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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Plant Polymer Research » Research » Research Project #428704

Research Project: Conversion of Polysaccharides and Other Bio-based Materials to High-Value, Commercial Products

Location: Plant Polymer Research

2016 Annual Report


Objectives
The overall goal is to produce novel bio-based materials from agricultural commodities to increase the market demand and value of U.S. non-food agricultural products and by-products, as well as to reduce the environmental impact from the plastics industry. Objective 1. Enable, from a technological standpoint, the commercial production of new bio-based polymers, graft-copolymers, composites, and blends from polysaccharides. Sub-Objective 1A. Selectively modify polysaccharides to provide higher product value using state-of-the-art, chemical methods and physical techniques, such as microwave, ultrasound, supercritical fluids, and on-line monitoring to produce materials suitable for coatings, personal care, food, and pharmaceutical applications. Sub-Objective 1B. Synthesize and evaluate bio-based polymers, polymer blends and polymer composites for environmentally responsive plastics, controlled release materials, and composite materials using industrial, continuous production methods such as extrusion.


Approach
Environmental concerns over the production and disposal of polymeric materials have prioritized the creation of new bio-based materials from agricultural feedstocks. Sustainable processing technologies are also needed to replace industrial and consumer products made from petroleum based feedstock. This project focuses on making bio-based polymeric materials with useful applications from agricultural products such as starch and associated low cost corn processing and harvesting co-products. Modified biopolymers with new properties will be prepared using the latest technologies available. Specific objectives for this project include: 1) Develop novel carbohydrate-based materials, such as starches, celluloses, and chitosan, with novel structures and/or through the use of microwaves, autoclave heating, reactive extrusion, jet cooking, and other green chemical methods; and 2) Demonstrate that the biobased polymeric materials can be used in high-value applications such as composite materials, packaging, controlled release devices, and environmental responsiveness. As an example, starch-based copolymers with novel and unique properties will be compounded by reactive extrusion, characterized, and processed into films or fibers and then evaluated for targeted properties and specific applications. Overall, this research will lead to bio-based polymer products with new or improved properties, have lower cost, are more environmentally friendly, and thus more acceptable to consumer markets. It will also generate new bio-based technologies enabling new market opportunities for agricultural products while reducing the environmental footprint relative to polymeric materials based on non-renewable resources.


Progress Report
Bio-based polymer systems are being developed and characterized for different applications such as 3D printer filaments, green polymer composites, and active packaging for food products. There were three technological challenges addressed this year. One of the technological challenges in using bio-based materials for 3D printing versus other methods of molding plastics (injection molding, extrusion, and blowing) is that there is no shear in the melting chamber of the 3D printer. Many unmodified bio-based materials do not “melt” and “flow” in the same way as commodity plastics. Over 25 different combinations were screened in order to find the right mix to melt in the chamber and be expressed by the nozzle. The second challenge is the ability of the printed plastic strands to adhere to each other in a 3D structure while printing and cooling. The plastic must remain melted enough to stick together for strength but solidify quickly enough to hold its shape. The bio-blend is lightly cross-linked, allowing a rapid solidification at the end of printing. All components are commercially available and biodegradable. Cyclodextrins (CD’s) are well known starch derived material. We developed a microwave-assisted method to modify CD molecules with diisocyanates to produce polyurethanes. As compared to conventional heating, this new synthetic method saved energy, significantly reduced reaction time, and yet improved the product yield. The reaction products have been fully characterized with nuclear magnetic resonance (NMR) spectroscopy. Our modified CD could complex with a variety of substances, e.g., drug molecules for improved solubility or controlled release, fragrance molecules for controlled release, cholesterol removal in the food industry, and removal of toxic substances from the environment. It also has the potential to be used for the detection of mycotoxins for food safety applications. A manuscript on this work was published. Cellulose is the earth's most abundant bio-polymer and is of tremendous economic importance. To expand the uses of cellulose acetate, studies and testing were done on the physical and mechanical properties of cellulose ester-based films incorporating essential oils (EO) from lemongrass, rosemary pepper, and basil at concentrations of 10-20% (v/w). The EO acted like a plasticizer and increased the flexibility of the polymer. Water barrier property was effectively improved when the film was composed of 20% of the three types of essential oils. However, the EO somewhat decrease the transparency of the films. This study indicates that EO-embedded cellulose ester films are particularly suitable for food packaging that requires low water vapor exchanges and decreased sensitivity to light. Farmers may benefit since this work potentially expands the applications of cellulose acetate, which is derived from cellulose from agricultural resources. A manuscript on this work was published. Devised chemometric algorithms, based on our novel Relative Differential Spectral Deconvolution theory, that compute relative strengths and free energies of noncovalent interactions between the multiple polymeric components in thermoplastic bio-based composites by Fourier transform infrared (FTIR) spectrometry. These colligative intermolecular and intramolecular interactions, which are caused by weak bonding, such as Van der Waals and London forces from induced dipole moments, are determined by measuring statistical changes that occur in the FTIR absorbance band parameters. This will facilitate the combination of bio-based polymers with synthetic polymers and help develop the concurrent technology for ensuring optimum performance. Acquisition of quantitative structure property relationships (QSPR) between components (proteins, polysaccharides, polylipids, and other bio-materials) will enable ARS research scientists in Peoria, Illinois, and collaborators to tailor bio-based composites for improved properties and more environmentally-friendly behavior.


