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Bioplastics: A burgeoning industry

By Lynn Crandall

Spray foam insulation, made from the soy-based polyol SoyOyl, provides high performance at a cost comparable to traditional fiberglass batting. Photo courtesy of United Soybean Board.

As Kansas farmer Eric Niemann stands under a summer sun surveying his fields of soybeans, a warm breeze blows, rippling the sea of green. Scanning the horizon, Niemann sees his more than 900 acres stretch to meet the sky, and knows hes not only helping feed the world; hes partnering with researchers to enhance the future by turning crops into marketable, costeffective plasticsbioplastics. We want to see what we can do with soybeans in industrial uses, said Niemann, United Soybean Board (USB) new uses chairman. We look around and everything is made of plastic. Derived from natural resources, bioplastics hold the hope of eventually replacing petroleum-based counterparts in the big business of plastics production. Nearly all of the 90 billion pounds of plastics synthesized each year in the United States are made from petroleum-based polymers (polyethylene, polypropylene, polyvinyl chloride, polyurethane, unsaturated polyesters, and epoxies). The current interest in biopolymers is fueled mainly by environmental concerns as well as interest in finding new uses for renewable agricultural products, said Eugene Stevens, a professor in the Department of Chemistry at State University of New York at Binghamton. Stevens has conducted biopolymer research for more than 30 years. Virtually all plastics are made from fossil fuels, which are not renewable, and also there is concern over the accumulation of waste and pollution, he said.

The manufacturing of petrochemical plastics currently uses nearly 300 million tons of oil and natural gas annually from the worlds supply. According to Stevens, world petroleum supplies are estimated at around 200 billion tons and are expected to last perhaps only another 50 years at the present rate of consumption; natural gas could run out about the same time; coal in about 300 years. But before raw materials run out, production costs will rise to reflect depleting supplies. Then theres the problem of biodegradability. The qualities that make petroleum-based plastics so attractive also make them a burden to the planetary ecosystem. More than 60 billion pounds of plastics find their way into the waste stream each year in the United States and 35 billion pounds in Western Europe.
U.S.
L E A D S R E S E A R C H E F F O RT S

Although most researchers agree that European countries are ahead of the United States in terms of recycling and environmental awareness, the newest technology in bioplastics is largely being generated by U.S. efforts, said Richard Wool, professor of chemical engineering at the University of Delaware and director of the Affordable Composites from Renewable Sources (ACRES) program. In Europe rapeseed has been looked at as a lubricant. It could be used to make composite resins, but no one is currently doing that, Wool said. The automotive industry is probably the most aggressive in terms of coming up with bio-based components. Theyre looking primarily at natural fibers and using petroleum-based resins. In the search to create high-quality, cost-effective bioplastics, researchers have turned to different raw materials, from cornstarch, canola, and castor seed oil to rapeseed and soy protein. But a plentiful supply of soybean oil has made it a likely choice as a renewable plastics feedstock

