Biopolymers

Sid Carson Justin Schmader Charlie Hanecek Jesse Gadley

The chemical basis of most every commercial type of plastic used in industry currently is petrochemical. Fossil fuels such as oil are the primary source in the development and manufacturing of these materials, and as of recent years there have been a growing number of concerns over the use of and dependence on oil in everyday life. Many of todays modern conveniences would not be possible if not for the drilling, refining, and manufacturing of petroleum and other fossil fuels, but these fuels are not unlimited resources. They will all eventually run out. Not only this, but environmental concerns over all aspects of using fossil fuels for energy and production are also raised and need to be addressed. All of these concerns are tied in with the concept of Sustainability. In a basic sense, for civilization to live in a sustainable nature, the resources that it consumes must be used at a rate by which they can also be restored by the planets natural cycles. The accepted definition of Sustainability today is meeting the needs of the present without compromising the ability of future generations to meet their own needs. This encompasses many environmental concerns, such as producing waste, drying up sources of natural resources, etc [10]. A movement in the plastics industry towards sustainability is the research and development of biopolymers. By definition, a biopolymer is an organic strain of polymer that is produced naturally by living things. This includes plants of many types, such as corn and soybeans, but can also come from different types of trees and even some bacteria [12]. However, there are a few different classifications of biopolymers. Strictly speaking, a biopolymer is only the building block of the different types of bioplastics [11]. A biopolymer can be used for more than just the formation of a processable plastic resin, but the plastics industry is mainly concerned with using these biopolymers to form more sustainable materials for mass plastic production. These naturally occurring structures are either produced by living organisms or are polymerized through the manipulation of renewable sources. Either is an effective, sustainable, and renewable method of creating plastic resins. One major advantage of these bioplastics is that they are also fully capable of biodegradation at accelerated rates, because of their naturally occurring structure. This means that parts and goods made out of these bioplastic materials can be produced from natural, renewable biopolymers, reducing the strain on the supply of fossil fuels; and at the end of the parts life cycle, it can be composted or disposed of in a manner that it will degrade back into water and carbon dioxide, reducing the waste produced from these commercial goods. However, an important distinction should be made between strict biopolymers and biodegradable polymers; a biopolymer is biodegradable in large part because of its chemical makeup, but a biodegradable polymer can be made up of a petroleum base and still be biodegradable to some degree. Therefore, a biopolymer is classified by how it is constructed or obtained, with biodegradability being a welcome effect of its structure, while a biodegradable polymer is classified as such because of its biodegradability, not its structure [11] [12]. There are a multitude of bioplastics currently being researched and attempting to be commercialized, but only a few are actually being used for large scale production. Among these successful ones are Polylactic Acid (PLA), Polyamide (Nylon) 11, and Polycaprolactone (PCL).

Names, Structures, and Polymerizations Polylactic Acid (also known as Polylactide) is the most common biopolymer currently on the market. As such, it has a variety of brand names associated with it, such as Bio-Flex, Biomax, Cereplast, and NatureWorks [4].

Its chemical name is derived from the lactide molecule that it is polymerized from. Lactide is derived from sources such as starches in corn, potatoes, beets, and other plants. In the United States, it is primarily taken from corn starch; in the rest of the world, sugar cane starches are used. The polymer chain of PLA is made up of these molecules [3]:

http://en.wikipedia.org/wiki/File:Pla_synthesis.png

These lactide molecules are then processed through a ring-opening polymerization (addition reaction that involves the joining and breaking of rings through heat) to form a chain like this [13]:

http://en.wikipedia.org/wiki/File:Pla_synthesis.png

The structure of the molecule is relatively unique, with a methyl group and double carbon to oxygen bond. The method of polymerization is also unique in that it is usually conducted in more than one step. To obtain a lactide ring molecule, two lactic acid molecules must be dehydrated, which releases a water molecule in the process. For this reason, lactic acid cannot be directly polymerized in a long chain, as the water molecule formed when dehydrating the lactic acid breaks down the chains that would form, causing a very low molecular weight throughout the produced polymer. Therefore, the lactic acid is formed into the lactide ring, which then undergoes the ring-opening process and formed into long chains. This reaction does not produce water, allowing it to obtain high molecular weights. NatureWorks provides for a large share of the market and breakthroughs for PLA, with over 20 different grades of PLA available in pellets or powders. Its tacticity, therefore, is difficult to specify because of the multitude of different manufacturers and grades. This applies to the rest of the biopolymers discussed as well. There has been research into copolymerizing PLA with Cysteine in order to form a scale inhibitor for applications that use hard water, such as piping, pumps, boilers, and condensers. What this copolymerized chemical would do is be added to water in small amounts to reduce or stop the scale buildup in the water handling processes because the chemical would eliminate or carry the chemicals that cause the scale buildup through the channel. The advantage of using

