Research Terms
This cost-competitive bioplastic is more environmentally friendly than plastics made from petrochemicals. Most plastics are produced from crude oil or natural gas, disappearing resources that will continue to rise in price in the long term. One common petroplastic, polyethylene terephthalate (PET), is expected to be the fastest growing product segment, growing at a CAGR of 8.5 percent until 2020. Researchers at the University of Florida have designed a sustainable alternative to PET using lignin, the second-most abundant naturally occurring organic polymer found in plants. This bioplastic is the first truly viable substitute for PET, as it matches the important thermal properties of this commercially dominant polymer. Available bioplastics, such as those made from corn, usually rely on costly fermentation processes and have sub-standard thermal properties, both major obstacles to their widespread success. Because lignin is an inexpensive byproduct of paper production, plastics derived from this material can compete on cost with traditional PET. This lignin-based bioplastic has impressive market potential. Global demand for bioplastics is expected to reach 6 million metric tons in 2019. Competitive prices could help bioplastics capture an even larger proportion of the total global plastics market, which was valued at $381.83 billion in 2013.
Biodegradable, eco-friendly polymer made from plant materials for the production of synthetic fibers, food/beverage containers, films and resins
Researchers at the University of Florida have developed a cost-competitive "green" alternative to the petroplastic polyethylene terephthalate (PET). They employed a two-step process that uses readily available lignin extraction products, vanillin or ferulic acid, as a starting material for the production of poly (dihydroferulic acid) (PHFA). In one embodiment of the invention, the researchers derived acetyldihydroferulic acid from lignin and then combined this monomer with a catalyst to initiate polymerization (i.e. plastic formation). The starting materials are byproducts of paper production and the polymer decomposition product is dihydroferulic acid, a common plant metabolite. Thus the new PHFA bioplastic is an attractive, ecofriendly alternative to PET.
This water-degradable polyester made from biorenewable itaconic acid represents an environmentally-friendly alternative to the non-degradable plastics used in the short-term packaging industry. The commercial plastics industry relies on a handful of commercial polymers, such as polyethylene terephthalate (PET) and polystyrene (PS), because of their unique properties and low cost. Made from nonrenewable fossil fuels, such polymers persist in the environment, causing wide-spread global pollution, plastics leakage into the ocean, plastics consumption by marine animals, and oil depletion. A practical alternative to these non-degradable polymers could appreciably improve the sustainability of numerous industries, most notably short-term packaging. Polyesters hold a great deal of promise for this application, as they can be water-degradable, structurally diverse, and made from biorenewable building blocks. The most successful biorenewable polyester is polylactic acid (PLA), but it is limited by poor thermal resistance and requires industrial composting conditions for biodegradation.
Researchers at the University of Florida have developed a polyester, synthesized from bio-based itaconic acid, that exhibits a higher level of thermal resistance than PLA and degrades rapidly when in contact with water.
Biorenewable, water-degradable polymer to replace PET-based blister packaging, short-term PS or PLA packaging, or disposable polyethylene-based medical devices, such as syringes
Itaconic acid is mass-produced via glucose fermentation. When combined with a primary amine, it produces a 2-pyrrolidone ring system. Using this synthetic strategy, UF researchers formed a polymer that is stable in humid air but degrades back to its monomer components over a year-long period when in contact with water. Itaconic acid is an inexpensive and naturally occurring molecule, rated as one of the top 12 renewable chemicals available from biomass by the U.S. Department of Energy National Renewable Energy Laboratory because of its scalability, sustainability, and nontoxicity. Thus, this polymer is inexpensive, biorenewable, and biodegradable, without sacrificing thermal resistance, and an appropriate solution to the plastics pollution problem.
This extraction process produces ferulic and coumaric acid from either ligno-cellulose or carbohydrate-depleted ligno-cellulose (lignin) with a shorter hydrolysis process. Ferulic acid serves many industrial purposes with uses in food flavoring and preservation, packaging, cosmetics, and medications because of its antimicrobial, antioxidant, anti-inflammatory, and anti-cancer properties. Coumaric acid similarly plays a vital role in human health due to the same demonstrated activities. Available industrial hydrolysis processes are low-yielding and take as long as 20 hours to complete, thereby limiting production rates.
Researchers at the University of Florida have developed a high-yield extraction process that shortens the hydrolysis time down to two hours and down to 15 minutes in some cases, by combining the hydrolysis process with high pressure, ultrasound, or microwaves. This protocol works with both ligno-cellulose and cellulose-depleted biomass and uses common, environmentally friendly materials.
