Grantee Research Project Results

2004 Progress Report: Development of Novel Plastics From Agricultural Oils

EPA Grant Number: R829479C005
Subproject: this is subproject number 005 , established and managed by the Center Director under grant R829479
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: National Research Program on Design-Based/Model-Assisted Survey Methodology for Aquatic Resources
Center Director: Stevens, Don L.
Title: Development of Novel Plastics From Agricultural Oils
Investigators: Larock, Richard C.
Institution: Iowa State University
EPA Project Officer: Aja, Hayley
Project Period: October 1, 2003 through September 30, 2004
Project Period Covered by this Report: October 1, 2004 through September 30, 2005
RFA: The Consortium for Plant Biotechnology Research, Inc., Environmental Research and Technology Transfer Program (2001) RFA Text |  Recipients Lists
Research Category: Targeted Research , Hazardous Waste/Remediation

Objective:

The objective of this research project is to optimize the reaction conditions, procedures, and processes for the cationic, thermal, and free radical copolymerization of natural oils, such as soybean, corn, and linseed oils, for the preparation of novel new bioplastics of commercial interest.

Progress Summary:

Our research has focused on the thermal and free radical polymerization of conjugated soybean and linseed oils. A variety of novel opaque, white polymers ranging from rubbery materials to tough and rigid plastics have been prepared by thermal polymerization at 85-160°C of varying amounts of 87 percent conjugated linseed oil, styrene, and divinylbenzene. Gelation of the reactants typically occurs at temperatures higher than 120°C, and fully cured thermosets are obtained after post-curing at 160°C. The fully cured thermosets have been determined by Soxhlet extraction to contain approximately 35-85 percent crosslinked materials. The microcomposition of these polymers, as determined by ¹H NMR spectroscopy, indicates that the crosslinked materials are composed of both soft oily and hard aromatic phases. After solvent extraction, the insoluble materials exhibit nanopores well distributed throughout the polymer matrices. Dynamic mechanical analysis of these polymers indicates that they are phase-separated with a soft rubbery phase having a sharp glass transition temperature of -50°C and a hard brittle plastic phase with a broadened glass transition temperature of 70-120°C. These polymers possess crosslink densities of 0.15-2.41 x 10⁴ mol/m³, compressive Young’s moduli of 12-438 MPa, and compressive strengths of 2-27 MPa.

These materials are thermally stable below 350°C and exhibit a major thermal degradation of 72-90 percent at 493-500°C.

Thermoset plastics of various compositions have been prepared using free radical copolymerization of conjugated soybean and linseed oils. One-hundred percent conjugated low saturation soybean oil has been prepared by the conjugation of commercial low saturation soybean oil. This oil has been copolymerized with acrylonitrile and divinylbenzene or dicyclopentadiene, which also serve as crosslinking agents. The best results from the point of view of oil incorporation in the polymer, clearness, hardness, and mechanical properties are achieved when the composition of the polymer is between 40-60 percent by weight of the oil. Work is underway to fully characterize these materials (DMA, TGA, compression, etc.) and to improve the process by which they are prepared.

We also have investigated the free radical copolymerization of 100 percent and 87 percent conjugated linseed oil plus acrylonitrile and divinylbenzene to make thermoset plastics. The high degree of unsaturation and the facile polymerization of conjugated oils make these oils particularly attractive as starting materials. As expected, as the percent of conjugation increases, the incorporation of oil into the thermoset also increases, as indicated by the extraction and mechanical analysis data. Oils that are not conjugated do not react well and produce undesirable materials. The amount of oil used in the thermosets varies from 50 to 75 percent by weight, with 50-60 percent providing the most promising new materials. Substitution of the divinylbenzene by dicyclopentadiene or norbornadiene currently is being investigated. More work on the thermal degradation and mechanical properties of these materials is necessary before we can ascertain their commercial promise.

One full paper on the thermal polymerization of conjugated linseed oil has recently been submitted for publication, and another full paper on these materials is in preparation.