PLA with this application is the same as any other biopolymer application; it is made from a renewable, sustainable resource that will also biodegrade at the end of its life cycle. In this case, the chemical will mostly likely end up in some water treatment facility, where it will degrade through the treatment procedures [1]. Normal grades of PLA are also being reinforced and enhanced through research to improve their strengths and advantages so that it will be able to compare with current thermoplastic materials. One such method is the research of reinforcing PLA grades with cellulose based plant fibers (fibers obtained from the stem, skin, seed, etc. of plants [2]). What this reinforcing does is improve the heat resistance, rigidity, and moldability of normal PLA grades. Also, the rate of crystallization within the polymer matrix can be greatly enhanced through the interaction of the polymer and the plant fiber; this can reduce molding cycles and increase the heat resistance of the molded material. This is a particularly useful enhancement because of its sustainability angle, using natural sources to enhance the properties of another natural material [2]. Another biopolymer being used for its sustainability initiatives is a variation of Polyamide, known as Polyamide 11. A company at the front of PA 11 research and development is Arkema, Inc. Their version of this polymer is named Rilsan PA11. It is also referred to as Nylon 11, as it falls under the category of polyamides. According to Arkemas Rilsan website, the polymer is supplied in powder or pellet form, and can be processed by injection molding, extrusion, blown film extrusion, extrusion blow molding or rotomolding. It is also available in rigid, semi-flexible, and flexible grades, as well as reinforced and conductive [6]. PA11 is polymerized much in the same way as the entire family of polyamides. A molecule with an acid group at both ends is reacted with two molecules that contain amine groups. The acid and amine act as the functional groups in the condensation reaction. These molecules then react with of the acid and amine functional groups to produce the long chain of polymers. The main difference with PA11 is the source of the basic structure and the end structure of the monomer. The monomer that makes up the PA11 chain is presented as such:

http://www.polymerprocessing.com/polymers/PA11.html

The (CH2)10 represents a CH2 group repeated ten times through the course of the monomer, while the dashes outside of the brackets represent where one monomer ends and another starts. PA 11 has very similar properties to that of PA6 or other materials in the Polyamide family. Polycaprolactone is a biopolymer belonging to the polyester family. A few commercial types of this polymer are called Boltaron, Tone, and LACTEL (the latter is a general name of a line of biopolymers produced by DUCTEL Inc., which includes PLA). PCL is primarily available in pellet form. It is produced from the -caprolactone ring molecule, which is derived from crude oil. Its molecule looks like this, displayed on the next page:

http://en.wikipedia.org/wiki/File:Pcl_synthesis.png

This is polymerized by a ring-opening process as well, taking place as an addition reaction, which joins rings of the molecule together with heat to form the long polymer strands. This results in this monomer structure [8]:

http://en.wikipedia.org/wiki/File:Pcl_synthesis.png

PCL is also used as an additive for other polymers. Other bioplastics such as PLA use PCL as an additive to improve impact resistance and enhance biodegrading capability. It can also be used as a natural plasticizer for PVC [7].

Biodegradable Additives Interestingly, there is even research into making traditional plastic materials take on properties of bioplastics, specifically biodegradation. Bio-Tec industries has a product available called Bio-Batch that is used as an additive in processing to make a traditional plastic material biodegradable in its end life in a landfill or a compost; it has been tested on most commercial polymers, and specific ones include polystyrene, polypropylene, polyethylene, polyethylene

terephthalate, and polyvinyl chloride. It is used the same way as a colorant. According to BioTecs explanation, the process goes as follows: [our] technology expands the molecular structure of the plastic, scissoring the polymer chain and adding in nutrients and other organic compounds that weaken the polymer chain for microbial action to colonize in and around the plastic. These microbes then secrete acids which break down the entire polymer chain. Bio-Batch will give you a biodegradable end product that will have indefinite shelf life until placed in an active microbial environment, such as a landfill.
http://www.bio-tec.biz/products.html

The additive is not supposed to weaken the properties of the resin in any way, and the degradation process only begins and occurs in an environment like a landfill or a compost; some place where the plastic will be exposed microbes that will have attempted naturally to break down the polymer structure. What this additive does is speed up this process. This is a different take on the biopolymer initiative; instead of form completely new and different polymer types, what Bio-Tec is attempting to do is take the current industry standards and give them the beneficial properties of some biopolymers without adding much cost [14].

Overall Effects on Sustainibility PLA and other starch based biopolymers account for about 50% of the current market and usage of bioplastics. It is currently in use for packaging and bags in supermarkets and stores, gradually replacing the traditional polyethylene bag. In the state of California, petroleum based plastic bags are banned from being used in stores; a step that is being taken towards a more sustainable and renewable industry [5]. As the production of plastic materials and goods continues to grow, so will the waste that is produced. The Recycling initiative was the route chosen for industry many years ago, and when carried out properly and with the right equipment, the procedure is successful. However, bioplastics and biodegradable materials are becoming more and more of a viable alternative to this because of the seeming unsuccessfulness of the recycling initiative (due to lack of participation or improper recycling procedures). Unrecycled material will be able to be composted when made from bioplastics; this will in turn create less waste and pollution. PA11 is made from a vegetable oil derived from castor beans. While it is not biodegradable, it is classified as biopolymer because of its completely renewable origins. [6] PCLs part in the sustainability platform is based off of its ease of biodegradability. While it is derived from a petrochemical source, it is completely biodegradable and therefore is classified as a bioplastic. PCL has a large biomedical application range. One of the applications currently being researched and put into place is PCL as an implantable biomaterial, as it is an FDA approved material for use on and in the human body; it also will not degrade within the human body, and will mesh well with the makeup and structure of the living organism it will be implanted in. One method of copolymerization of PCL involves the addition of a crosslinking agent to the polymer matrix in order to produce a safe scaffold for bone regeneration within the human body. After the PCL copolymer is injected into the human body, it does not require the

