Day 2 :
Keynote Forum
Etienne Grau
University of Bordeaux, France
Keynote: Fully bio-based non-Isocyanate polyurethanes (NIPU) via cyclic carbonate/amine route
Time : 10:00-10:25
Biography:
Etienne Grau was trained in chemistry and physical chemistry at the ENS Cachan (France) and then undertook a PhD in polymer chemistry at CPE Lyon (France), where he studied the radical and catalytic polymerization of ethylene and its copolymerization with polar monomers in the C2P2 laboratory under the supervision of Dr. Vincent Monteil, Dr. Christophe Boisson and Dr. Roger Spitz (2007-2010). During a first post-doctoral stay, he studied Ziegler-Natta catalysis merging theoretical (with Prof. Phillipe Sautet at the ENS Lyon), surface (Prof. Christophe Copéret at ETH Zurich) and polymer chemistry (with Dr. Vincent Monteil at C2P2). Then in 2012, he moved to the group of Prof. Stefan Mecking in Konstanz (Germany) to work on Pd catalysis of the synthesis of monomers from lipids and terpenes. He was recruited by LCPO in 2013 as Assistant Professor in the group of Prof. Henri Cramail for his expertise in polymer chemistry and catalysis. He published around 30 articles and 10 patents. He received the best 2011 thesis prize of the French polymer group (GFP).
Abstract:
Thermoplastic poly(hydroxyurethane)s (PHUs) raised industrial and academic research curiosity, since their synthesis is achieved via the ring-opening of bis-cyclic carbonates with diamines, enabling the replacement of phosgene and isocyanates employed in the classical polyurethane (PU) manufacture. Due to fossil fuel depletion and environmental concerns, the use of building-blocks from renewable resources is highly investigated. Combining PHUs synthesis and bio-based compounds, a large platform of fatty acid-based cyclic carbonates as poly(hydroxyurethane) precursors was synthesized by epoxidation/carbonation routes. However, such monomers exhibited a slow polymerization rate towards amines, due to the electron-releasing alkyl chains, which deactivate the cyclic carbonates. rnAn alternative route consists in inserting a heteroatom nearby the cyclic carbonate to improve/activate its reactivity. Herein, the synthesis of new activated lipidic cyclic carbonates from glycerol carbonate and epichlorohydrin has been achieved, leading respectively to an ester or an ether linkage in β position of the carbonate. After kinetic investigations of the cyclic carbonate aminolysis on model compounds, the corresponding activated bis-cyclic carbonates were polymerized with two diamines and exhibited enhanced reactivities. A specific focus on the side reactions that could occur in both model reaction and polymerization is also discussed. rnOn the other hand, a new route to access bio-based diamines using mild and green conditions has been set up through an optimization of aliphatic alcohol oxidation into the corresponding nitriles, followed by an hydrogenation. The resulting diamines were subsequently polymerized with activated cyclic carbonates in order to obtain fully bio-based poly(hydroxy urethane)s.
Keynote Forum
David Grewell
Iowa State University, USA
Keynote: Sustainable plastics and the center for bioplastics and biocomposites
Time : 10:25-10:50
Biography:
Dr. David Grewell received a BS, MS and Ph.D. in Industrial Systems and Welding Engineering from The Ohio State University. He holds 14 patents, has been given numerous honors and awards and as well as numerous publications, including two books. His interests include joining of plastics, micro-fabrication, laser processing of materials, bioplastics and biofuels. He currently works at Iowa State University as a Professor in the department of Agricultural and Biosystems Engineering. Dr. Grewell is the Director of the NSF Center for Bioplastics and Biocomposites, is the Chair of the Biopolymers & Biocomposites Research Team, a Board Member of the Ultrasonic Industry Association, Society of Plastics Industry and Society of Plastics Engineers. He also has a position at the University of Erlangen in Germany and is Fellow of the Society of Plastics Engineers.