Accomplishments
1. Bio-based filaments for 3D printing. ARS scientists in Peoria, Illinois, have developed and tested a thermoplastic material composed of components which are commercially available. The blend is plasticized and extruded to form filaments with a suitable diameter to be used by commercially available 3D printers. The biodegradable filaments have similar properties to existing plastics, although the cooling period of the printing process requires quicker response times to prevent slumping of the final product. The biobased material would reduce the carbon and energy footprint of existing plastic materials providing cost and environmental benefits. This agriculturally sourced product can be recycled or composted at the end of its use.

2. Developed a solventless and catalyst-free green pathway to incorporating nitrogen into cardanol. ARS scientists in Peoria, Illinois, have developed a catalyst-free green pathway to incorporating nitrogen into cardanol, a phenolic lipid obtained from cashew nutshell liquid (CNSL), which is a byproduct of cashew nut processing. In an effort to develop new industrial uses of cardanol, they discovered these new materials which can find use as coatings, cements, surfactants, lubricants, and cosmetics. It is possible that they may even have antimicrobial or pharmaceutical activities. A new use for cardanol was discovered.

3. Development of amino cardanol. ARS scientists in Peoria, Illinois, have developed a water-based environmentally-friendly green method to incorporate an amine group into cardanol with the help of an ionic liquid catalyst. New materials prepared can be used as improved, more stable lubricants, coatings, cosmetics, and agricultural chemicals. The material modified with formaldehyde can be formulated into adhesives, curing agents for epoxy resins, fuel cell materials, or water purification media. Furthermore, the modified cardanol can be a convenient carrier for fragrance or drug molecules.

4. Synthesis of an amine-oleate derivative using an ionic liquid catalyst. In this work, we reported the discovery of a new environmentally-friendly fast method to attach amine (nitrogen atom) to bio-oil. This technology (U.S. Patent No. 8,841,470 B1) provides a way to prepare new oil-based materials. Industrial chemical manufacturers will benefit from this discovery of new oil-based materials which can be used as ingredients in lubricants, coatings, cosmetics, biodiesel fuel, agricultural chemicals, spandex fibers, antioxidants, and pharmaceuticals.

5. A novel chemometric method was devised that corrects Fourier transform infrared (FTIR) spectra of biomaterials in KBr disks by mathematically eliminating water interference. As a result, the interference from water contained in the KBr, which has frustrated research chemists and infrared spectroscopists for almost 70 years, is no longer a problem. Now this problem is finally solved once and for all. Using this new mathematical solution, research efforts to eliminate water interference from KBr disks will be defeated no longer. Consequently, the correction method represents a significant advance toward practical infrared spectrometric analyses of solid biomaterials in nature. It has been described as an important breakthrough that removes a long-standing barrier to quantitative analyses of solid biomaterial structure in agricultural and many other fields of scientific research.


