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Issue 01/2020

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Highlights: Automotive Recycling Cover Story: Biobased Fur

new series By: Barry

new series By: Barry Dean, Naperville, Illinois, USA BIOPLASTIC patents U.S. Patent 10,392,317 (August 27, 2019),”Methods of Producing Para-Xylene And Terephthalic Acid”, Makoto N. Masuno, Ryan L. Smith, John Bissell II, Patrick B. Smith, Dennis A. Hucul, Edmund J. Stark, Daniel R. Henton, Adina Dumitrascu, Katherine Brune and Dimitri A. Hirsch- Weil (Micromidas Inc, West Sacramento, CA) Ref: WO2014/043468 Micromidas Inc along with Virent Inc, Anellotech Inc and Gevo are pursuing technologies to bio p-xylene with focus on bio terephthalic acid. In this citation, Micromidas teaches a process for the conversion of dimethylfuran and/or 2,5– hexanedione to p-xylene via the Diels Alder reaction with ethylene. The dimethylfuran and/or 2,5-hexanedione are bio derived while the ethylene can be fossil fuel or bio derived rendering bio p-xylene that is partially or wholly 100 % biogenic carbon content. The process described teaches the use of a catalyst and optionally a solvent to achieve Diels Alder yields of p-xylene that are >/= 90 %. The selection of catalyst and optionally solvent are broad based; the catalyst can be selected from metal salts, Lewis acids, sulfonic acids or heteropolyacids. Metal salts are selected from Groups 3, 9, 10, or 11 as well as the lathanide series in the periodic table The solvent(s) taught can be selected from the polar aprotic solvents, ethers/glymes and other solvent classes offering good thermal stability. An illustrative examples involves reacting dimethylfuran with ethylene at 250 °C with an initial ethylene pressure of 500 psi for seven hours using copper triflate catalyst to achieve a 90 % yield of p-xylene. This section highlights recent IP(patent) activity that is relevant to the field of bioplastics. The information offered is intended to acquaint the reader with a sampling of know-how being developed to enable growth of the bioplastics and bioadditives markets. U.S. Patent 10,407,547 (September 10, 2019), “Methods of Producing Compounds From (5-Halomethyl)Furfural”, Makoto Nathanael Masuno, Dimitri A. Hirsch-Weil, Ryan L. Smith and John Albert Bissell II (Micromidas Inc West Sacramento, CA) Ref: WO 2015/175528 In this patent processes are taught for converting (5-halomethyl)furfural more specifically, (5-chloromethyl) furfural to a variety of nylon precursors. Prior art has shown processes for conversion of cellulosic materials to (5-chloromethyl)furfural (shown below) rendering biogenic carbon available for further conversion to other chemical structures. Processes are taught for converting (5-chloromethyl) furfural to cyclohexanone, hexanediol, hexamethylene diamine and caprolactam; all precursors to nylon with biogenic carbon content. The processes described and illustrated all involve multi-step synthesis with dependence on the use of precious metal catalysts in select chemical conversions. For example the route to caprolactam, starting monomer for making nylon 6, is a four step synthesis involving oxidation, amination, reduction and reductive elimination. Bio-based nylons are a target for commercialization in the automotive and sporting goods markets. 42 bioplastics MAGAZINE [01/20] Vol. 15

