ADVANCED MATERIALS AND CHEMICALS

Hybrid Plastics

Innovative Research Makes Novel Nanostructured Material Viable

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A new class of chemicals called polyhedral oligomeric silsesquioxanes (POSS) was first researched by General Electric in the 1960s and then developed by the U.S. Air Force in the early 1990s. This novel material was a hybrid of organic and inorganic molecules; its unique characteristics were enhanced further by its nanometer size (one-billionth of a meter). The size and structure of the POSS molecule significantly increased the ways this material could be used. However, producing just one pound of POSS cost as much as $5,000 and took three months. If less costly manufacturing was possible, POSS material could be widely used yielding huge benefits to the US economy.

Finding a new, cost-effective and efficient way of manufacturing POSS entailed significant effort to find new raw materials and processes. Hybrid Plastics, a small company that had spun off from the Air Force Research Laboratory, had innovative ideas about POSS manufacturing but not the funds to support its implementation. In 1998, the company successfully applied for and received an Advanced Technology Program (ATP) award to start the research. Their ATP-funded project lasted three years.

In this research, Hybrid Plastics discovered ways to produce POSS from cheaper materials reducing production cost to $10-50 per pound and processing time to just one day. Because POSS molecules were of a nano size, they were called POSS nanostructured chemicals. When formed into polymers, the POSS material was lightweight, odorless, fire and heat resistant, disposable, and emitted no vapor. Furthermore, it proved to have selective permeability, good barrier properties and radiation resistance. The company developed a POSS product line of 158 types of materials; all were based on a common “cage-like” molecular structure but used different raw materials.

The chemicals and plastics industries viewed Hybrid Plastics’ innovation as one of the most promising developments since the 1950s. In 2005, the President of the United States issued a Presidential Determination that POSS nanostructured materials were in the “strategic national interest,” a recognition that will have a tremendous economic impact. The company plans to produce 2 million pounds of POSS materials in 2009 compared to 20,000 pounds in 2005. Since 2004, the company has received additional research grants from the National Institutes of Health, U.S. Air Force, National Aeronautics and Space Administration, and National Science Foundation. As of 2006, Hybrid Plastics has won numerous awards and been issued 10 patents for its POSS technology.

COMPOSITE PERFORMANCE SCORE
(based on a four star rating)
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Research and data for Status Report 98-01-0059 were collected during April – June 2006.

Novel Nanostructured Material Costly to Produce In the late 1990s, a growing number of businesses began exploring nanotechnology as a means to improve

common and/or highly specialized materials. (Nanotechnology is the science and technology of building devices from single atoms and molecules.) For example, nanostructured pigment used in suntan lotion

showed greater protective effects against harmful ultraviolet radiation, and common plastics could be made fire-retardant at lower cost and without the use of hazardous chemicals by using nanotechnology. The nanometer, which is the basic measuring unit in nanotechnology, is one-billionth of a meter. On this scale, the width of the average human hair is about 80,000 nanometers. Researchers had shown that materials this small could affect the property characteristics of the materials into which they were inserted. Manufacturers wanted to take advantage of this unexpected behavior by combining nano-sized materials with other materials such as sand, silicon, metal, or plastic to improve their products. The chemicals and plastics industries lacked an economical manufacturing process; a pound of POSS material cost between $1,000 and $5,000 to manufacture, and production took as long as three months. Using nanotechnology, the U.S. Air Force developed a new class of hybrid material called polyhedral oligomeric silsesquioxanes (POSS) for aerospace applications. Originally discovered by General Electric in the 1960s, POSS was a hybrid organic–inorganic molecule that, when formed into a polymer, showed properties of organic polymers and ceramics. POSS polymers were lighter, more durable, and able to withstand higher temperatures than conventional polymer formulations. It was widely believed in the chemicals and plastics fields that POSS polymers might launch the first new wave of high-performance plastics and polymer applications since the 1950s. However, the industry lacked an economical manufacturing process: a pound of POSS material cost between $1,000 and $5,000 to manufacture, and production took as long as three months. Hybrid Plastics Plans to Explore New Production Techniques A small spin-off company, Hybrid Plastics, was created by Air Force researchers to commercialize these nanomaterials and is the sole supplier of POSS material. In the late 1990s, they proposed to find new feedstock (raw materials) to manufacture POSS more

