. J. Science Advances, Vol. 4, Issue 4 https://doi.org/10.1126/sciadv.aap8060	journal	April 2018
Poly(butylene adipate-co-terephthalate) Polyester Synthesis Process and Product Development No authors listed Polymer Science, Series C, Vol. 63, Issue 1 https://doi.org/10.1134/s1811238221010045	journal	January 2021
Film Blowing of Linear and Long-Chain Branched Poly(ethylene terephthalate) Härth, Michael; Dörnhöfer, Andrea Polymers, Vol. 12, Issue 7 https://doi.org/10.3390/polym12071605	journal	July 2020
Shear and Extensional Rheology of Linear and Branched Polybutylene Succinate Blends Bourg, Violette; Valette, Rudy; Le Moigne, Nicolas Polymers, Vol. 13, Issue 4 https://doi.org/10.3390/polym13040652	journal	February 2021
A Brief Review of Poly (Butylene Succinate) (PBS) and Its Main Copolymers: Synthesis, Blends, Composites, Biodegradability, and Applications Aliotta, Laura; Seggiani, Maurizia; Lazzeri, Andrea Polymers, Vol. 14, Issue 4 https://doi.org/10.3390/polym14040844	journal	February 2022
The Use of Branching Agents in the Synthesis of PBAT Nifant’ev, Ilya E.; Bagrov, Vladimir V.; Komarov, Pavel D. Polymers, Vol. 14, Issue 9 https://doi.org/10.3390/polym14091720	journal	April 2022
Polyhydroxybutyrate (PHB)-Based Biodegradable Polymer from Agromyces indicus: Enhanced Production, Characterization, and Optimization Adnan, Mohd; Siddiqui, Arif Jamal; Ashraf, Syed Amir Polymers, Vol. 14, Issue 19 https://doi.org/10.3390/polym14193982	journal	September 2022
Polymers Use as Mulch Films in Agriculture—A Review of History, Problems and Current Trends Mansoor, Zinnia; Tchuenbou-Magaia, Fideline; Kowalczuk, Marek Polymers, Vol. 14, Issue 23 https://doi.org/10.3390/polym14235062	journal	November 2022
Long-Chain Branched Bio-Based Poly(butylene dodecanedioate) Copolyester Using Pentaerythritol as Branching Agent: Synthesis, Thermo-Mechanical, and Rheological Properties Niu, Ruixue; Zheng, Zhening; Lv, Xuedong Polymers, Vol. 15, Issue 15 https://doi.org/10.3390/polym15153168	journal	July 2023
The Relation of Transition Temperatures to Chemical Structure in High Polymers Boyer, Raymond F. Rubber Chemistry and Technology, Vol. 36, Issue 5 https://doi.org/10.5254/1.3539649	journal	November 1963

Similar Records

Synthesis and characterization of biobased copolyesters based on pentanediol: (1) Poly(pentylene dodecanoate–co–furandicarboxylate)

Journal Article · Thu Jul 25 00:00:00 EDT 2024 · Polymer Engineering and Science · OSTI ID:2406994

Biodegradable High-Molecular-Weight Poly(pentylene adipate-co-terephthalate): Synthesis, Thermo-Mechanical Properties, Microstructures, and Biodegradation

Journal Article · Thu Sep 14 00:00:00 EDT 2023 · ACS Sustainable Chemistry & Engineering · OSTI ID:2283539

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
Biodegradable
Branched
PBAT
Pentanediol
Polyesters

Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate–co–terephthalate)

Citation Formats

References (58)

Similar Records

Related Subjects