presence of an external, toxic crosslinking agent to harden and build within the body. This is useful because PCL and its copolymer are not harmful to tissue in the human body, while the external crosslinking agent used for this process traditionally sometimes can be [15]. These three particular biopolymers are only three of a very wide range of different types. They were chosen, however, to exemplify the disparities between materials and polymers within the biopolymer family. Each one of them has a very wide and different range of properties and applications. The properties of these three biopolymers are a good indication on how bioplatics are being looked at today; as safer, more environmentally conscious alternatives to traditional resins and materials. The market for these types of polymers is projected to grow greatly over the next few years as well. Currently, it is estimated that approximately 85 thousand tons of bioplastics are commercially developed and used; by 2012, that is projected to grow to numbers upwards of 1.5 million [11]. There is, however, debate on how effective the current methods of producing bioplastics are in terms of sustainability. A major point of bioplastics is that they are from renewable resources instead of petrochemicals; however, when processing these materials, they are still dependent on oil and petrochemicals within the production chain [10]. While this seems counterproductive, it also has to be pointed out that bioplastics are only one part of the sustainability initiative. Research into alternative fuels and replacing petrochemicals in other areas will ultimately determine how effective bioplastics and other sustainability initiatives end up being. Bioplastics, however, are a single step towards this goal.

Resin Properties The resin properties of a material are very important. These properties dictate if a polymer is suitable for specific application based off how the polymer performs in numerous standardized tests. These tests determine the modulus, yield point, toughness, impact strength, and various other properties possessed by a certain material. The combination of all of these properties gives a general insight into how the plastic will perform, while also providing a basis of comparison between different types of materials. This information is extremely valuable to designers and processers because it gives a basic understanding of how the polymer will function. Biopolymers are no exception. They are the material of the future and must also be tested to give designers and processers a guideline to follow. The following chart was constructed to demonstrate the properties of Nylon 11, PCL, and PLA. The information for Nylon 11 was referenced from a datasheet in which unreinforced Nylon 11 was tested [16] [17]. The information for PCL was derived from datasheets that tested Solway PCL and Lactel PCL [18] [19]. The mold shrinkage value and flexural modulus for PCL was taken from Dow Pellethane 2102-90AR, which is a Polyester Polycaprolactone based material [20]. The information in the following chart corresponding to PLA was taken from Natureworks PLA polymer 3001D, which is a general purpose injection molding grade material [21]. The service temperatures, thermal conductivity, heat capacity, and dielectric strength for each of the following resins were referenced from CES Edupack 2008 using the properties of the unfilled material [22]. The viscosities and degradation temperatures were found on the Moldflow database, and the given values are from the ranges of 3000/sec to 5000/sec, which is in the processing range [23]. If a specific value for a particular property could not be obtained, then a general range of values were used. The viscosity for PCL could not be obtained from any of the mentioned sources, possibly because proper testing has not yet been documented.

Resin Comparisons: Commodity Thermoplastics vs. Bioplastics It is not enough to understand the properties of just a single resin or even one group of resins, such as biopolymers. It is crucial to understand the properties of a wide range of different polymer resins so comparisons between different resins can be made. These comparisons are very important during the design process of a product. A part will require that the resin it is constructed from meets certain specifications such as, but not limited to; stiffness, impact strength, toughness, and hardness. Designers look at a wide range of polymers to find one that will meet all of these specifications while remaining as inexpensive as possible. Other factors such as density need to be factored in when purchasing a resin to determine the final price of the quantity of plastic required. It is also important for mold designers to know the mold shrinkage of the material quoted to construct the part to design mold cavities and runner systems. It is important to make these comparisons early in the design process to avoid costly mistakes. With the current push in the plastics community to move towards using more biodegradable polymers, it is extremely important to draw comparisons between biopolymers and the commodity polymers most commonly used today. Plastics such as polyethylene, polypropylene, and polystyrene are used frequently in the plastic industry to create many disposable products. This means these are they materials ending up in landfills and on the side of the road, basically these are the plastics that biopolymers are going to the most beneficial in replacing. So how do Nylon 11, PCL, and PLA compare to these commodity polymers? In the

following graphs of density, tensile strength at yield, and glass transition temperature, it can be seen that the biopolymers compare well to the listed commodity plastics. This shows that there is a green plastic that could replace a commonly used, fossil fuel based plastic based off several common material properties.