Abstract:
In this presentation, we review the basic concepts and history of bioplastics and biocomposites. We then provide an overview of the current state of the field. While there have been many early developments in bioplastics and examples of biocomposites in the last 60 years, today this technology has gained increased interest with many applications, and there are new products and materials under development and commercialization. The National Science Foundation (NSF) has recently funded an Industry/University Cooperative Research Center (I/UCRC) focused on bioplastics and bioplastics. Designated as the Center for Bioplastics and Biocomposites (CB2), this center is led by Iowa State University and Washington State University. The thrust of this new NSF center will be reviewed along with the center’s benefits to the bioplastics and biocomposites industry.
Coffee Break: 10:50 - 11:10 @ Foyer
- Track 11: Biopolymer Applications
Track 4: PlasticPollution and Waste Management
Location: Texas B
Chair
Amar Mohanty
University of Guelph, Canada
Co-Chair
Johan Pluyter
International Flavors and Fragrances, USA
Session Introduction
Johan Pluyter
International Flavors and Fragrances, USA
Title: Biopolymers in flavor and fragrance delivery systems
Time : 11:10-11:30
Biography:
Johan Pluyter completed his PhD at the University of North Carolina at Chapel Hill in Physical chemistry with an emphasis in Polymer Science. Following his PhD he worked at Procter & Gamble. Next, he lead physical, polymer and colloid characterization at National Starch and Chemical Company (under Unilever and ICI). Since 2002 he leads research in delivery systems at International Flavors and Fragrances (IFF) where he is a Senior Research Fellow. He is inventor and co-inventor of 21 granted US patents (Intl. as well) and many pending applications.
Abstract:
The use of microcapsules in fragrance has since 2006 become a key technology in home care (fabric softeners and detergents) and personal care (antiperspirants/deodorants) to enable efficient delivery of fragrances during the product use. The aim here is to obtain performance benefits such as a longer lasting release of the fragrance, a higher quality longer lasting fragrance (lasting freshness), and fragrance release during handling of wet and dry fabrics, release of fragrance during enhanced physical activity of the wearer, and enhanced bloom during application. As such, a key aspect of the microcapsule performance is to deposit as many capsules as possible during product application. Another challenge is minimizing the fragrance diffusion out of the capsules into the consumer product as this negatively impacts shelf life and transportation in hot climates. However, it is imperative that the fragrance is released during use of the product and wear of the substrates. Biopolymers are used in many facets of encapsulation of flavors and fragrances. Biopolymers are used in encapsulation techniques based on complex coacervation (gelatin), spray drying (starch), and emptied cells (yeast, spores). Furthermore, biopolymers are used as dispersants/emulsifiers in encapsulation (i.e. beverage emulsions), as rheololgy modifiers in aqueous-based microcapsule dispersions. In addition, biopolymers or modified biopolymers can be used to modify capsule surface as to improve their deposition ability in rinse-off applications (detergent, shampoo, hair conditioner, body wash). This presentation will provide an overview flavor/fragrance encapsulation as well as examples of where biopolymers and biobased materials are being used.
Birendra B. Adhikari
University of Alberta, Canada
Title: Development of bio-based plywood adhesive utilizing protein recovered from hydrolyzed specified risk materials
Time : 11:30-11:50
Biography:
B.B. Adhikari has completed his PhD in chemistry from Saga University, Japan, and postdoctoral studies in chemistry from California State University Long Beach, CA, USA. Currently, he is pursuing another postdoctoral studies in bioresource engineering at University of Alberta, AB, Canada. His reseaerch experiences lie in multidisciplinary areas combining organic and analytical chemistry as well as chemical and bioresource engineering. He has published 16 papers as the first author, and has shared authorship in 15 papers in reputed peer reviewed journals publishing in chemistry and chemical engineering.
