Biobased and Biodegradable polymers from P-Dioxanone Michigan State University & Bioplastics Polymers LLC Chetan Tambe and Ramani Narayan Commercial Impact Origin of Technology Biobased and biodegradable polymers are eco friendly and are replacing conventional polymers made from petroleum sources. It helps in decreasing the carbon footprint by sustaining nature’s carbon cycle. Polylactic acid (PLA) and Polybutylene adipate-co-terephthalate (PBAT) are commercially available biobased polymer. PLA is produced by NatureWorks llc and PBAT is produced by BASF. Poly(p-dioxanone) (PPDX) is a completely new polymeric system that is 100% biobased and biodegradable. It is a poly ester-ether and has an advantage because of vital ether linkages in the degradation. PPDX can be efficiently prepared from diethylene glycol which can be completely prepared from biobased sources. PPDX has great potential in the market in the area of food packaging, non-food packaging, compost bags and kitchen utensils etc. The main advantages are: Poly(p-dioxanone) is prepared by ring opening polymerization of p-Dioxanone P-Dioxanone can be synthesized from ethylene glycol or diethylene glycol Vapor phase catalytic dehydrogenation of DEG is found to be more efficient Polymerization can be carried out in the extruder- one step process Fig 4 : Reaction pathway in the synthesis of Poly(p-dioxanone) Catalytic dehydrogenation can be carried out in fixed bed tubular reactor Purity of the monomer is most important to get high molecular weight polymer, so recrystallization and vacuum distillation can be employed PPDX is 100% biobased and biodegradable which has a positive effect on the environment and minimizes the use of fossil fuel resources PPDX has better physical properties than PLA and PBAT in terms of brittleness, elongation break, tensile strength Easy to degrade as of ether linkages which can be easily broken down by hydrolytic cleavage Value Proposition Poly(p-dioxanone) is 100% biobased Fig 5 : Schematic of a Packed bed tubular reactor Fig 6 : Simplified process flow diagram for the production of monomer (p-dioxanone) and further polymer (PPDX) Conventionally made from petroleum feedstock which can be replaced biobased renewable feedstock It’s the intrinsic zero material carbon footprint value proposition Additionally PPDX is Biodegradable following ASTM D6400, EN 13432 Commercialization Team Biobased Materials Research Group (BMRG) design and engineer new biobased and biodegradable-compostable polymer materials and bio processes using agricultural crops and residues (soybean, and corn), lignocellulosic biomass, and algae. These biobased products find commercial application in films for plastic bags, injection molded articles, thermoformed products, foamed sheets for protective and insulation packaging, arts and crafts and toy materials, and biomedical applications. The group’s biobased materials technology platform is covered by 27 patents; 145 peer reviewed publications, and eight technologies have been licensed or resulted in a spin-out company. There are nine graduate students, several undergraduate students, two senior research staff, one postdoctoral and several visiting research fellows in the group. BioPlastic Polymers LLC is a technology development and commercialization company operating under a licensing agreement with Michigan State University for select BMRG technologies. The company identifies and creates strategic industrial and business partnerships to de-risk and bring to investment grade the BMRG technologies through start-up companies, JV’s or partnerships, and licensing agreements. References: Fig 1 : Biobased route for the synthesis of Poly(p-dioxanone) vs conventional route using non-renewable petroleum feedstock Narayan R, "Carbon footprint of bio-plastics using bio-carbon content analysis and life-cycle assessment," MRS Bull, V. 36, No. 9, Sep. 2011, pp. 716-21. Raquez JM, Coulembier O, Duda A, Narayan R, Dubois P, "Recent advances in the synthesis and applications of poly(1,4-dioxan-2-one)based copolymers," Polimery, V. 54, No. 3. 2009, pp. 165-78. Raquez JM, Degee P, Dubois P, Balakrishnan S, Narayan R, "Melt-stable poly(1,4-dioxan-2-one) (Co)polymers by ring-opening polymerization via continuous reactive extrusion," Polym Eng Sci, V. 45, No. 4, Apr. 2005, pp. 622-9. Forschner T.C. VCA, , Gwyn D.E., "Method for Preparing Poly-p-Dioxanone Polymer," US Patent, No. 5,652,331. 1997. Jeong, "Method for manufacturing ultrafine p-Dioxanone," International Patent, No. WO 2009/017261. 2009. Fig 2 : Tensile strength and elongation map (PPDX property comparison) PPDX can elongate 6 times longer than PLA Biaxial films- 5X tougher than LDPE Fig 3 : Physical property comparison with conventional fossil fuel based polymers i.e., Polycaprolactum (PCL), Low density polyethylene (LDPE), High density polyethylene (HDPE), Polypropylene (PP) ©  Michigan State University Biobased Materials (Narayan’s Research Group)