Progress 09/01/20 to 04/30/21

Outputs
Target Audience:The target audience for the technology developed in this project is the manufacturers of polyurethane dispersions, water based polyurethane coatings, high performance two component polyurethane coatings and manufacturers of synthetic leather. They will either be customers who buy this technology, or licensees who will license this technology to manufacture themselves. There is a growing demand for synthetic leather as well as water-based coatings, and both of these markets utilize a significant amount of water based polyurethane technology because of its toughness and durability. The irony is that though water based coatings, adhesives and elastomers seem like they are environmentally friendly, they are currently derived from petrochemicals and highly toxic isocyanates that use phosgene, the chemical war gas, as a raw material. These plastics are also not biodegradable. Water based coatings and artificial leather sell into the retail market, which has become very interested in environmentally friendly raw materials. Natural hemp and biodegradable plastics are making their way more and more into the marketplace. Consequently, manufacturers of polyurethane coatings, adhesives, elastomers and artificial leather will be very interested in the technology of this project that will enable them to produce their polyurethane products using sustainable raw materials and avoid the use of isocyanates. But aside from the environmental benefits of this new non-isocyanate technology, the performance of this technology relative to current polyurethane systems will be possibly even more important to these manufacturers. This is because of the oxetane crosslinker specially designed for use with the emulsions of this technology. Even for markets with little interest in environmental matters, the performance will help water based polyurethane technology displace solvent based systems. Instrumental Polymer Technologies produces and sells aliphatic polycarbonate resins and crosslinkers to manufacturers of polyurethane dispersions. We will use our current distributors and sales force to educate these potential customers. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?During this project personnel from Instrumental Polymer Technologies have met with coatings companies including Stahl, a manufacturer of coatings for leather (shoes and automotive), and Target Coatings, a manufacturer of coatings for wood furniture. These companies currently use polyurethane dispersions for manufacturing their coatings. These are both current customers of our crosslinker, QUICKSTAR 94XAC, of which they add to the polyurethane dispersions they obtain from companies like BASF or Covestra. We described the application and performance characteristics of the non-isocyanate polyurethane technology developed in this project. They were very excited about being able to formulate coatings with a higher solids content and would not be sensitive in storage at cold or warm temperatures. They were also very interested in the physical performance that could be achieved. These customers were given samples to apply and test themselves. Randy Cameron also met with his distributors and sales force so they could discuss this technology with other customers. Brochures are currently being produced to describe this technology and the website www.instrumentalpolymer.com is being revised to include this technology. How have the results been disseminated to communities of interest?The owner of Instrumental Polymer Technologies (IP TECH), Randy Cameron, and his sales force including Garry Murphy and Zachary Cameron as well as the distributors of IP TECH, will meet with potential customers around the world. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? The purpose of this research is to use industrial crops to supply raw materials for one of the fastest growing fields of plastics; that being polyurethane dispersions (PUDs) that are used in coatings, adhesives and sealants as well as the growing field of artificial leather. Current PUDs are produced from petrochemically sourced raw materials, some of which are highly toxic, such as isocyanates. In this project we use the bioderived chemical building blocks glycerol, carbon dioxide, methanol, butanol, acetone, L-lysine, ammonia and water to produce PUDs. To achieve properties better than current PUDs, we planned to use a proprietary emulsion crosslinker with reactive oxetane groups, QUICKSTAR 94XAC, currently marketed by our company, Instrumental Polymer Technologies, (IPTECH). It too is derived from bio-derived butanol, methanol and carbon dioxide. The crosslinker, which can be stored in the emulsion to make a single component system, will cure the system to have properties similar to two component solvent-based systems. The technical objectives for this Phase I project are to synthesize all the required raw materials and then 36 samples of polyurethane dispersion, perform application testing on them and physical testing on them. There are 4 variables that were studied in this project. The effect of the acid value, that is the amount of L-Lysine incorporated in the polyurethane. Three levels of L-Lysine were to be used. The amount of branching, that is the amount of triamine used. So three levels of trimethylol triurethane amine were to be used. This would lead to 9 samples, The nature of the neutralizing amine. Both ammonia and triethyl amine were to be used, leading to 18 samples as each of the 9 samples will be neutralized in two different ways. The amount of oxetane crosslinker. To each of the 18 samples we will test with and without a 10% by weight loading on the solids of the polyurethane with QUICKSTAR 94XAC. This additive is known to improve coalescing and flow as well as improve the toughness, chemical resistance and adhesion of the emulsions. During this project we successfully synthesized two required intermediates and the 36 samples, which included the QUICKSTAR 94XAC crosslinker. A surprise was that two thirds of the samples were absolutely soluble in water, rather than being emulsions. This is a huge benefit firstly because PUDs suffer from instability if stored in freezing or too warm of temperature and the homogeneous solution should be much more stable. Secondly, PUDs are usually 20-30% solids in water because the viscosity becomes too high and the emulsion becomes unstable and gels. The homogeneous clear samples we made are 50% solids, which enables them to be used in common urethane coating applications that require a thicker coating to be applied. It's an important note that these solutions aren't really polyurethane dispersions at all and are rather water based polyurethane thermosetting lacquers, or water-based PUTLs as we are now calling them with our customers. We were able to finish all of the testing including chemical resistance, scratch resistance, abrasion resistance and impact resistance and found the technology to have performance much better than current polyurethane dispersions but not quite as good as the highest performance two-component polyurethane coatings qualified by Boeing for use on aircraft. However, we expect with some more work this technology will be able to compete with two component polyurethane systems, not just current PUDs. Our company has selected our best performing system, which we call AVERTISO 384PUTL and have sampled it to 22 companies so far. All of the companies currently produce water based coatings based on PUDs, and most of them also sell high performance coatings based on two component polyurethane systems.