Abstract:
Currently, production of composite wood products relies almost exclusively on petrochemical-based resins, more especifically the formaldehyde-based resins, as adhesives. As petrochemicals are obtained from non-renewable resources and formaldehyde is a known carcinogen, this research was conducted with the aim to develop a formaldehyde-free plywood adhesive system utilizing waste protein as a renewable feedstock. The feedstock for this work was specified risk material (SRM), which constitutes the bovine tissues that are completely banned from any food, feed, and fertilizer applications, and are being disposed of either by incineration or landfilling with severe environmental and economic impacts. In this work, we developed a technology for utilization of SRM protein in value-added applications. In particular, the SRM was thermally hydrolyzed, protein fragments were recovered from the hydrolyzate, and the recovered protein fragments were chemically crosslinked with polyamidoamine-epichlorohydrin (PAE) resin to formulate an adhesive system for bonding of veneer sheets to make plywood specimens. The effects of crosslinking time, the ratio (wt/wt) of protein fragments and PAE resin in the formulation, and hot pressing temperature on the strength of resulting plywood specimens were investigated by lap shear strength testing method. Adhesive formulations consisting of as much as 78% (wt/wt) protein fragments met the minimum requirements of ASTM specifications for urea formaldehyde resin type of wood adhesives in dry as well as soaked conditions. Under optimal conditions of specimens preparation, some formulations yielded plywood specimens having shear strength comparable to that of commercial phenol formaldehyde resin in both dry and soaked conditions.
Jinrui Huang
Chinese Academy of Forestry, China
Title: Fabrication of Multifunctional Biopolymer Composites with High Performance by Controlling the Dispersion and Distribution of Graphene in the Composites
Time : 11:50-12:10
Biography:
Jinrui Huang has completed his PhD from Chang Chun Institute of Applied Chemistry, Chinese Academy of Sciences (China). Now, He works at the Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry (China). He has published nine papers in reputed journals.
Abstract:
Graphene (GE) has received great attention owing to its extremely high surface area and exceptional mechanical, electrical, and thermal properties. Recently, graphene has been added into a host of biopolymers to produce multinational composite materials. It is known that the properties of the composite not only depends on the properties of the fillers, but also depends on the distribution and dispersion of the fillers in the polymer matrix. In this study, thermally conductive biopolymer composite with high thermal conductivity at low GE loading is fabricated by trapping GE at the interface of a poly(ε-caprolactone)/poly(lactic acid) blend with co-continuous structure via utilizing adsorption-desorption of polymer chains on the GE surface. On the other hand, the dispersion of graphene in the polymer matrix also determines the performance of graphene/polymer composite. In this study, the strong p–p interactions between graphene oxide and dehydroabietic acid, which is the purified product of the renewable resource disproportionated rosin, is utilized to in-situ synthesize graphene/rosin-based polyamine. It is found that graphene can be uniformly dispersed in the epoxy matrix after curing epoxy resin with the in-situ synthesized graphene/rosin-based polyamine.
Chengguo Liu
Chinese Academy of Forestry, China
Title: Novel tung oil-based unsaturated ester macromonomer for thermosetting polymers
Time : 12:10-12:30
Biography:
Chengguo Liu has completed his PhD from Nanjing University. He has published more than 30 papers in reputed journals
Abstract:
A novel unsaturated co-ester (co-UE) macromonomer containing both maleates and acrylates was synthesized from tung oil (TO) and its chemical structure was characterized by FT-IR, 1H-NMR, 13C-NMR, and gel permeation chromatography (GPC). The monomer was synthesized via new synergetic modification of TO by introducing maleic groups first and acrylic groups subsequently onto TO molecules. The influence of experimental factors on thermo-mechanical properties of the cured bioresins was evaluated to better understand structure-property relationships of the biomaterials and optimize experimental conditions. The obtained TO-based co-UE monomer possessed a highly polymerizable C=C functionality (2.27 per fatty acid), consequently resulting in rigid bioplastics with high crosslink densities (νe) and excellent mechanical properties. For instance, the bioplastic prepared under the optimal synthesis conditions demonstrated a νe of 4.03×103 mol/m3, storage modulus at 25°C of 2.40 GPa, glass transition temperature (Tg) of 127°C as well as tensile strength and modulus at 36.3 MPa and 1.70 GPa, respectively. A new theory for determining optimal comonomer concentration was further developed according to the copolymerization equation. The proposed theory accurately predicted the best styrene dosage for the co-UE monomer. Finally, the hydroxyethyl acrylate (HEA)-modified TO-based resin was compared with the unmodified one in thermo-mechanical properties, thermal stability, microstructural morphologies, and curing behaviors. The new co-UE bioresin showed higher C=C functionality and crosslink density, superior properties including Tg and thermal stability, and similar curing behaviors. The developed eco-friendly rigid biomaterials provide potential application in structural plastics such as sheet molding compound.