Density
0.05 0.045 0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 HDPE PP GPPS Nylon 11 PCL PLA

Density (lb/in3)

Density

Material

Manufacturers Several of the major manufacturers of polymers are involved in the biopolymer frontier. Companies such as Dupont and Bayer are involved in biopolymers. Also, some companies have formed specifically as a biopolymer manufacturer. Companies such as Natureworks LLC, dedicate their efforts toward the production and research of biopolymers. The manufacturers and compounders of biopolymers are on the cutting edge in a fierce competition to improve the renewability of plastics while retaining or increasing material properties.

Natureworks Natureworks LLC headquarters is located in Minnetonka, Minnesota. Natureworks LLC also has a manufacturing facility in Blair, Nebraska and has corporate offices in both the Netherlands and Japan. The company is considered one of the leading producers of biopolymers consisting of 100% renewable resources. Focusing on the manufacturing of PLA Natureworks LLC offers a plethora of options in the biopolymer world in the form of Ingeo. Ingeo is Natureworks patented line of biopolymers. The company is supported just over 80 distributers that distribute to the United States. They also have additional distributors that operate all over the world. Depending on the supplier, material can be purchased in everything from individual bags to a pallet level. The facility located in Blair, Nebraska is capable of producing 300 million pounds of PLA per year and the lactic acid plant there can produce 400 million pounds of lactic acid yearly.[32] As a general average the Ingeo biopolymers sell for around $1 per pound but this is a rough estimate for average because the price is heavily dependent upon the grade of the material. Annual income of Natureworks LLC is not released due to the private ownership status of the company. The main goal of Natureworks is to provide all of their services to satisfy the customer while leaving the smallest environmental footprint possible.

Structure Natureworks is a limited liability company (LLC). The company formed from a collaboration of Cargill and Teijin Limited of Japan. This partnership resulted in the formation of a vertical business structure that is owned partially by each of the groups mentioned above. Once formed, Natureworks LLC acts as a standalone company yet is considered privately owned. Services Technical services are available to aid in product selection, uses, handling instructions, storing instructions, disposal procedures, and information dealing with specific material properties. These are primarily performed by phone consultation. However, Natureworks LLC offers a very useful technical resource database on their website. This database provides information specific to the Ingeo biopolymers including technical data, processing guides, material property charts, and material safety charts. Local sales are dependent upon the region and the distributor. While Natureworks LLC itself offers technical resources, sales information is available from individual distributors.

Dupont Dupont is a worldwide corporation that exists in 70 plus countries. DuPont owns over 20,000 worldwide patents and over 14,000 worldwide patent applications.[38] Their office headquarters in the United States is located in Wilmington, Delaware along with a technology center. The company has resin distributors located in both Columbus, Ohio and Lamont, Illinois.. These materials are sold as the Biomax and BioStrong line of products which are Duponts patented lines of biopolymer materials. The additives are specifically tailored for use with PLA as well as the other materials offered such as the thermoplastic starches (TPS). In speaking to the project manager of the biopolymer department, specific information on these products was obtained. The most common materials that Dupont sells are injection molding grades of the materials. Specifically, Biomax PTT and Biomax TPS are popular materials. The Biomax PTT sells for around $1.75 and is sold in 55lb bags as well as gaylords. The Biomax TPS is only available in 55lb bags and ranges from $1.50 to $3.00 per pound depending on the grade. The BioStrong products which include resins such as PLA are sold in all sizes from bags up and range anywhere from $1.50 and up depending on the grade and amount purchased. Grades for higher end applications can be very pricy [35]. In 2007 Dupont gained $30.6 billion in revenue which created a net income of $2.98 billion. Structure The corporation is headed by a board of directors and is comprised of a horizontal structure that has subdivisions due to regions. The structure then becomes a vertical structure within the regional divisions. This configuration allows for the much easier management due to the presence of subdivisions. Services Dupont offers a full range of technical help and support depending on the amount and price of the material that was purchased. Services available to consumers include product testing, process suggestions, uses, handling, storage, and specifications. These services are accomplished by Duponts ability to perform a complete analysis by way of a full audit. Although this takes

some time the results are very thorough. The technology services strive to weed out all unrelated data and supply only the most pertinent information. By some sources, Dupont has been named the leading supplier of technical services on a global level. Sales representatives and customer services are available nationwide in the United States depending on the service required and the region of both the customer and the facility.

Bayer Bayer is considered one of the largest suppliers of polymers in the market and is heavily researching biopolymers. The corporation deals with many venues and has a strong focus on material science and is a frontrunner in the global market. They are listed as a manufacture of PLA and are expanding research to improve on the environmental side of polymers. Full technical services are available from material testing to guidelines on processing, handling, and use. Overall Bayer wants to improve life for mankind while putting focus on biotechnology when dealing with high tech materials.

Bayer Material Science Net External Sales Gross Cash Flow Net Cash Flow

2006 2007 10,161 10,435 1,166 1,228 1,281 1,147 Ref [27] Note: Values are in millions of Euros.