economically and efficiently. Finding new feedstock would eliminate the need to use expensive and exotic feedstocks, which had thus far limited the widespread application of POSS materials. The company also proposed to develop alternate manufacturing methods that would allow POSS to be produced in high volume and at low cost. The economic impact of such a breakthrough would be significant for the plastics industry. A wide variety of new products like contact lenses, automotive components, carpets, golf balls, and watercraft could be improved with POSS materials. Construction materials like acrylics and urethanes could be enhanced by using POSS; resin manufacturers could use POSS as an additive in manufacturing flame-retardant materials; and sporting goods manufacturers could use POSS materials in golf accessories, wet suits, and lighter, damage-resistant surfboards. While the development of new feedstock and the subsequent mass production of POSS nanostructured material would significantly benefit the plastics and chemicals industries, major chemical companies and venture capitalists still considered the project speculative in the late 1990s. They were not interested in investing in this kind of research, and Hybrid Plastics did not have the capital necessary to fund the research. Because of the high technical risk and the innovation required to develop an efficient and high-volume production method for POSS, and because the properties of POSS had wide application in fields as diverse as aerospace and microelectronics, Hybrid Plastics applied for and won an ATP award for a three-year research project starting in October 1998. As Hybrid Plastics co-founder Dr. Joseph Lichtenhan said, "When we started, it took up to three months to make a pound [of POSS] and it cost $5,000. The government is the only organization that could afford to lead the charge. No one else would be patient enough." Major subcontractors on this project were the U.S. Air Force Research Laboratory (Edwards Air Force Base) and the Department of Chemistry at the University of California at Irvine. It was projected that if Hybrid Plastics succeeded in its research, the company could generate estimated annual sales within the plastics industry alone of $66 million. Even if the costs to manufacture POSS

materials were reduced by only one order of magnitude, this project had the potential to bring substantial economic and technological benefits to the nation. Researchers Face Three Problems The three problems that vexed Hybrid Plastics researchers were the cost and source of feedstocks, inefficiency of production processes, and economies of scale (lowering of unit production cost for higher output). They expected to resolve these problems by exploring options to produce POSS from (1) low-cost and readily available silane feedstock produced in large scale by the silicones industry, (2) low-cost and readily available resin waste from the silicones industry, (3) sand, or (4) readily available silicate feedstocks. Because silicon in the form of silicates or sand is one of the most abundant components of the earth’s crust, Hybrid Plastics researchers considered this the most promising ingredient for POSS feedstock. In fact, the first phase of their research would consist of a comparative evaluation of feedstocks from silanes, sand, and resin, and the next phase would explore methods of manipulating POSS feedstock to improve the variety of materials that could be made. If these methods and techniques proved successful, the third and final phase would comprise intended advances to the POSS production process. Figure 1. POSS Molecular Structure POSS’ organic–inorganic molecular structure was unique. As depicted in Figure 1, it was built as an inorganic cage made up of silicon (Si) and oxygen (O) atoms surrounded by organic groups (R) attached to the silicon around the outside. By varying the identity of

the surrounding R groups, a whole new family of nanostructured materials became possible. A monomer is a single molecule of a chemical compound that can chemically combine with identical molecules of similar reactivity to form a long-chain molecule known as a polymer. To build a POSS monomer, researchers needed to construct the cage-like portion of the molecule shown in Figure 1 from different silanes. They reached a significant technical milestone in the first quarter of the ATP-funded project when they developed a low-cost POSS monomer by using a vinyl compound at the R points of the molecular structure. In early 1999, Hybrid Plastics researchers made another breakthrough when they developed a low-cost method for producing a wide variety of POSS derivatives. They also confirmed that POSS nanostructures could improve the mechanical properties, hardness, abrasion resistance, and fire resistance when added to other plastic materials. The development of new feedstock and the subsequent mass production of POSS nanostructured material would significantly benefit the plastics and chemicals industries. In September 1999, the Hybrid Plastics team discovered a way to produce POSS nanostructures by mixing inexpensive silanes, such as methyl, ethyl or vinyl. This expanded the number of inexpensive silane feedstocks that could be used in building POSS nanostructures. Because methyl silane was one of the cheapest feedstocks, its conversion into a POSS nanostructured material was one of Hybrid Plastics’ research goals. But when researchers actually succeeded in this effort, their enthusiasm was dampened because the resultant POSS product was extremely insoluble. In December 1999, they finally identified several organic solvents for methyl-based POSS. By this time, the estimated large-scale production cost of POSS nanostructures had been trimmed to $76 per pound, with additional reductions anticipated in the next phase of the project. Hybrid Plastics Creates a Buzz in the Industry As their research progressed, Hybrid Plastics attracted attention from the chemicals and plastics industries.