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Review Publications
Bastos, M.S.R., Laurentino, L.S., Canuto, K.M., Mendes, L.G., Martins, C.M., Silva, S.M.F., Furtado, R.F., Kim, S., Biswas, A., Cheng, H.N. 2016. Physical and mechanical testing of essential oil-embedded cellulose ester films. Polymer Testing. 49:156-161.
Biswas, A., Alves, C.R., Trevisan, M.T.S., Berfield, J., Furtado, R.F., Liu, Z., Cheng, H.N. 2016. Derivatives of cardanol through the ene reaction with diethyl azodicarboxylate. Journal of Brazilian Chemical Society. 27(6):1078-1082.
Biswas, A., Appell, M., Liu, Z., Cheng, H.N. 2015. Microwave-assisted synthesis of cyclodextrin polyurethanes. Carbohydrate Polymers. 133:74-79. doi: 10.1016/j.carbpol.2015.06.044.
Kim, S., Adkins, J., Biswas, A. 2015. Fabrication of latex rubber reinforced with micellar nanoparticle as an interface modifier. Journal of Elastomers and Plastics. 48(4):317-330. doi: 10.1177/0095244315576242.
Liu, Z., Sharma, B.K., Erhan, S.Z., Biswas, A., Wang, R., Schuman, T.P. 2015. Oxidation and low temperature stability of polymerized soybean oil-based lubricants. Thermochimica Acta. 601:9-16.
Biswas, A., Kim, S., He, Z., Cheng, H.N. 2015. Microwave-assisted synthesis and characterization of polyurethanes from TDI and starch. International Journal of Polymer Analysis and Characterization. 20(1):1-9. doi: 10.1080/1023666X.2015.975017.
Kim, S., Adkins, J., Aglan, H.A., Biswas, A., Selling, G. 2016. Polymer composites prepared from heat-treated starch and styrene-butadiene latex. Journal of Elastomers and Plastics. 48(1):80-93. doi: 10.1177/0095244314538440.
Biswas, A., Liu, Z., Cheng, H.N. 2016. Polymerization of epoxidized triglycerides with fluorosulfonic acid. International Journal of Polymer Analysis and Characterization. 21(1):85-93.
Gordon, S.H., Mohamed, A.A., Harry-O'Kuru, R.E., Biresaw, G. 2015. Identification and measurement of intermolecular interaction in polyester/polystyrene blends by FTIR-photoacoustic spectrometry. Journal of Polymers and the Environment. 23(4):459-469.
Selling, G.W., Utt, K.D., Finkenstadt, V., Kim, S., Biswas, A. 2015. Impact of solvent selection on graft co-polymerization of acrylamide onto starch. Journal of Polymers and the Environment. 23(3):294-301. doi: 10.1007/s10924-015-0714-y.
Melo, A.M.A., Alexandre, D.L., Furtado, R.F., Borges, M.F., Figueiredo, E.A.T., Biswas, A., Cheng, H.N., Alves, C.R. 2016. Electrochemical immunosensors for Salmonella detection in food. Applied Microbiology and Biotechnology. 100(12):5301-5312.
Biswas, A., Liu, Z., Berfield, J.L., Cheng, H.N. 2015. Synthesis of novel plant oil derivatives: Furan and Diels-Alder reaction products. International Journal of Agricultural Science and Technology. 3(2):28-35.
Xu, J., Solaiman, D., Ashby, R.D., Garcia, R.A., Gordon, S.H., Harry-O'kuru, R.E. 2016. Properties of starch-polyglutamic acid (PGA) graft copolymer prepared by microwave irradiation - Fourier transform infrared spectroscopy (FTIR) and rheology studies. Starch 68:1-7. doi: 10.1002/star.201600021.
Patel, J.S., Gao, E., Boddu, V.M., Stephenson, L.D., Kumar, A. 2016. Accelerated long-term assessment of thermal and chemical stability of bio-based phase change materials. Journal of Building Physics. doi: 10.1177/1744259115624178.
Fanta, G.F., Felker, F.C., Selling, G.W., Hay, W.T., Biswas, A. 2016. Poly(vinyl alcohol) composite films with high percent elongation prepared from amylose-fatty ammonium salt inclusion complexes. Journal of Applied Polymer Science. 133(42).
Xu, J., Krietemeyer, E.F., Finkenstadt, V.L., Solaiman, D., Ashby, R.D., Garcia, R.A. 2016. Preparation of starch-poly-glutamic acid graft copolymers by microwave irradiation and the characterization of their properties. Carbohydrate Polymers. 140:233-237.