Hydroxycinnamic acid extraction process that decreases hydrolysis time and increases yield
This extraction process maximizes the efficiency of ligno-cellulose and lignin hydrolysis by combining the reaction with high pressure, ultrasound, or microwaves. The process involves loading ligno-cellulose or lignin into a glass vessel with sodium hydroxide along with the addition of one of the three reaction-assisting variables. Running the reaction at 150 °C results in the generation of 20 psi of steam pressure needed for the high pressure variation of the process. In conjunction with the 20 psi of steam pressure or ultrasound sonication, the hydrolysis process runs for two hours, while the combination that uses 50 watt microwaves at a maximum temperature of 90 degrees Celsius allows for a 15-minute process. After hydrolysis, acidifying the solution with hydrochloric acid produces the hydroxycinnamic acids, followed by additional extractions from the remaining solute as necessary using ethyl acetate as a safe and reusable solvent.
These biorenewable polyesters can replace polyethylene terephthalate (PET) to produce versatile plastic products including packaging, films, fibers and single-use beverage bottles. PET is a common commodity plastic currently comprising 13 percent of all plastic production worldwide. However, PET derives from chemicals extracted from fossil fuels, which continue to diminish and require significant time and resources for conversion to useful materials.
Researchers at the University of Florida have developed biodegradable aromatic polyesters derived from biobased succinic acid, providing a substitute for PET and other plastics manufactured from fossil fuels. Plastics that originate from biobased feedstocks can decompose back to their original materials, completing a relatively benign environmental cycle.
Recyclable or degradable aromatic polyesters synthesized from biobased succinic acid supplant fossil fuel-based PET plastic products
Polymeric or monomeric biobased carbohydrates are readily fermented into succinic acid, a dicarboxylic acid. The succinic acid undergoes esterification with methanol, yielding dimethyl succinate which dimerizes and then oxidatively aromatizes into dimethyl-2,5-dihydroxyterephthalate. From this intermediate two terephthalic acid analogues can be produced: 2,5-dihydroxyterephthalic acid (DHTA) or 2,5-dimethoxyterephthalic acid (DMTA). These dicarboxylic acids, once synthesized, can incrementally or fully replace terephthalic acid in copolymerizations with diols, yielding biorenewable aromatic polyesters for use in plastic production.
These polymers derive from renewable camphoric acid to produce commodity plastics that degrade in water and exhibit high heat resistance comparable to acrylic glass and polystyrene foam. Plastic is an essential material for almost all industries, including the sizeable packaging, building and construction, and automotive industries. Analysts expect the global plastics market to grow to $715 billion by 2025. While the plastic industry is prolific, it is also the source of major environmental issues. Most common commercial plastics derive from nonrenewable fossil fuels that require environmentally harmful processes to extract. They also have low recycling rates and take hundreds to thousands of years to degrade. Available renewably sourced polymers do not have thermal properties suitable for many high heat commercial applications such as transportation. Other polymers, despite being fully plant-based, do not biodegrade easily, and their products often end up in landfills just like conventional plastics.
Researchers at the University of Florida have developed biodegradable plant-based polymers from natural camphor, a product of the camphor laurel tree, and now derived from the pinene in turpentine in scalable quantities. Camphor is one of the most common commercial aroma chemicals, so it is cheap and easy to access. The synthesized polymers form plastics products that are water-degradable and highly heat resistant.
Plant-based biodegradable commodity plastic replacement for packaging, bottles, bags, utensils, etc.
These biodegradable polymers derive from natural camphor (found in the camphor laurel tree), which is presently made by the flavoring/aroma industry from the terpene alpha-pinene found in turpentine. A kilogram of camphor costs $3, which is competitive with the low-cost nonrenewable substances common in plastic production. The nitric acid oxidation of camphor yields the camphoric acid monomer, which reacts with a diol using a catalyst to yield the final polyester material. Combining camphoric acid with different diols yields polyesters with a variety of properties. The polyesters have a high glass-transition temperature, making them as robust as many as fossil fuel based plastics. Polyethylene terephthalate (PET) is a common recyclable plastic used to package electronics, food, bathroom, and cleaning products. Replacing the terephthalic acid in PET with camphoric acid forms polyethylene camphorate, which degrades easily by agitation in water over just 14 days. This duration can be extended with other copolymer formulations. Other combinations yield polyesters with heat resistance exceeding that of polystyrene (95 °C) and PET (72 °C). The versatility of camphor makes it a perfect monomer for synthesizing plant-based, biodegradable polyesters with commercially attractive properties.