The researchers were invited to present their findings at several professional and scientific conferences and symposia while the company experienced a surge in the sale of POSS nanostructured chemicals. The ATP-funded research created significant interest within the United States at a time when the chemicals industry was facing pressure because of POSS developments in Japan and China. The company attributed this growing interest to the ATP funding. Hybrid Plastics researchers made another breakthrough when they developed a low-cost method for producing a wide variety of POSS derivatives. By June 2001, Hybrid Plastics had demonstrated that nanostructured POSS molecules could be incorporated in other polymers for various applications. For instance, unlike ordinary silicates, POSS nanostructured molecules could be linked chemically to other types of polymer molecules for widespread application. POSS materials could be made available as powders, oils, and waxes; they could be melted, dissolved, or blended into plastics as filler; or they could be used as a surface coating or lubricant. The resulting POSS Polymer System was an unprecedented feat in the nanostructured materials field. Researchers Build Unique POSS Structure By the end of the ATP-funded project, Hybrid Plastics had accomplished all their major goals. They overcame technical challenges to significantly lower the manufacturing cost of POSS nanostructured chemicals from a range of $1,000 to $5,000 per pound to $30 to $50 per pound and had reduced production time from three months to less than one day. Furthermore, it was now possible to use POSS material as an important additive or reactant to improve the characteristics of plastics on a large-scale basis. Hybrid Plastics also built a unique process by which they could vary the organic component of the POSS molecule (shown as “R” in Figure 1) to build several types of compounds, including those having the ability to bond

chemically with other substances. While the cage-like framework of the POSS molecule provided stability and hardness, the organic component provided reactivity to form polymers with toughness and the ability to be processed by conventional techniques. This unique feature of POSS brought commercial success to Hybrid Plastics. Indeed, the ATP-funded project enabled the company to build a platform technology for a POSS product line with 158 products. In 2006, the company experimented with incorporating metal atoms at the vertices of the same silicon–oxygen cage to create a new nanostructured material called polyhedral oligomeric metaloquioxanes (POMS). These POMS materials are now being commercialized. POSS Gains National Recognition Hybrid Plastics won numerous awards for its POSS technology during and after the ATP-funded project. Some of these awards are listed below: · “2000 Award for Excellence in Technology Transfer” from the Federal Laboratory Consortium for the transfer of POSS nanotechnology to the private sector · "R&D 100 Award" in 2001 as one of the 100 globally most technologically significant new products that year by R&D Magazine · "Collaboration Success Award" in 2002 for best collaboration among business, academia, and government by the Council for Chemical Research · Finalist for "2002 Best of Small Tech Award" from Small Times Magazine for the best product globally in nanotechnology, Microelectromechanical system (MEMS), and microsystems in November 2002 · Received a Presidential Determination^1 in 2005 that POSS is in the "strategic national interest of the United States.” Hybrid Plastics has commercialized the technology developed in the ATP-funded project for products ranging from dental products to food packaging to space based applications. Typically, POSS nanostructured materials are used in applications where manufacturers face problems with a conventional material. For example,

¹Presidential Determination under Section 303(A)(5) of Defense Production Act dated December 20, 2005

when conventional meat-packaging material could not stop meat spoilage, POSS nanostructured material was tried, and it successfully improved the shelf life of packaged meat products. Hybrid Plastics has entered into joint development or cost-shared collaborative agreements with other companies and agencies. The company has received 10 patents started by its work in the ATP-funded project. Current Product Line is Diverse “Hybrid Plastics…is working with several partners to roll out a rather impressive little molecule with a plethora of possible applications,” wrote Robert Dixon in the October 28, 2002 issue of Small Times Magazine. The company has lived up to market analysts’ expectations by offering a diverse range of POSS nanostructured products based on the ATP-funded technology. As of 2006, their product line includes the following: · Nanobond UV curable adhesive · POSS acrylics · Firequench 1287 and 1288 · Molecular silica · Silanol-POSS polymer systems · POSS phenolics · Nanostructured POSS cure promoters and accelerators · Nano-reinforced POSS polyamide · Nano-reinforced cellulose propionate acetate · Nano-reinforced polybutylene terephthalate Custom Applications of POSS Impact Economy In 2003, Hybrid Plastics teamed with the University of Southern Mississippi to collaborate in the research, development, and commercialization of POSS polymers and derivative nanocomposites. Together, they set up a Nanotechnology Center of Excellence to promote nanotechnology in agricultural products, cosmetics, electronics, polymers, coatings, paints, and composites. In 2004, the company built a manufacturing plant for POSS nanostructured chemicals with annual production

