Ramin Amin-Sanayei, Roice Wille, John Stuligross, Kurt Wood, and Kevin Hanrahan (pictured from left to right), winners of the 2014 American Chemical Society Team Innovation Award, are recognized for their work leading to the introduction of Kynar Aquatec® emulsion resins, a new polymer platform for highly weatherable waterborne coatings.
Industrial coatings based on Kynar 500® polyvinylidene fluoride (PVDF) resins were first commercialized in 1965 and offer outstanding exterior durability, color retention, and resistance to dirt-pickup, with a demonstrated 30+ year service life. However, these traditional PVDF-based coatings are solvent-based and require high-temperature baking, necessitating factory application to control emissions and metal substrates to withstand the high bake temperatures. To bring the excellent PVDF coating performance to other substrates (composites, glass, polymers, wood, etc.), and to improve sustainability, the Arkema Inc. team invented, developed, and commercialized novel water-based fluoropolymer technology. Low VOC coatings formulated with this technology can now be used over multiple substrate types in both air-dry field applications and lower-bake temperature factory applications, ultimately delivering the same durability and performance as traditional solvent-based PVDF coatings.
This multidisciplinary team overcame several technical challenges to make Kynar Aquatec® emulsion resins a success. In conventional solvent-based PVDF coatings, the liquid paint formulation contains both PVDF and acrylic resins that must “alloy” at high temperature. This team was tasked with delivering the PVDF/acrylic morphology on a molecular level through in-situ emulsion polymerization, and with maintaining this morphology throughout the coating application process and the lifetime of the product.
Three key inventions were made: generation of a stable “fluoropolymer seed” dispersion (latex), identification of acrylic monomers that would be thermodynamically miscible with the seed, and an elegant acrylic staging process. The chemistry to make the fluoropolymer seed was especially innovative because it is very difficult to synthesize and stabilize a fluorosurfactant-free fluoropolymer aqueous dispersion with small particle size, high solids, and low crystallinity. This challenge was overcome by using a combination of theories (surface energies, partitioning coefficients, and compatibility parameters) to predict surfactant properties, ultimately ensuring the surfactant did not interfere with the polymerization kinetics. The choice of initiator type and structure also played a major role in successfully synthesizing the fluoropolymer seed. These discoveries enabled the team to produce stable fluoropolymer/acrylic hybrid dispersions that deliver the required lower-temperature film formation, substrate adhesion, and weathering resistance.
Subsequently, the team successfully tackled new technical issues relating to inadequate mixing and coagulation as the process was taken to pilot scale and commercial manufacturing. Throughout the entire development process, the applications team developed and optimized coating formulations incorporating Kynar Aquatec® emulsions, to ensure compliance with end-use customer application requirements.
The Kynar Aquatec® team, through the development of this innovative technology, has enabled access to markets and applications that was considered impossible just a few years ago. With several customers already in each major geographic region, Arkema predicts double-digit growth for the next 10 years. In fact, the technology has already been highlighted in many flagship projects throughout the world. This technology is currently used for, but is not limited to, the following applications:
-- Field-applied reflective white roof coatings: “Cool roof” technology has received increasing national attention as a key component of energy conservation initiatives, and is being mandated through new regulations (e.g., California Title 24). To qualify for an Energy Star® rating, low-slope roofs must have an initial total solar reflectance (TSR) of >65%, with a three-year aged TSR of >50%. This aged TSR value has been a weak point for other roof coating systems due to poor dirt, microbial, and weathering resistance. A typical white paint based on Kynar Aquatec® emulsion resin has an initial TSR of about 81%, dropping to only ~78% after five years of exterior exposure. With so little reflectance loss, this paint technology exceeds current mandates for reflectivity retention and extends energy savings by many years. When the longer lifetime of the Kynar Aquatec® coating system and the energy savings are factored in, its life cycle cost is lower than traditional roof coatings.
-- Factory-applied low-bake durable coatings: Component manufacturers can now provide building components (e.g., trim, moldings, siding, shutters, window and door profiles, fencing, railing, decking) with long-lasting Kynar Aquatec® emulsion resin-based topcoats, regardless of which substrate is used to manufacture the article. Some examples include cellular PVC siding for homes, pultruded composite window profiles that combine the strength of aluminum profiles with the excellent insulative properties of non-metallic construction materials, and aluminum doors with thermal breaks, which are coated after assembly.
The development and commercialization of this patented and innovative technology has been a major project at Arkema, and has been possible only through the efforts and contributions of the entire Kynar Aquatec® emulsion resin team. Furthermore, this technology continues to enable new fluoropolymer chemistries for use in numerous next-generation, high-durability, water-based coatings applications.
