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Developing Renewable Bioplastics from Bio-Derived Monomers

Publication Date
Authors
Author Name
Preeti Jain
Author Organization
University of Kansas
Author Name
Charles Fields IV
Author Organization
University of Delaware
Author Name
Pranabesh Sahu
Author Organization
Pittsburg State University
Author Name
Kirk Snavely
Author Organization
University of Kansas
Author Name
Hyun Jin Lee
Author Organization
University of Kansas
Author Name
Raul Lobo
Author Organization
University of Delaware
Author Name
Tim Dawsey
Author Organization
Pittsburg State University
Author Name
Ram Gupta
Author Organization
Pittsburg State University
Author Name
Bala Subramaniam
Author Organization
University of Kansas

Enhancing the efficiency of material processing, utilization, and recycling is pivotal for advancing sustainability in modern society. The objective of this study is to create sustainable methods for converting non-food biomass into recyclable polymers. One key compound, 4,4'-biphenyldicarboxylic acid (BPDA), is used as an additive in copolymer production and as a blending agent to improve the properties of polyester. BPDA was synthesized through the oxidation of 4,4'-dimethylbiphenyl (DMBP), a compound that can be efficiently derived from biomass-sourced 2-methylfuran. Palladium acetate was used as a catalyst in the oxidative coupling of 2-methylfuran with oxygen, and La-triflates were employed to catalyze the tandem Diels-Alder-Dehydration of 5,5’-dimethylbifuran and ethylene to form DMBP, yielding 83% DMBP in 18 hours. DMBP was continuously fed into a stirred reactor in the molten state and oxidized at Mid-Century (MC) process conditions using Co/Mn/Br salts dissolved in acetic acid at 20 bar and 195 °C. BPDA was obtained in solid form at 91.2% yield and 98.7% purity and with complete DMBP conversion and ~92% carbon balance. Our findings thus indicate that the industrial production of BPDA can be achieved via the MC process. Subsequently, BPDA was esterified with methanol to yield 85% 4,4'-biphenyldicarboxylate (BPDC) with 99.7% purity. Polymerization of BPDC is then performed by combining 20-30% BPDC as a co-monomer with dimethyl terephthalate (DMT) in ethylene glycol, catalyzed by Ti(OBu)4. This results in a blended polyester suitable for applications in films and fibers, demonstrating the potential for sustainable polymer production from biomass-derived feedstocks.

Source
University of Kansas
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