%Change +2.7 +5.3 -10.5

Headquarters for Bayer is located in Leverkusen, Germany and in the United States Bayer has a regional headquarters in Pittsburgh, PA for material science as well as various locations throughout the country. Structure Bayer is a global corporation. The corporation is laid out into three subgroups one of which is high tech materials represented by the Material Science division. These groups are headed by a board of representatives which strings the divisions out in a horizontal business structure. The divisions themselves, such as Material Science, consist of vertical business structures individual to that division. Furthermore, these divisions are broke down into regions that represent sites in specific areas. The goal of this layout is to allow for centralized control that still allows the regions to be somewhat independent. This set up also allow for quick feedback to the upper tiers so that adjustments can be made. Services The services that are available are dependent upon the level of the customer. The totals services offered entail problem solving, product performance evaluation, onsite services, seminars, and other related services. A customer who purchases large volumes on a regular basis will be qualified for the highest level of full service including testing services from a full range of testing procedures depending on the customers needs. If a customer is a lower level customer then they may only be offered consultation and problem solving services. Locally, a sales representative and customer service is available at the Material Sciences regional headquarters in

Pittsburgh. Through these resources and a full online data base, specific information on their products is available. This information includes case studies, processing technology information, and testing technology information that is obtainable to answer as many questions about the materials as possible. Any questions that are left unanswered will be referred to other branches if necessary. Recycling of Biopolymers The two sides of the sustainability platform that happen to directly oppose one another are recycling and degrading of polymer materials. As of late, the balance of the two seems to be heavily weighing toward the biopolymers and steering away from recycling. Despite the primary reason for the initiative of biodegradable resins being introduced into common, everyday uses, such as degradable bags and bottles, the other side of the sustainability platform is being researched. The recyclability of biodegradable resins seems to be slightly odd, as the primary reason for the use of these materials is to dissipate to eliminate the need to recycle. As it turns out, the products made from degradable resins do see some degree of recycling. But as with any recycling process it is not cost effective to recycle. Recycling is an expensive and difficult process that turns used products into new ones. In addition, biopolymers offer even more levels of problematic scenarios while recycling. It is inferred, though from limited resources, that recycling these resins can produce yield loss from contamination and incompetent critical mass. This means that when recycled bottles are received to again be recycled, ones that possess a degree of biodegradable material must be separated because of the losses associated with them. They can prove to hinder the performance of the primary material in bottles, PET. It is a suggestion to not include these materials in applications that do typically see a lot of recycling since they can augment to the economic burdens even in minimal amounts of contamination. This also denotes that one should take note when deciding applications for use of these materials. Especially ones that overlap products typically recycled, unless the critical mass can be achieved easily. [40] Despite the complexity in recycling, NatureWorks has announced a plan for postconsumer PLA bottles that is designed to institute a large-volume "buy-back" system for the problematic resin. Through their buy-back program, MRFs, or municipal recycling facilities in strategic locations will separate the used PLA bottles into specific PLA bales meeting a preset specification. Then, for a predetermined price, NatureWorks will purchase these bales and direct them to a suitable end-of-life purpose based on location of collection and popular market demands. PLA can be sorted from other plastics using standard near-infrared equipment. It is said that through hydrolysis, the MRFs will have the ability to separate PLA so that it can mechanically or chemically be depolymerized into its monomer. This NatureWorks program also makes possible an alternative landfill waste division option for the resin. Even with some recourses complaining that the recycling of PLA can produce problems for the larger scale recycling of resins like PET and HDPE, some arbitrary independent studies have verified that PLA can subsist with negligible influence on the current recycling medium. [44]

Costs With the rise of technology and effort into naturally occurring plastics it is hopeful that the polymerization of these materials will continue to decrease in cost. Despite being more expensive, the long-term motive of the plastics industry and environmentalist is to see the

production of biomaterials as more economical and feasible than their oil-based contenders. As the fermentation and the generic engineering of plants as bioreactors becomes more and more studied to polymerize soy protein, vegetable oil, starches, cellulosics, triglycerides and bacterial polyesters, a steep decline in costs of these can be anticipatedly made possible. [41] Taking a closer look at the cost of the biomaterials that are being studied in this paper, it can quickly be noticed that not only are these biomaterials more expensive; they are much more expensive. Glancing at PCL or Polymorph as it is often referred too, the first thing observed is that these prices are measured in dollars per ounces rather than dollars per pound like most resins. Some huge materials complexes have posted that PCL can range anywhere from $1.16 to $1.50 per ounce. To put this into perspective, this base material would be roughly $18 to $24 per pound. The material called Friendly Plastic or Shapelock turns out to not have a very friendly price. These values were found from The Compleat Sculptor Friendly Plastic in NYC, Sunshine Discount Crafts of Florida, and ShapeLock Plastics of California. Despite being overly expensive, not all biomaterials cost as much as PCL. Since biomaterials are polymerized using many different materials such as corn and bacterial polyesters, it really depends initially how much those materials are that determines the end price of the synthetic plastic. As showed in the graphs below, the rising cost of agriculture products may hinder the ability of these materials to drop much in cost like hoped for. [42]