Dr. Ramin Amin-Sanayei is a Principal Research Scientist at Arkema Inc. in the Fluoropolymers R&D synthesis group. He was the lead scientist developing the process for the small particle size, fluorosurfactant-free seed latex used at the base of the first KYNAR Aquatec® products. Beyond this, he has designed, synthesized, and commercialized many other new fluoropolymer products including low crystallinity fluoropolymers, co-continuous alloys of fluoropolymers, “ultra-High-MW” PVDF, binders for membranes and lithium ion batteries, and open-cell foams based on waterborne fluoropolymers. Most of these products are made using more environmentally friendly “fluorosurfactant-free” processes, based on several new classes of surfactants discovered by Dr Amin-Sanayei. He received a BASc. In Chemical Engineering from Sharif University, Tehran, Iran, and an MASc and Ph.D. in Polymer Synthesis & Characterization/ Chemical Engineering, from the University of Waterloo, Waterloo, Canada. He joined Arkema Inc. in 1994.
Kevin Hanrahan is currently General Manager for Arkema’s Specialty Polyamides- North America business. Prior to becoming Global Business Director, Coatings Market for the KYNAR® PVDF business, he was a Business Development Manager playing a key leadership role in commercializing several new technology platforms including the Kynar Aquatec® platform. The commercial success of the KYNAR Aquatec® platform depended on Mr. Hanrahan’s design and implementation of a development strategy across diverse markets, focusing on end-use education and pull-through marketing. The strategy was launched through a strong “cold call” methodology to identify and cultivate new partner customers. .In previous positions with the predecessor sister companies of Arkema, Mr. Hanrahan was an Internal Auditor for Total, N.A., and Technical Service Manager & R+D Manager for Cook Composites and Polymers, where his team won Atofina’s “Prix de l’Innovation” award in 2000. Prior to that, he worked in ink formulation for JM Huber Corporation and BASF Corporation. He received a B.Sc. in Industrial Chemistry from the University of Limerick.
John Stuligross is a Principal Process Technology Engineer in the KYNAR® PVDF Kynar Process Technology group at Arkema Inc. He was the principal engineer working on the commercial scale up both of the small particle size, fluorosurfactant-free seed latex used as the base of the first KYNAR Aquatec® products, as well as the processes for several of the products themselves. He also coordinates pilot plant activities, and provides process support and optimization for Arkema PVDF plants worldwide. Before joining Arkema, he worked as a process engineer at hte (equipment design and operation for high throughput experimentation), PPG Industries (new product development, and process development and support for several businesses), and OxyChem (process development ans support for chlorination and fluorination processes). Mr. Stuligross received a B. A. in Chemistry from Lawrence University, and an M.S. in Chemical Engineering from the University of Wisconsin-Madison.
Dr. Roice Wille is a Principal Scientist at Arkema Inc. in the Fluoropolymers R&D synthesis group. He was involved in some of the earliest studies to develop the KYNAR Aquatec® resin platform, and is the main scientist developing processes for new Kynar Aquatec® products and improving the manufacturing processes for existing products to improve environmental stewardship and process reliability. Beyond this, he has also overseen the development, from laboratory through commercial scale up, of several other new PVDF product lines in the Arkema fluoropolymers business including Kynar Flex® 3120 for extrusion and molding applications, Kynar Powerflex® LBG for lithium batteries, and Kynar Superflex® for extrusion and molding applications. He has made significant contributions in the area of promoting environmentally sound materials and practices, both in Arkema’s processes, and also in the larger fluoropolymers industry through work with the Fluoropolymers Manufacturing Group. Dr Wille received a B.B.A. in Business Administration from the University of Michigan, a B.S. in Chemistry from Michigan State University, and an M.S. and PhD. in Chemistry from Rensselaer Polytechnic Institute. He joined Arkema Inc. in 1990.
Dr. Kurt Wood is a Principal Scientist at Arkema Inc. in the Fluoropolymers R&D Coatings Applications group, where he is a new product development specialist. For many of the KYNAR Aquatec® developments, including the first commercial product launch, he has served as the main technical interface with potential customers—working both with Synthesis colleagues on product design, and with customers’ formulation scientists to develop coating formulations with the developmental products which will fully meet end-use performance requirements. One important contribution was to develop new methodology for the rapid prediction of weatherability for 30-year PVDF coatings, leading to the identification of composition and morphology requirements that would permit optimum weatherability in KYNAR Aquatec® latex-based coatings. This work has lead to a more general interest in service life prediction and he has been an active contributor to international consortia and conferences on this topic. Dr. Wood received a B. S. in Chemistry from the University of California at Davis, and a PhD. in Physical Chemistry from the University of California at Berkeley. He worked for a number of years in Industrial Coatings R&D at the Rohm and Haas Company and then joined Arkema Inc. in 1996.
Kynar Aquatec® and KYNAR 500® are trademarks of Arkema, Inc.