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for many projects, said basically a low-cost, surNiemann. plus by-product of the The United States food industry where the produces about 20 soy protein usually has billion pounds of soythe higher value. Through bean oil annually, the ACRES program, accounting for 80% Wool has developed of seed oils produced applications in pressurein this country. sensitive adhesives, sheet Another 20 billion molding compounds, pounds of soybean oil wood substitutes, and is produced in South agricultural and automoAmerica. Through the tive equipment, including Soybean Checkoff side and back panels for a program, which col2002 model of a John SoyOyl, a soy-based polyol, is being used in the manufacture of a lects 0.5% of soybean Deere combine in collabspray-on truck bed liner sold by Midwest Line-X of Sioux Falls, sales for research and oration with industrial South Dakota. Photo courtesy of United Soybean Board. promotions, the USB partners. Wool said the has funded numerous highest-volume applicasoy-based research projects and added thane used each year for a variety of tion for the plastics has been in the prodnew uses for a soy-based polyol. products from steering wheels to mat- uct used for the John Deere combines, The polyol market in the United tresses to shoe cushions to seat or head- comprised of soy and corn oil resins, but States is nearly four billion pounds. rest cushions, our goal is to get 20% of its only the tip of the iceberg. Worldwide, we use about nine billion the world market in five years. That The agricultural equipment business pounds of polyols, Niemann said. translates into a new market for 140 is large and thats where it started, but We started out doing research work million bushels of soybeans. And the the automotive business is larger and with universities. In the past four to thing is were looking at a cost that the housing industry is several magnifive years weve changed our focus a lit- runs 10 to 15% less than petroleum- tudes greater, he said. So were in the tle bit to working with industry part- based polyurethane. And its renew- process of setting up infrastructure to ners to get the products out into the able. Thats the really exciting part. tackle these other high-volume areas. marketplace. The market for soy-based polyol sigCarpet with a soy oil-based backing nificantly expanded in June when The A P P L I A N C E A P P L I C A T I O N S was recently installed in an office and Dow Chemical Company and Dalton, Researchers in the chemistry departconference room at a U.S. Department Georgia-based Universal Textile ment at Iowa State University have of Agriculture (USDA) building as part Technologies, a major carpet backing been developing a soybean oil-based of a government effort to utilize bio- supplier, announced that Biobalance plastic that could be used as a lining to based products. The carpet backing, a polymers containing USSs SoyOyl will dampen sound and reduce vibration in appliances such as washing machines. thin layer between the fibers and foam be used in commercial carpet backing. cushion that keeps the carpet fibers Wools research with ACRES at the The material, created by professor bound together, was made from University of Delaware is a collaborative Richard Larock and postdoctoral felSoyOyl, a soy oil-based polyol manu- effort with Kansas State University and low Fengkui Li through funding from factured by Urethane Soy Systems numerous industry partners. The pro- the Iowa Soybean Promotion Board Company, Princeton, Illinois, as a gram has developed a broad range of (ISPB), offers a competitive product petroleum polyol alternative. Tom chemical routes to utilize natural triglyc- with advantages over petro plastics. The plastics we get have some Kurth, president of the company, said eride oils as the basis for polymers and the carpet backing is just one of the composite materials, incorporating nat- unique features that most petroleumnew uses for soybean oil. ural fibers, such as flax, chicken feath- based plastics dont. . . . And these mateWe have an industrial plant that has ers, and hemp. Although the work has rials also have shape-memory properthe capacity to produce 325 million included corn oil, flax oil, and linseed ties. They will return to their original pounds of polyol, Kurth said. With oil, Wool said soybean oil is ideal shape after being heated, reshaped, about 20 billion pounds of polyure- because it is a high-quality oil but is cooled, and reheated, said Larock.
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Technology for bioplastics production isnt confined to oil- and fat-based resources
In April, Minneapolis, Minnesotabased Cargill Dow LLC opened a plant in Blair, Nebraska, that is expected to use up to 40,000 bushels of corn per day in production of NatureWorks PLA (polyactide), a plastic resin derived from cornstarch, and NatureWorks fibers. The Nebraska plant, a joint endeavor between Cargill and The Dow Chemical Co., Midland, Michigan, is capable of producing 300 million pounds of NatureWorks PLA annually. Cargill Dow spokesperson Michael OBrien said the effort started 12 years ago with a small research and development company at Cargill, and represents investments of nearly $750 million to develop the technology. At the time, Cargill was heavily involved in corn wet-milling, or starch processing. Based on this business and their market research, the group decided to pursue production of PLA, OBrien wrote in an e-mail. Because we use corn instead of petroleum, PLA requires 2050% fewer fossil resources than traditional plastics. Production of the product emits 60% fewer green house gases than those emitted in production of traditional plastics, and PLA completely biodegrades in compost facilities, OBrien wrote. Plans include shipping the product around the world for use in an array of consumer applications, including clothing, food packaging, and bedding. The Coca-Cola Co. served drinks in a NatureWorks PLA compostable cup at the 2002 Olympic Winter Games in Salt Lake City, Utah. IPER, a leading supermarket chain headquartered in northern Italy, has made commitments to convert their fresh food packaging to NatureWorks PLA. Randy Howard, president and CEO of Cargill Dow, said the appeal of
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NatureWorks PLA is based on its overall performance. People buy products based on value and performance, Howard said. What we have done is expanded the definition of both. Howard said the result of the new plant coming on-line will spell a dramatic increase in the commercial availability of NatureWorks PLA and fibers, as well as pave the way for a number of consumer products scheduled for introduction throughout 2002 and 2003. Researchers at the Center for Crops Utilization Research (CCUR) at Iowa State University have developed technology for converting soy protein into a bioplastic compatible with numerous industrial techniques including extrusion, compression molding, and injection molding. We add biodegradable polymers to the soy material. We add plasticizers to help in the processibility, and compatibilizers to help mix the two components, said Jay-Lin Jane a professor in the department of Food Science and Human Nutrition who developed the new compound with research scientist Perminus Mungara. Basically we mix all the ingredients together and then it would be extruded and chopped into pellets. The material is then used for making different products. Soy Works Corp., a developmentstage company based in Woodridge, Illinois, acquired worldwide exclusive commercial rights for the researchers patented technology in 1998. Roy Taylor, president and CEO of SoyWorks, said the company has formal and informal agreements with companies interested in the materials and expects to introduce an array of products by 2003.