Shinji Hirai
Muroran Institute of Technology, Japan
Title: Creation of Keratin Resin and Fibroin Resin Using Fibrous Animal Waste Products
Time : 12:30-12:50
Biography:
Shinji Hirai obtained his Ph.D. in Engineering from Waseda University (Japan) in 1988. In 1990, he joined the Department of Materials Science and Engineering, Muroran Institute of Technology as an Associate Professor. In 1992–1993, he trained under Professor Emeritus L. Brewer at the UC Berkeley. In 2003, he acquired the position of Full Professor and his research interests expanded to include high-performance biomass plastics created using animal fiber waste and effective utilization of rare earth sulfides. Since 2012, he is concurrently serving as the Director, Research Center for Environmentally Friendly Materials Engineering. Recently, as part of the ImPACT national project, he is involved in the study of resinification of artificial spider silk.
Abstract:
Keratin resin and fibroin resin have been prepared from silk or hornet silk powder, composed of fibroin protein, and from wool or chicken feather powder, composed of keratin protein, respectively, by heating at 100–180 °C under pressures of 20–40 MPa. The mechanically ground powders of wool waste or chicken feathers and pulverized waste silk, all of which are waste materials, can be used as the raw materials. In the case of wool, woven wool fabric also serves as a raw material after removal of the cuticle layers. For resinification, the powder was simply placed in a jig; in the case of woven fabric, it was stacked into the jig after punching to the size of the jig and was then heated under pressure using a hot press. The resins derived from silk or wool powder showed glass transition temperatures close to 200 °C and three-point bending strengths and flexural moduli superior to those of polycarbonate resins. On the other hand, the resin derived from wool powder had a very small expansion coefficient, with a value comparable to metals such as copper or aluminum. Moreover, the three-point bending strength of the resin derived from woven wool fabric increased to 116 MPa. Furthermore, upon applying stress to the resin, reversibility to woven fabric was observed, resulting in excellent impact resistance that is superior to that of ABS resin. Compared to the resins derived from wool and silk powders, the resin derived from chicken feather powder had a lower glass transition temperature and a larger thermal expansion coefficient, whereas the three-point bending strength, the elastic modulus, and the Vickers hardness were found to be lower. However, with the sole exception of the inferior three-point bending strength, the other features of this resin were comparable with those of polycarbonate.
Somayeh Mollasalehi
University of Manchester, UK
Title: Isolation and characterization of polyvinyl alcohol (PVA) degrading fungal strains from soils
Time : 12:50-13:10
Biography:
Dr Somayeh Mollasalehi has completed her PhD at the University of Manchester and she is working as a researcher at the University of Manchester.
Abstract:
During the last thirty years, extensive research has been conducted to develop biodegradable plastics as more environmentally benign alternatives to traditional plastic polymers (Larry et al., 1992). Polyvinyl alcohol (PVA) is a water-soluble polymer which has recently attracted interest for the manufacture of biodegradable plastic materials (Solaro et al., 2000). PVA is widely used as a paper coating, in adhesives and films, as a finishing agent in the textile industries and in forming oxygen impermeable films (Larking et al., 1999). Consequently, waste-water can contain a considerable amount of PVA and can contaminate the wider environment where the rate of biodegradation is slow (Lee &Kim, 2003). Despite its growing use, relatively little is known about its degradation and in particular the role of fungi in this process. In this study, we used culture enrichment to isolate fungal degraders from eight uncontaminated soil samples which were shown to have very different fungal populations and dominant species revealed by denaturing gradient gel electrophoresis (DGGE). While all soils contained fungal degraders, the number of recovered species was restricted with the most common being Galactomyces geotrichum and Trichosporon laibachii. One thermophilic strain, Talaromyces emersonii was recovered at 50°C. For G. geotrichum, a molecular weight range of 13-23 KDa, 30-50 KDa or 85-124 KDa had no significant effect on the growth rate (mean doubling time 6.3 to 6.9 h-1) although there was an increased lag phase for the higher molecular weight PVA.