However, the unstable price of crude oil continues to emphasize the growing need for renewable-resource-based substitutes. The cost of the Natureworks trademark Ingeo biopolymer (PLA) is analogous to other conventional plastics materials. The Ingeo biopolymer has the potential to even become even more cost advantaged to standard resins. Natureworks has even commented their prices competitive to that of PET and PS which happens to be in the range of $.85 to $1.00 per pound. [44]

COST COMPARISON OF RESINS

25 COST PER POUND, USD 20

15
10 COST 5 0 PLA PCL GPPS HDPE PVC RESIN PET PA6/6 PHB PC

It is difficult to group the cost of all biopolymers into one because it is really a completely different process to polymerize each type of resin. Even if the biomaterials in general are more expensive than conventional resins of equal or better processability, it is other ways that the biomaterials pick up for the lack of price advantage. Wal-Mart plans to use 114 million PLA containers a year, which company executives estimate will save 800,000 barrels of oil annually, as a quote from Smithsonian Magazine states. [43] Also, being a biopolymer, the idea of the resin is to be easily depolymerized into the resin again and yet again made into a useful product. As previously said, biopolymers can have a huge drawback of higher pricing compared to conventional polymers. While the generally used polymers can be grouped to costing roughly around $1000 to $1500 per MT, biopolymers can cost anywhere from $4000/MT to as high as $15,000/MT for material such as polyhydroxybutyrates (PHB). However, more commonly used biopolymers like PLA based polymer are at the lower end of the spectrum like Natureworks had noted. Again, as the preliminary stage of progress gets over and manufacturing plants conquer higher productivity, prices are projected to decline significantly. However, despite being the up and coming way of the plastics industry, bio-resins will likely never peak the level of use of petroleum based polymers. Currently, from an overall price comparison standpoint, to sum up the comparison in costs, biopolymers are 2 to 7 1/2 times more expensive than traditional establishment resins. Yet, only five years ago, biopolymers were 35-100 times more expensive than existing non-renewable, fossil fuel based equivalents. Thus, proving then downward spiral trend of bio-resin prices. [45]

Local Supplier/ Compounder The largest local supplier of Biopolymer resins is located in Avon Lake, Ohio. Not only local, but PolyOne is the worlds premier provider of specialized polymer materials, services, and solutions. They boast yearly revenue of $2.7 billion and have active operations in North America, South America, Europe, and Asia. Offering more than 35,000 products, PolyOne has greater than 10,000 regular customers in 35 countries, including 51 manufacturing facilities and 13 warehouses in 20 countries. PolyOne emphasizes strategy in specialization, commercial excellence, globalization, and operational excellence. PolyOne uses a business model of the base polymer and the addition of additives and pigments to create custom compounding, color and additive masterbatches, and polymer distribution. These outputs are then passed on to the processor, OEM, or consumer. PolyOne has many technological focus areas including Color Appearance & Sensory Technology, Impact Modification, FR Technology, and Characterization; however, for the purposes of this report, the focus will be on PolyOnes Bio-Material Technologies. [46]

Driving Force of Biopolymers In terms of what is driving Bio-Materials, all are gaining momentum. The price history of fuel cannot match a more stable alternative, the sustainability initiative plays a huge role, and Innovation & Image also contribute to the need for these resins. In essence, the corporation is taking a new chain of action in order to produce the materials. The initiative is changing from a chemical industry to a bio chemical industry, and what PolyOne does is take the agricultural based polymer and uses downstreaming processing for the distribution, compounding, addition of colorants and additives, and consulting to create the final component. PolyOne connects raw material suppliers to market needs. [46]

Life Cycle As previously touched on, not all biomaterials are biodegradable or even all made utilizing biobased resins. There is a very fine line between biobased and petroleum based resins, and also a difference between biodegradable and non-biodegradable resins. The base of the material is the beginning of life option of the polymer. This is how the material was polymerized, from oil or starches, etc. The end of life option decides whether the resin can successfully be broken down into its harmless monomer or if it cannot degrade. The below charts thoroughly map out the possibilities of mixing and matching different beginning and ending of life options and what some example resins of each are.

-Obtained from PolyOne PowerPoint from presentation at February 2009 SPE meeting. Property of PolyOne.

-Obtained from PolyOne PowerPoint from presentation at February 2009 SPE meeting. Property of PolyOne.