Were working on building materials, meat trays, burger clam shells and take-out food containers, cutlery, golf tees, packaging and packaging components, stretch wraps and mulching films. Theres a long list of things we feel really good about, he said. Products can be manufactured using equipment standard to the plastics industry and at very competitive costs. Jane said her biodegradable materials offer 50% biodegradability within 10 to 14 days in soil or water environments. Additionally, studies have shown growth enhancement when articles formed from the material are ground up and applied to crops. Procter & Gamble Co., Cincinnati, Ohio, has taken steps to commercialize its family of bio-based, biodegradable aliphatic polyesters (polyhydroxyalkanoates: PHA), called Nodax. To produce the materials, a variety of microorganisms will be used, said Norma McDonald, associate director of External Business Development and Global Licensing, and the companys researchers are still exploring both animal- and vegetable-based substrates as carbon sources. Nodax polymers are adaptable to a wide range of applications, including fibers/nonwovens, foams, synthetic papers, films, extrusion coatings, adhesives, latex, and injection- and blow- molded articles. According to McDonald, the family starts with short-chain materials where the first co-monomer is C4 (polyhydroxybutyrate). The side chains provide varying degrees of branching and vary in length from C6 (polyhydroxyhexanoate) to C24. Kaneka Co., Osaka, Japan, is the first licensed producer of C4C6 and is expected to gain large-scale commercialization within two to three years.

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from 340 to 400C for 15% weight loss values in air. Although the material offers a competitive price advantage, the researchers are continuing to explore other possible cross-linking agents that would be cheaper and more environmentally friendly, Larock said. Theyre also expanding the work to include composites with agricultural fibers and are looking for industrial partners to help develop their patented plastic. Currently, the Center for Advanced Technology Development and Iowabased Sheaffer Pen, Souvenir/ Norwood, Jebro Inc., Heartland Resource Technologies, Creative Composites, and Municipal Pipe Tool are working to explore commercial possibilities. Larock said that although soybean oils abundance and cost-effectiveness strengthen its advantage as a bioplastic feedstock, his work has included a basic survey of corn, fish, tung, peanut, sunflower, walnut, and other natural oils with results consistent with soybean oil. Joseph Jen, USDA undersecretary for research, education, and economics, shows off carpet backed with a soybased material that was recently installed in some of the USDAs offices in Washington, DC. Photo courtesy of United Soybean Board.
U S DA R E G I O N A L R E S E A R C H CENTERS RESEARCH

over polyethylene mulch in ease of use and biodegradability. Theres a lot of polyethylene film used in agriculture to keep weeds out, heat up the soil, and retain moisture. On the order of 300 million pounds a year are used in the United States and 1 billion pounds worldwide, Shogren said. The problem is in the disposal. Its difficult to remove from the field and expensive. Then, once its removed, you either have to landfill it, which many landfills wont accept, or burn it, which is illegal in many places. The biodegradable mulch can be simply tilled into the soil at the end of the season. Although the up-front cost of the bio-based mulch currently is higher than its petroleum counterpart, Shogren said it is comparably priced when the cost for removal and disposal of polyethylene is factored in. Beyond its biodegradability and ease of use, Shogrens product has demonstrated numerous benefits pleasing to farmers. The kraft paper/soy oil mulch resists penetration by certain weeds capable of penetrating plastic mulch, thus reducing the need for application of methyl bromide (a chemical currently raising concerns over its contribution

The soy bioplastics are prepared by the cationic polymerization and copolymerization of regular, LoSat, and conjugated soybean oils (3065 weight percent) with commercial comonomers, including styrene and divinylbenzene. The plastics possess petro plastic characteristics with room temperature moduli ranging from 6 106 to 2 109 Pa and glass-transition temperatures ranging from 0 to 105C. The maximum tensile strength of the materials reaches as high as 21 MPa. The thermal stabilities range