Lunch Break: 13:10 - 14:00 @ Texas A
Asma Said Khalid Al Hosni
University of Manchester, UK
Title: Biodegradation of biopolymers under soil and compost conditions
Time : 14:00-14:20
Biography:
Asma Alhosni is a PhD student at the University of Manchester, She has completed her MSc from Nottingham University in UK..She is working as a lecturere at the Higher college of Technology in the Sultanate of Oman.
Abstract:
Over the last six decades, the use of plastic materials has had a major impact on our daily lives and has become essential for modern societies due to their extensive and diverse range of applications. However, the recalcitrant nature of many plastics means that they are problematic in terms of disposal and are a major industrial waste product and environmental pollutant. The use of biodegradable polymers can aid in resolving a number of waste management issues as they are degraded ultimately to CO2 and water and can be directed to conventional industrial composting systems. Four different biodegradable polymers, namely polycaprolactone, polyhydroxybutytate, polylactic acid and poly(1,4 butylene) succinate were used to study the time required for biodegradation to occur in soil and compost under laboratory conditions. Degradation of polymer discs was measured by monitoring changes in disc weight, thickness and diameter over a period of more than ten months at three different temperatures: 25°C, 37°C and 50°C. Degradation rates varied widely between the polymers and the incubation temperatures. Polycaprolactone showed the fastest degradation rate under all conditions and found to be completely degraded when buried in compost and incubated at 50°C after 91 days. Fungi from the surface of the polymers discs following colonisation were isolated and identified by ITS rDNA sequencing.
- Workshop Session
Location: Texas B
Session Introduction
Dean Webster
North Dakota State University, USA
Title: High Performance, high bio-content thermosets for composites and coatings
Biography:
Dean C Webster is Professor and Chair in the Department of Coatings and Polymeric Materials at North Dakota State University (NDSU). He received a BS in Chemistry and a PhD in Materials Engineering Science both from Virginia Tech. Prior to joining NDSU in 2001 he worked for Sherwin-Williams and at Eastman Chemical Company. He is the recipient of the 2011 Roy W Tess Award in Coatings Science given by the American Chemical Society, the 2013 Joesph Mattiello Lecture award given by the American Coatings Association, and the Waldron Research Award given by the NDSU Alumni Association. His research is in the area of new high performance polymer systems for coatings and composites, nanocomposites, polymers for marine antifouling coatings, and use of renewable resources in polymers and coatings systems.
Abstract:
While vegetable oils and other bio-based raw materials have been used in coatings resins for decades, new concepts are needed to transform bio-based raw materials into coatings resins that meet today's demanding performance needs. Highly crosslinked petrochem.-based thermosets are used in broad applications due to their high performance properties. Designing bio-based resins having a high no. of appropriately distributed functional groups per mol. can lead to thermosets having exceptional performance properties. Sucrose ester resins from vegetable oils, such as soybean oil, having a high degree of substitution can be epoxidized to yield biobased epoxy resins (e.g. Epoxidized sucrose soyate, ESS) having a high degree of functionality. These epoxy resins can then be crosslinked using several different mechanisms such as via anhydride-epoxy reactions, catalytic polymerization, and so on to yield coatings having high crosslink d., good hardness, excellent solvent resistance and adhesion. In addition, polyols can be derived from the epoxidized sucrose soyate resins via reaction with alcohols such as methanol to yield methoxy sucrose soyate polyol (MSSP). These highly functional polyols can be crosslinked using melamine-formaldehyde resins or polyisocyanates to yield thermoset coatings having performance properties comparable to their petrochemical counterparts and exceeding the performance of traditional vegetable oil based polyols.
Coffee Break: 15:45 - 16:05 @ Foyer