As one might infer, it is critical for the producer to understand exactly the consumers specific needs and objectives of the desired biomaterial in terms of biodegradability and origin. [46]

Market Challenges Although the progression of biopolymers continues to grow, there are still very apparent market challenges presented to the inspiration. There is limited application of biomaterials for many reasons beginning with the simple fact of limited availability as most of the common resins are in a state of short supply for the actual demand of the resins. Next, the performance of the virgin material without the influence of additives is deemed as subpar. There has been and continues to be advancements in the addition of additives to make the materials useful and not just desired because of sustainability. Problem resins also introduce difficulties during processing, poor intellectual properties, and another significant disadvantage of these polymers is their cost which will be discussed later. However, putting all negatives aside, the goal of

PolyOne and others alike is to change the material solutions from neat biopolymer resins toward complex compounds with extended functionality. [46] Like the old clich annunciates, challenges present opportunities. The current and most likely application of the materials is integrated into short term, essentially throw-away, disposable products such as food containers, blister packs, bottles, and any other package that is likely to be tossed along the roadside. What understandably possesses the greatest potential for opportunity is the product line of durables, where biomaterials could someday make a vital contribution into products such as computer housings, cell phones, and vehicles components. The model below shows the relationship of where the materials are applicable to a designated timeline. It clearly shows that the initiative will likely progress to durables over time as advances in properties take place. [46]

-From PolyOne presentation, Courtesy of Natureworks LLC.

Technical Challenges/ Opportunities (Local Tech Services) PolyOne explains that the same properties of the biopolymers that present challenges are also the greatest areas for opportunity. Some of these areas include but are not limited to poor impact, low melt viscosity, sticking to metal, coloration, crystallization kinetics, density, cost, degradation, odor, and the simple natural appearance of the materials. The chart on the next page gives ideas that PolyOne would consider to implement the base resins to generate more useful properties out of them. [46]

-Obtained from PolyOne PowerPoint from presentation at February 2009 SPE meeting. Property of PolyOne.

Case Studies One study that had presented particular interest to PolyOne was the PLA Heat Resistance Enhancement opportunity. They explained that current approaches include stereocomplex formation of the polymer, and using crystallization. However, the necessary PDLA isomer is not presently commercially available at a viable cost for the stereocomplex formation method, and efficient nucleants still do not provide required performances. With that said, the objective was to improve the heat performance of PLA. The alternative solutions offered are crosslinking, filler/fiber reinforcement, and polymer blends.

-Obtained from PolyOne PowerPoint from presentation at February 2009 SPE meeting. Property of PolyOne.

Above shows the improvements in HDT which directly correlates to the Heat Resistance of PLA.

-Obtained from PolyOne PowerPoint from presentation at February 2009 SPE meeting. Property of PolyOne.

The Performance Comparison graph displays the ranges of HDT and Notched Impact Izod Test to show the performance of the solution blends to the Heat Resistance problem of PLA. It can be seen that PolyOne has developed biopolymer blends with parallel performances to engineering polymers like polycarbonate. The only drawback is that the blends sometimes consist of a large portion of additives to biomaterial ratio. [46] Availability and Contacts The majority of the data for the local sales of biopolymers was obtained from PolyOnes presentation at the February 2009 SPE meeting. The presenters and local sales persons that could be contacted are Roger Avakian and Jason Zhu. The services of PolyOne have been discussed in detail as they can mix the blends and send out material to the consumer, hence the link between raw material and the market needs. They produce masterbatches and can ship out gaylords, bags, trucks, or railcars of material for any application. Lastly, it can be said that despite the growth being slowed by availability, processability, performance, and economics, biopolymer solutions will continue to penetrate the existing market. [46]

MATERIAL CONTENT REPLACED: 1) Domestic and Import Markets replaced with overall effects of different materials (PLA, PCL, PA11) on sustainability 2) Available grades replaced with explanation of plant fiber reinforcement and explanation of biodegradable additive 3) Volume Discount Schedule replaced with technical challenges 4) 5 year price history market challenges 5) Real price vs. published price driving force of biopolymers 6) Price Negotiations life cycle routes of biopolymers 7) Is off-spec material available at a discount, how off spec is it, and cost for recycled material case studies and different blends

SOURCES
-

Copolymerization of PolyLactic Acid with Cysteine and the Potential Use of the Copolymer as a Scale Inhibitor in Hard Water o www.utm.edu/departments/cens/chemistry/old_site/Minesh%20ACCM04.ppt [1]
Development of Plant Fiber-Reinforced Polylactic Acid (PLA) Plastic