Soy oil-based bioplastic research at the National Center for Agricultural Utilization Research (NCAUR) in Peoria, Illinois, is finding a variety of applications. Randal Shogren, research chemist in the plant polymer division at the center, is field-testing agricultural film at the University of Florida, Cornell University, and Mead Westvaco, a paper company that grows trees. The film, kraft paper coated with polymerized soybean oil, has demonstrated advantages

Scientist Randal Shogren installs agricultural film in a field to prepare for a test of the product he developed. Photo courtesy of NCAUR.
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to ozone depletion). The paper mulch can be made water-permeable, an advantage to farmers who do not irrigate with drip lines under plastic mulch. Shogrens mulch also enhances the potential for a cleaner crop for tree and cotton farmers, who often find their harvest contaminated with black plastic flecks from the polyethylene mulch. Sevim Erhan, research leader in the Food and Industrial Oil Research division at the center, and postdoctoral research associate Zengshe (Kevin) Liu have applied for a patent for their bioplastic application of solid free-form fabrication (SSF), a system that uses epoxidized soybean oil-based polymer slurries for use in fabricating objects without the need of a mold. The system utilizes a motorized syringe mounted on an xy drive. A computer program instructs the syringe to write a thin stream of slurry, made of soybean oil, fiber, and gelling agent, much like a three-dimensional pen plotter. Moving over a support surface, the syringe traces out the first layer of the object, then moves up successive steps, writing additional layers to form a solid object. The object is then heatcured. The researchers have found the technique cost-effective and easily adaptable for different end-use applications. The bioplastic product exhibits durability equal to petroleum-based plastics and can be altered by using different carbon, glass, mineral, or natural fibers. Although the material is capable of working with current mold technology, the ability to create any object without a mold affords greater flexibility, Liu said. We can make any shape by telling the computer to do it, and there is no problem with releasing the object from the mold or with having seams, he said. Erhan said the process would be particularly useful for making parts that are detailed or one-of-a-kind. The technique is attracting a lot of attention from companies with a variety of interests.
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A research team led by Daniel Solaiman is developing a fermentationbased biotechnology process to make PHA. Photo courtesy of ERRC.

A research team led by Daniel Solaiman, a lead scientist in the Fats, Oils, and Animal Coproducts Research Unit of the Eastern Regional Research Center, Agricultural Research Service, USDA in Wyndmoor, Pennsylvania, is developing a fermentation-based biotechnology process to convert animal fats, plant oils, and their co-products, as well as waste streams into, among other things, poly(hydroxyalkanoates) (PHA). [PHA were discussed by Vanessa Bongcam and Yves Poirer of the University of Lausanne, Switzerland, in the August 1999 issue of inform (10:768774).] A biodegradable polyester, PHA is synthesized and sequestered in intracellular granules by microorganisms and extracted with solvent. The biopolymers created in this process can have properties ranging from those of thermoplastics and elastomers to adhesives, depending on the makeup of the polymers. In nature, there are many bacteria that will produce plastics. But not all of them can use fats and oils directly. So what we do is select strains that can produce plastics, use genetic modification to make them able to use fats and oils, and vice versa, Solaiman said. Furthermore, by selectively feeding the bacteria with, for example, soybean oil, we can produce one kind of plastic. If we feed them another oil, we get

other types of characteristics. So by selective feeding we can manipulate or tailor the characteristics of the biopolymers. Solaiman said an advantage of his teams process over other methods is that it can utilize not only renewable agricultural oil but also by-products and waste streams of oil and fat processing and recycled materials. By using renewable and recycled materials as feedstocks, the process is ecologically advantageous and helps contain the cost of the bioplastic. Although PHA are not currently widely used in commercial applications, Solaiman said there is an immense potential for the product in a host of applications, such as adhesives, coatings, fibers, films, and tissue engineering. He and his group continue to manipulate the PHA-forming process while also investigating the fermentation of the same feedstocks to surfactants using yeasts.
THE
FUTURE

While many consider the technology of bioplastics an emerging field, it is actually a resurgence, Stevens said. He noted that many natural polymers were commercialized in the 19th century in products such as animal horn snuffboxes, billiard balls, hairpins, and buttons. The most widely used commercialized product was celluloid, used in motion picture films, combs, and other decorative items. And in 1941, Henry Ford made prototype automobile parts out of soy meal. But the technology was primitive and was set aside when World War II diverted industrial interest to defense efforts. While petroleum-based plastics continue to dominate the market, prospects of bioplastics taking a substantial share will ultimately depend on consumer acceptance and government encouragement, Stevens said. Lynn Crandall is a freelance writer based in Ludlow, Illinois.