Future Activities:

We plan to continue to examine the thermal, free radical, and cationic copolymerization of soybean, corn, and linseed oils, as well as many other naturally occurring oils. We will optimize the processes and the properties of the resulting materials. A second paper on the thermal polymerization of conjugated linseed oil will be submitted for publication soon. Currently, we are finishing up work on the cationic copolymerization of a wide range of other natural oils and expect to submit a full paper on this work soon. A poster on our bioplastics work will be presented in October 2004 at a special American Oil Chemists’ Society meeting on biorenewables in Chicago. Invitations to speak at biorenewables symposia at the Great Lakes Regional American Chemical Society meeting, and the American Chemical Society and American Oil Chemists’ Society national meetings next spring have been accepted. Possible industrial collaborations with Creative Composites in Iowa, Itochu in Japan, Natural ASA in Norway, and ADM in Illinois are being explored.

Journal Articles:

No journal articles submitted with this report: View all 5 publications for this subproject

Supplemental Keywords:

soybean, corn, linseed, agricultural oils, co-monomers, elastomeric material, polymers, sustainable industry/business, treatment/control, agricultural engineering, environmental engineering, genetics, geochemistry, new/innovative technologies, technology, bioenergy, bioengineering, biotechnology, linseed oil, plant biotechnology, plant genes,, Scientific Discipline, TREATMENT/CONTROL, Sustainable Industry/Business, Genetics, Geochemistry, Technology, New/Innovative technologies, Environmental Engineering, Agricultural Engineering, agricultural oils, bioengineering, plant genes, biotechnology, plant biotechnology, bioenergy, linseed oil

Relevant Websites:

http://www.cpbr.org

Progress and Final Reports:

Original Abstract

Final

Main Center Abstract and Reports:

R829479    National Research Program on Design-Based/Model-Assisted Survey Methodology for Aquatic Resources

Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R829479C001 Plant Genes and Agrobacterium T-DNA Integration
R829479C002 Designing Promoters for Precision Targeting of Gene Expression
R829479C003 aka R829479C011 Biological Effects of Epoxy Fatty Acids
R829479C004 Negative Sense Viral Vectors for Improved Expression of Foreign Genes in Insects and Plants
R829479C005 Development of Novel Plastics From Agricultural Oils
R829479C006 Conversion of Paper Sludge to Ethanol
R829479C007 Enhanced Production of Biodegradable Plastics in Plants
R829479C008 Engineering Design of Stable Immobilized Enzymes for the Hydrolysis and Transesterification of Triglycerides
R829479C009 Discovery and Evaluation of SNP Variation in Resistance-Gene Analogs and Other Candidate Genes in Cotton
R829479C010 Woody Biomass Crops for Bioremediating Hydrocarbons and Metals
R829479C011 Biological Effects of Epoxy Fatty Acids
R829479C012 High Strength Degradable Plastics From Starch and Poly(lactic acid)
R829479C013 Development of Herbicide-Tolerant Energy and Biomass Crops
R829479C014 Identification of Receptors of Bacillus Thuringiensis Toxins in Midguts of the European Corn Borer
R829479C015 Coordinated Expression of Multiple Anti-Pest Proteins
R829479C016 A Novel Fermentation Process for Butyric Acid and Butanol Production from Plant Biomass
R829479C017 Molecular Improvement of an Environmentally Friendly Turfgrass
R829479C018 Woody Biomass Crops for Bioremediating Hydrocarbons and Metals. II.
R829479C019 Transgenic Plants for Bioremediation of Atrazine and Related Herbicides
R829479C020 Root Exudate Biostimulation for Polyaromatic Hydrocarbon Phytoremediation
R829479C021 Phytoremediation of Heavy Metal Contamination by Metallohistins, a New Class of Plant Metal-Binding Proteins
R829479C022 Development of Herbicide-Tolerant Energy and Biomass Crops
R829479C023 A Novel Fermentation Process for Butyric Acid and Butanol Production from Plant Biomass
R829479C024 Development of Vectors for the Stoichiometric Accumulation of Multiple Proteins in Transgenic Crops
R829479C025 Chemical Induction of Disease Resistance in Trees
R829479C026 Development of Herbicide-Tolerant Hardwoods
R829479C027 Environmentally Superior Soybean Genome Development
R829479C028 Development of Efficient Methods for the Genetic Transformation of Willow and Cottonwood for Increased Remediation of Pollutants
R829479C029 Development of Tightly Regulated Ecdysone Receptor-Based Gene Switches for Use in Agriculture
R829479C030 Engineered Plant Virus Proteins for Biotechnology