o http://www.toray.com/news/pla/nr070517.html [2] Material Properties and Biocompatibility of Self-Crosslinkable Poly(caprolactone fumarate) copolymer as a Scaffold for Guided Tissue Regeneration o http://www.nt.ntnu.no/users/skoge/prost/proceedings/aiche2004/pdffiles/papers/089e.pdf [15] Polylactic acid o http://en.wikipedia.org/wiki/Polylactic_acid [3] o http://www.ides.com/generics/pla.htm [4] o http://www.worldcentric.org/biocompostables/bioplastics [5] o http://www.natureworksllc.com/product-and-applications/ingeobiopolymer/technicalresources/~/media/Product%20and%20Applications/Ingeo%20Biopolymer/Te chnical%20Resources/Technical%20Data%20Sheets/TechnicalDataSheet_30 01D_pdf.ashx [21] PA 11 o http://www.arkema-inc.com/index.cfm?pag=109 [6] o http://www.matweb.com/search/DataSheet.aspx?MatGUID=ec7ea4063a2a4c7 09e89177103059919 [16] o http://www.goodfellow.com/E/Polyamide-nylon11.html [17] Polycaprolactone o http://www.ides.com/generics/PCL.htm [7] o http://en.wikipedia.org/wiki/Polycaprolactone [8] o http://www.biodeg.net/bioplastic.html [18] o http://www.absorbables.com/properties.htm [19] o http://www.matweb.com/search/datasheet.aspx?MatGUID=c1d8836d69fc4cd c953f91040cd29425 [20] General Information o http://www.biobasics.gc.ca/english/View.asp?x=790 [9] o http://en.wikipedia.org/wiki/Sustainability [10] o http://en.wikipedia.org/wiki/Bioplastic [11] o http://en.wikipedia.org/wiki/Biopolymer [12] o http://en.wikipedia.org/wiki/Ring-opening_polymerization [13] o http://www.bio-tec.biz/products.html [14] o CES Edupack 2008 [22]

o Moldflow material database [23]

-

Bayer o http://www.bayermaterialscience.com/internet/global_portal_cms.nsf/id/testin g_technology_en [24] o http://www.bayermaterialsciencenafta.com/businesses/OurLocations.htm [25] o http://www.bayermaterialscience.com/internet/global_portal_cms.nsf/id/Tech nical_Support_en [26] o http://www.annualreport2007.bayer.com/en/bayer_annualreport_2007.pdfx [27] Nature Works o http://www.natureworksllc.com/About-NatureWorks-LLC.aspx [28] o http://www.plastemart.com/upload/Literature/Biopolymerhasagoodgrowthpro spects.asp [29] o http://www.bayermaterialsciencenafta.com/products/index.cfm [30] o http://natureworks.custhelp.com/cgibin/natureworks.cfg/php/enduser/std_adp.php?p_faqid=271&p_created=1072 207417&p_sid=BJ1XHYrj&p_accessibility=0&p_redirect=&p_lva=&p_sp=c F9zcmNoPSZwX3NvcnRfYnk9JnBfZ3JpZHNvcnQ9JnBfcm93X2NudD0yM jEsMjIxJnBfcHJvZHM9JnBfY2F0cz0mcF9wdj0mcF9jdj0mcF9zZWFyY2hfd HlwZT1hbnN3ZXJzLnNlYXJjaF9ubCZwX3BhZ2U9MQ**&p_li=&p_topvi ew=1 [31] o http://natureworks.custhelp.com/cgibin/natureworks.cfg/php/enduser/std_adp.php?p_faqid=64&p_created=10596 62994&p_sid=csndSZrj&p_accessibility=0&p_redirect=&p_lva=&p_sp=cF9 zcmNoPSZwX3NvcnRfYnk9JnBfZ3JpZHNvcnQ9JnBfcm93X2NudD0yMjEs MjIxJnBfcHJvZHM9JnBfY2F0cz0mcF9wdj0mcF9jdj0mcF9zZWFyY2hfdHl wZT1hbnN3ZXJzLnNlYXJjaF9ubCZwX3BhZ2U9MQ**&p_li=&p_topview =1 [32] Dupont o http://www2.dupont.com/Plastics/en_US/Knowledge_Center/index.html [33] o http://www2.dupont.com/Biomax/en_US/ [34] o Phone Interview 2/12/09 3:10 PM: Suzan Homan in management of Biopolymer development. [35] o http://www2.dupont.com/Biomax/en_US/assets/downloads/biomax_strong.pd f [36] o http://nyjobsource.com/dupont.html [37] o http://archive.corporatewatch.org/profiles/dupont/dupont4.htm#food_chain [38]

Poly One o http://www.polyone.com/enus/products/bioproducts/Pages/OnCapBIOAdditiv es.aspx [39] Biopolymers in the Existing Postconsumer Plastics Recycling Stream o http://www.springerlink.com/content/h861m8705632h010/ [40] How Plastics Work o http://science.howstuffworks.com/plastic6.htm [41] Polymorph o cap-polymorphftir.jpg&imgrefurl=http://reprap.org/bin/view/Main/Polymorph&usg=__n96Y Lvnxm4AfbH3XAnchJWwkMTA=&h=427&w=800&sz=132&hl=en&start= 12&um=1&tbnid=jhaY0ZsAyx9H2M:&tbnh=76&tbnw=143&prev=/images %3Fq%3Dprice%2Bhistory%2Bof%2BPolycaprolactone%26um%3D1%26hl %3Den [42] Corn Plastic to the Rescue smithsonian mag o http://www.smithsonianmag.com/science-nature/plastic.html [43] NatureWorks o www.natureworksllc.com [44] Biopolymer has good global growth prospects-plastemart.com o http://www.plastemart.com/upload/Literature/Biopolymerhasagoodgrowthpro spects.asp [45] *SPE February 2009 PolyOne presentation [46]