capacity of 50 tons. This capacity is now being upgraded to 1,000 tons annually. Hybrid Plastics has commercialized the technology developed in the ATP-funded project for products ranging from dental products to food packaging to space based applications. Hybrid inorganic–organic composites like POSS polymers hold significant promise because they combine the physical properties of ceramics and the chemical reactivity of organic materials. Because the POSS nanostructured material can be used to manufacture a diverse group of products, Hybrid Plastics has been able to successfully customize applications, as described below: · Dental adhesive: Pentron Clinical Technologies used POSS nanostructured polymers from Hybrid Plastics to develop dental bonding agents called Nano Bond. The company received a $750,000 research grant from the National Institutes of Health to pursue product research. · Electronic solder: Hybrid Plastics received a $100,000 research grant from the National Science Foundation to develop nanostructured materials to boost the performance of lead-free solders for the electronics industry. Teaming with Michigan State University in this project, the company will develop a POSS material to chemically reinforce these solders. · Meat packaging: The company used POSS’ barrier properties to develop a special casing for sausage packaging that has greatly increased the shelf life and stopped spoilage of meat by acting as a barrier to harmful bacteria. · Radiation shield: Hybrid Plastics received an $850,000 research grant from the Missile Defense Agency of the U.S. Air Force to develop low-cost radiation shielding. Generally, polymers used in the construction of space vehicles and platforms undergo severe degradation from exposure to radiation. Samples of nine different POSS polymers

were attached to the International Space Station and tested for durability (see Figure 2). Scientists found that POSS polymers formed a ceramic shell that withstood radiation bombardment at least 10 times longer than other materials. They determined that POSS materials held promise for the development of a new generation of novel, space-survivable materials. POMS also holds promise as an efficient coating for the exterior of a space vehicle . By reducing radiation damage, both POSS and POMS will lower costs in a wide variety of space applications. Figure 2. Scientists test POSS at International Space Station · Protective coating for solar cells: Hybrid Plastics has teamed with another company and a university group under a National Aeronautics and Space Administration (NASA) Glenn Research Center program to develop protective coatings for next-generation thin-film solar cells for space applications. R&D Magazine described Hybrid Plastics’ POSS nanostructured material as one of the most promising “among the products and processes that have brought us new conveniences, increased our well-being, and revolutionized the way we live.” Hybrid Plastics has even begun to be recognized by the popular press: the company's journey was featured in the February 22, 2005 issue of the New York Times. The Federal Government’s recognition of POSS technology as having "strategic national interest” has significantly boosted the importance of this ATP-funded technology, as well as the company’s potential to

commercialize it. Hybrid Plastics expects to raise its annual production level of 20,000 pounds of POSS material in 2005 to 2 million pounds in 2009. Conclusion A new class of chemicals, polyhedral oligomeric silsesquioxanes (POSS), was researched and abandoned by General Electric in the 1960s. It was then taken over and developed by the U.S. Air Force for aerospace applications in the 1990s. The POSS molecule is a nanostructured material with desirable properties. When incorporated into polymers, POSS can improve the material’s strength, selective barrier properties, weight, and flammability characteristics. However, the manufacturing process for POSS was too expensive and problematic for the Air Force itself to develop. In 1998, Hybrid Plastics was formed as a spin-off of the Air Force Research Laboratory to further develop and commercialize the technology. The ATP-funded research project successfully reduced the cost of POSS production from a range of $1,000 to $5,000 per pound to $30 to $50 per pound and the production time from three months to one day. This technical success has resulted in substantial economic impact. Hybrid Plastics is continuing to refine the manufacturing process and lower the cost of POSS to facilitate its use in consumer products and the commercial aerospace, biological, pharmaceutical, agricultural, packaging, and micro-electronics industries.

PROJECT HIGHLIGHTS
Hybrid Plastics

Project Title: Innovative Research Makes Novel Nanostructured Material Viable (Nanostructured Chemical Feedstocks: The Next Generation of High-Performance Polymeric Materials) Project: To discover a viable and cost-effective large-scale production process for polyhedral oligomeric silsesquioxanes (POSS) nanostructured material and refine it for diverse applications. Duration: 10/1/1998 - 9/1/2001 ATP Number: 98-01-0059 Funding (in thousands): ATP Final Cost              $1,988    91.0% Participant Final Cost      195 9.0% Total                            $2,183 Accomplishments: Hybrid Plastics achieved technical innovation, research awards, additional grants and collaborations, patents, and national recognition as it completed this ATP-funded research project. Its major accomplishments were the following: · Reduced the cost of production for POSS nanostructured material from $1,000 to $5,000 per pound to $30 to $50 per pound · Reduced production time for POSS nanostructured material from as long as three months to one day · Developed processes to make POSS from cheaper feedstock such as silane, sand, and other compounds · Increased the efficiency of POSS manufacturing processes by increasing yield and selectivity and reducing reaction time by developing a scalable manufacturing system · Controlled type and amount of functionality of POSS by creating a unique molecular structure · Collaborated with Pentron Clinical Technologies to introduce a new class of dental bonding agents, called "Nano-Bond," based on POSS materials · Partnered with the Air Force, National Aeronautics and Space Administration (NASA), and Boeing to send nine POSS samples to the International Space Station