Publications

Progress 09/01/20 to 04/30/21

Outputs
Target Audience:The Target Audience we reached out to during this reporting period were potential customers for this technology. Non-disclosure agreements and initial discussions were held with Sherwin Williams and Stahl, two major manufacturers of coatings containing polyurethane dispersions. Sherwin Williams manufactures many of the polymers used in their coatings. If things proceed with Sherwin Williams, they will license this technology from Instrumental Polymer Technologies and produce it themselves for their own use. Stahl is a primary manufacturer of coatings and adhesives for artificial leather used in automobiles and shoes. The plan would be for Stahl to purchase this technology from Instrumental Polymer Technologies. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Synthetic procedures for making reactant molecules were made during this period. This information will be used to train chemists within Instrumental Polymer Technologies, licensees of this technology and toll manufacturers of this technology in the future. How have the results been disseminated to communities of interest?Information on how to synthesize the reactant molecules developed during this reporting period have not been disseminated. A Nondisclosure Agreement has been signed off with Sherwin Williams Corporation, who may be a licensee in the future. What do you plan to do during the next reporting period to accomplish the goals?During the next period the best procudure for producing a polyurethane dispersion using industrial crops will be determined. This information will be disseminated to Sherwin Williams and other licensees.

Impacts
What was accomplished under these goals? This project addresses USDA NIFA SBIR Program objectives within the Section 8.8 Biofuels and Biobased Products by using industrial crops to supply raw materials for one of the fastest growing fields of plastics; that being polyurethane dispersions (PUDs). PUDs are displacing solvent-based polyurethanes in many other coatings markets like wood coatings and floor coatings. They are also one of the fastest areas of growth for water based adhesives and coatings because of their high performance relative to more commonly used acrylic emulsions. They've become particularly popular in the field of artificial leather used in shoes, clothing, furniture and automobiles where high abrasion resistance and resistance to cracking is needed. They're not only used in coatings for artificial leather, but the adhesives and elastomeric components as well. There's an irony with PUD's, though. Their use of water rather than solvent as a carrier would make one think they are completely environmentally friendly. But the truth is they are derived from petrochemicals and use toxic raw materials, like isocyanates, in their production. Furthermore, many of them aren't low in VOCs because they need volatile solvents to help the emulsion particles coalesce. They are also not biodegradable. They break apart in time to small particles of polyurethane that find their way in to all corners of our environment. Like all plastics derived from petrochemicals, it is essential the United States plays a leading role in replacing them with plastics derived from our strong agriculture base. In doing so, its important to assume most markets won't switch to a new coating or adhesive just because it is bio-based or biodegradable. In fact, biodegradability is a scary property for many of our customers, including those of construction adhesives coatings in which their customers demand a long work life for their products. Bio-based plastics for industrial use need to be designed to perform better than current plastics. Their sustainability and biodegradability should be an afterthought to the customer, if it is brought up at all. There is an opportunity to design a