Patents U.S. Patent 10,494,652 (Decembe 3, 2019), “Polyhydroxyalkanoic Acid Compositions And Methods For Generating Same”, Markus Donald Herrema and Kenton Kimmel (Newlight Technologies Inc Huntington Beach, CA) A process is taught for treating volatile organic compounds (VOCs) with a methane monooxyygenase (MMO) to render VOCs useful for microorganisms to convert to polyhydroxyalkanoates; whereas non treated VOC’s are toxic thereby limiting PHA growth within organisms. The VOCs contacted with a methane monooxygenase are fed into a reactor where the medium comprises microorganisms synthesizing the MMO, microorganism growth media and PHA synthesizing microorganism that have the capacity to use the MMO oxidized form of the VOCs for growth and PHA synthesis. The advantages taught are that this process can utilize VOCs emitted by a wide range of industrial processes rendering a waste product/environmentally harmful product as a potential low cost feedstock for the making of PHA polymers. The VOCs can be hydrocarbons, oxygenates and/or halogenated hydrocarbons. U.S. Patent 10,500,303 (December 10, 2019), “Self- Retaining Sutures of Poly-4-Hydroxybutyrate And Copolymer Thereof”, Said Rizik and Simon F. Williams (Tepha, Inc Lexington, MA) A material and method is taught for making a high strength, high hardness self retaining sutures. The polyhydroxyalkanoate taught is poly(4-hydroxybutyrate), ie 4-PHB. The monofilament structure is a sheath-core fiber with both sheath and core being PHB with the sheath exhibiting higher crystallinity than the core. Characteristics of the monofilament as illustrated are Young’s Modulus > 860 MPa, hardness of 0.07GPa and tensile strength of 0.25Kgf for a 0.070 – 0.149 mm diameter(where the tensile strength increases with fiber diameter. These properties illustrate the ability of the sheath-core 4-PHB to meet the minimum knot-pull tensile standard for sutures set by US Pharmacopia. The monofilament can be sterilized using ethylene oxide, electron beam radiation and gamma radiation. PHA copolymers are also taught as being useful in this invention. Another aspect of this invention which is taught and illustrated is the making of retain cuts into the sheath-core monofilament without compromising the knot-pull tensile performance. This type of suture is key for wound closures and other medical procedures. U.S. Patent 10,501,607 (December 10, 2019), “Polyphase Biodegradable Compositions Containing At Least One Polymer of Vegetable Origin”, Luigi Capuzzi (Novamont, S.P.A Novara, Italy) Ref: PCT/EP2011/063575 This patent teaches a composition and process for a renewable based material that can be competitive with polyethylene film in the shopping bag and wrapping applications for food at thicknesses of 18 – 20 um. The problem being solved by this teaching is lack of uniformity of mechanical properties of films(precursor to bags and wrappings) for biodegradable materials where starch is a dispersed phase. The composition taught is a polyphase biodegradable material having a continuous hydrophobic polyester phase(preferably 65 – 90 % by weight), a dispersed phase of vegetable origin(preferably 10 – 35 % by weight) and a plasticizer wherein 75 % of the plasticizer if derived from a mixture of diglycerol, triglycerol and tetraglycerol. The hydrophobic polyester taught can be an aliphatic and/or aliphatic-aromatic polymer. Examples cited include polylactic acid, polybutyleneadipate-co-terephthalate and the like. The dispersed phase of vegetable origin can be starch, cellulose and the like. A key teaching is the improvement and balance of machine and transverse direction properties of 20 um films (modulus and tear strength) when the plasticizer used has as majority components a mixture of diglycerol, triglycerol and tetraglycerol as compared to a reference 100 % glycerol. The teaching of this patent offers performance comparable to polyethylene films but with a composition that is biodegradable. U.S. Patent Application 2019/0359818 (November 28, 2019), “Biodegradable Polyester Resin Composition and Molded Article Formed From Said Resin Composition”, Tetsuya Minami (Kaneka Corporation Osaka-shi Japan) Ref: PCT/JP2017/003228 A composition is taught to improve the heat resistance and impact strength of polylactic acid (PLA) for applications in injection molding and extrusion flow molding. The composition is 30 – 60 % by weight PLA, 25 – 45 % by weight of poly-3-hydroxyalkanoate(3-PHA) , 5 – 25 % by weight aliphatic-aromatic polyester( eg polybutylene adipate-coterephthalate) for the continuous polymer matrix phase. A reinforcing additive to the ternary polymer blend is taught consisting of 10 – 40 weight % of a silicate(talc, mica, kaolinite or montmorillonite). Heat deflection temperature, Charpy impact strength and tensile elongation are shown to improve for the ternary polymer matrix with the silicate versus controls of PLA/silicate and binary polymer blends/ silicate. bioplastics MAGAZINE [01/20] Vol. 15 43

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