Hybrid Plastics won several awards for its ATP-funded research: · 2000 Award for Excellence in Technology Transfer from the Federal Laboratory Consortium for the transfer of POSS nanotechnology to the private sector · "R&D 100 Award" as one of the 100 globally most technologically significant new products for 2001 by R&D Magazine · "Collaboration Success Award" in 2002 for best collaboration among business, academia, and government by the Council for Chemical Research · Finalist for "2002 Best of Small Tech Award" from Small Times Magazine for best product globally in nanotechnology, Microelectromechanical Systems (MEMS), and microsystems in November 2002 · Received a Presidential Determination under Section 303(A)(5) of Defense Production Act dated December 20, 2005 that POSS is in the "strategic national interest” Hybrid Plastics has received the following 10 patents for its technology: · “Preceramic additives as fire retardants for plastics” No. 6,362,279; filed December 18, 1998, granted March 26, 2002 · “Functionalizing olefin bearing silsesquioxanes” No. 6,100,417; filed August 31, 1999, granted August 8, 2000 · “Process for the formation of polyhedral oligomeric silsesquioxanes” No. 6,972,312; filed August 4, 2000, granted December 6, 2005 · “Modifying POSS compounds” No. 6,660,823; filed November 14, 2000, granted December 9, 2003 · “Polyhedral oligomeric -silsesquioxanes, -silicates and -siloxanes bearing ring-strained olefinic functionalities” No. 6,911,518; filed December 21, 2000, granted June 28, 2005 · “Altering of poss rings” No. 6,770,724; filed February 16, 2001, granted August 3, 2004 · “Nanostructured chemicals as alloying agents in polymers” No. 6,716,919; filed March 26, 2001, granted April 6, 2004

PROJECT HIGHLIGHTS
Hybrid Plastics

· “Process for the functionalization of polyhedral oligomeric silsesquioxanes” No. 6,927,270; filed June 27, 2002, granted August 9, 2005 · “Polyhedral oligomeric silsesquioxane polymide composites” No. 6,767,930; filed September 9, 2002, granted July 27, 2004 · “Reactive grafting and compatibilization of polyhedral oligomeric silsesquioxanes” No. 6,933,345; filed January 23, 2003, granted August 23, 2005 Commercialization Status: Hybrid Plastics has commercialized the technology developed in the ATP-funded project for use in a wide range of applications, from dental products to meat packaging to space shuttles. Typically, POSS nanostructured materials are used in applications where manufacturers or end-users face problems with conventional materials. For example, when conventional meat-packaging material could not stop meat spoilage, POSS nanostructured material successfully improved the shelf life of packaged meat products. Furthermore, NASA scientists determined that POSS nanostructured composites could reduce radiation damage on space vehicles and the International Space Station. Hybrid Plastics has also entered into joint development or cost-shared collaborative agreements with other companies and government agencies for quick commercialization of the technology or material developed. Using the ATP-funded technology as a platform, the company has expanded its POSS product line significantly. Some of the POSS products already commercialized are Nano-Bond, Firequench, POSS acrylic, and molecular silica. To meet the growing interest in POSS nanostructured materials, Hybrid Plastics plans to raise its annual production level of 20,000 pounds in 2005 to 2 million pounds in 2009. Outlook: The outlook for the ATP-funded POSS technology is strong. Since the Federal Government recognized the POSS material and technology as having strategic national interest, the company is gaining capital resources and allocating these resources to the expansion of production infrastructure. The market for their products is expected to grow significantly in the next three years.

Composite Performance Score: * * * * Number of Employees: 3 at project start, 30 as of June 2006. Company: Hybrid Plastics 55 W.L. Runnels Industrial Drive Hattiesburg, MS 39401 Contact: Carl Hagstrom Phone: (601) 544-3466

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Research and data for Status Report 98-01-0059 were collected during April – June 2006.