PUD that helps our customers while making it from industrial crops. Currently PUD's don't offer the chemical and water resistance required for many applications. To remedy this painters often add aziridine, a highly toxic and carcinogenic amine, to the paint in order to get the PUD crosslink and have higher chemical resistance and toughness. Not only are aziridines toxic but they create a short pot life; once the aziridine is mixed in to the PUD coating it needs to be applied within a few hours or the coating will solidify. Painters are in need of a PUD that has performance similar to a solvent-based two component polyurethane system. IPTECH is in a unique position to design an appropriate PUD with improved performance properties because it has invented a polymer called QUICKSTAR® 94XAC that is derived from industrial crops and that is added to water-based emulsions like PUDs to improve their chemical and water resistance. Unlike aziridine it is nontoxic and can be stored in the PUD or paint, so there is no pot life issue. IPTECH can design a PUD that is particularly suited for performing well with QUICKSTAR® 94XAC. In this project IPTECH is synthesizing a PUD that is derived from industrial crops and doesn't use toxic isocyanates to create the urethane functionality. The fundamental chemicals used to produce the PUD of this project, listed by their volume of useage are: glycerine, butanol, acetone, methanol, carbon dioxide, ammonia and L-lysine (an amino acid). Glycerine forms the backbone of the polymer to be made, and is the byproduct of biodiesel production. For every 100lbs of biodiesel produced there are approximately 10 lbs of glycerine produced. It's beneficial to find profitable uses for this byproduct. Butanol, acetone, methanol and L-lysine are all made by the fermentation of biomass. Consumption of carbon dioxide is also an obvious benefits. There were two intermediates produced during the first half of this project; one was diglycerine dicarbonate and the other was trimethylol propane triurethane amine (TMPTUA). Diglycerine dicarbonate was produced during this project by reacting diglycerine with dimethyl carbonate. Diglycerine is commercially produced by condensing and dimerizing glycerine. Dimethyl carbonate (DMC) is available commercially and is so safe to the environment that the EPA considers it an exempt solvent and isn't counted as a volatile organic component in paint formulations. DMC is generally produced by condensing methanol with carbon monoxide, but can also be produced by condensing methanol with carbon dioxide. The synthesis of diglycerine dicarbonate was a success, and the product proved to be crystalline, so was easy to purify by crystallization from DMC. The synthesis of TMPTUA required the initial synthesis of trimethylol propane trimethylcarbonate (TMPTC). This was done by condensing trimethylol propane (TMP) with excess DMC. TMP is made commercially using butanol and methanol as feedstock. TMPTC was made with no problem and the product was analyzed by gas phase chromatography. We then condensed this with isophorone diamine. Isophorone diamine is produced commercially by condensing ammonia with isophorone. And isophorone is made by condensing acetone. We synthesized TMPTUA by condensing TMPTC with isophorone diamine and characterized the final product by GPC and fourier transfer infrared (FTIR) spectroscopy. Once we had these two intermediates, per our research plan we began synthesizing 18 variations of PUD by condensing this along with the amino acid L-Lysine. During the remainder of this project we will continue preparing PUD's using the intermediates synthesized. To some of these PUD's we will add the oxetane reactant QUICKSTAR 94XAC, which is commercially available by IP TECH. We will perform application and physical testing on coating samples made from these ingredients.

Publications