Cover Story Polyurethane and Polyetheramid applications used in sports (photo: Shutterstock) Info: Aliphatic diacids comprise two carboxylic acid functional groups linked by an aliphatic hydrocarbon spacer. The general formula for this class of compound is HO 2 C(CH 2 ) n CO 2 H. Typically, n is between 0 and 22. HO O ... O OH was improved over dodecanedioic acid — equivalent to PMMA and superior to polycarbonate and polystyrene [7]. Block copolymers of polyamides and polyethers, also known as polyetheresteramides, have been formed into shaped articles such as fibers, fabrics, films, sheets, rods, pipes, injection molded components or shoe soles. The polyetheresteramides that utilized C18 diacid afford a product with improved optical properties as compared to its shorter chain homologues [8]. Polyurethanes are typically synthesized via condensation polymerization of a di-isocyanate (typically MDI), a chain extender (typically butane diol) and a longer chain polyol (typically polyester or polyether). Long-chain diacids (such as C18) can also be used to make polyester polyols that make up the soft segment in polyurethanes. The use of the longer hydrophobic chain in the polyols is expected to result in a new class of polyurethanes with a very flexible, less polar soft segment with better elasticity at low temperatures, better hydrolytic stability (due to the lower ester content) and lower moisture pick-up in high-humidity environments such as automotive. Condensation polymers based on C18 diacid are also expected to have much lower moisture pickup than shorter chain diacids. When C18 diacid is incorporated into polar polymers — such as polyamides, polyesters and polyurethanes — the resulting polymers are expected to have hightemperature performance in high-humidity environments and exhibit better hydrolytic stability. This set of features is critical in under-the-hood automotive applications such as air intake manifolds, tanks for power steering fluids, coolant pumps, electronic housings, connectors and fuel lines. Other applications requiring high-humidity performance include sporting goods (e.g., roller wheels, ski boots, bicycle tires, horseshoes and athletic shoes), power tool housings, mobile phone housings, gears, sprockets, automotive panels, bumpers and airbags. Inherent C18 Diacid Sustainability Elevance’s products combine high performance with renewable content. The Elevance technology can use a diversity of renewable feedstocks, including palm, mustard, soybean and, when they become commercially available, jatropha or algal oils. Each of these feedstocks can be sourced locally, enabling Elevance and its customers to reduce the carbon footprint across the entire supply chain. High-performance polymers, used in durable goods, have had limited options for using renewable feedstocks, with castor oil being the most significant. With Inherent C18 Diacid and other products now possible using the Elevance technology, alternate renewable feedstock possibilities creating new material sourcing options and innovative performancebased solutions are available for high-performance polymer and durable goods manufacturers to expand their portfolios, supply chains and achieve sustainability goals. Summary The advantages of long-chain diacids, such as Inherent C18 Diacid, are numerous and varied. Incorporation of this monomer into polymers, pre-polymers and low molecular compounds is expected to impart low surface tension, better dispersion and miscibility, high crystallinity, low moisture pick-up, high optical transparency, low dielectric constant, and increased hydrolytic stability over shorter chain, more common diacids. Also contributing to this article: Brian Albert, Paul Bertin, Steve Cohen and Jordan Quinn www.elevance.com This article is based on a more comprehensive white paper. That is why the numbering of figures and references is not continuous. A full version of the white paper can be found at www.bioplasticsmagazine.de/201305. References 1. Data obtained from the Kirk-Othmer Encyclopedia of Chemical Technology, Dicarboxylic Acids, DOI: 10.1002/0471238961.040903 0110150814.a01.pub2. 2. Abraham, T.; Kaido, H.; Lee, C. W.; Pederson, R. L.; Schrodi, Y.; Tupy, J. U.S. Patent Application 2009/0264672. 3. Allen, Dave R., Patent Application WO2012/061094 4. Bennett, C.; Matthias, L. J. Journal of Polymer Science: Part A 2005, 43, 936−945. 5. Gavenois, J.; Mathew, A. K. U.S. Patent Application 2013/0052384. 6. Nataniel, T.; Heinrich, D. Eur. Patent Application 1,533,330. 7. Nataniel, T.; Heinrich, D. D. U.S. Patent 8,119,251. 8. Bühler, F. S.; Hala, R. U.S. Patent Application 2010/0144963. 10 bioplastics MAGAZINE [05/13] Vol. 8
Fibers & Textiles New high performance PLA grades for fibers NatureWorks announced the commercial availability of two new Ingeo high performance PLA grades designed for fibers and nonwovens applications. The two grades deliver lower shrinkage, faster crystallization, and higher melting points across the broad range of manufacturing processes used to produce fibers and nonwoven fabrics. The new grades broaden the application window for PLA use in the production of personal care and hygiene products, filtration media, medical fabrics, civil engineering fabrics (erosion control, reservoir lining protection, etc.), and geotextile and agricultural fabrics. The new Ingeo grades will extend the scope of applications, including velvet Ingeo 6100D is a mid viscosity grade designed for spunbond nonwoven and conventional staple fiber/filament melt spinning applications, while Ingeo 6260D is a low viscosity grade designed primarily for melt blown nonwoven applications. Both grades offer the highest melting points and fastest crystallization rates in the Ingeo fiber grade resins portfolio. “These new Ingeo grades provide benefits across all processing technologies and in a more extensive range of applications,” said Robert Green, fibers and nonwovens industry global segment manager, NatureWorks. “These grades are the result of intensive research and development and significant long-term investments in state-of-the-art production processes. These new grades are the first of a number of next generation solutions.” Key features and benefits of Ingeo 6100D and 6260D The reduced shrinkage of Ingeo fibers made from 6100D and 6260D leads to improved fabric dimensional stability. These grades deliver increased hydrolysis resistance, and offer ~30 % higher stiffness (modulus) at temperatures above their glass transition temperature. Both are capable of higher heat set temperatures, leading to higher melting/ sticking points during processing and use. Higher melting point creates advantages in bi-component systems in which the new grades are combined with existing Ingeo low melting point resins. All of these attributes contribute to a larger overall Ingeo processing window and greater ease of processing. Spunbond & Fibers Performance: When new Ingeo 6100D is compared to the existing Ingeo grade 6202D, one of the most often applied grades for fibers and spunbond nonwovens, NatureWorks scientists found: • Peak melting point increased by 8°C from 164 to 172°C • Melting shoulder increased by 15°C • Fiber crystallinity increased by ~20% • Quiescent crystallization rate increased three to four times • Lower stress required for stress induced crystallization In spunbond applications the fibers made from new Ingeo grade 6100D show a high strength to weight ratio with fibers in the 15-35 µm diameter range. These spunbond attributes make the new grades ideal for fabrics in geotextile, medical, automotive, and hygiene applications. Meltblown Performance: New 6260D grade for melt blown applications can generally produce fibers in the 2-7 µm diameter range with desirable attributes for a broad range of applications and products. Resultant fiber characteristics can be translated into attributes such as low pressure drop for filtration media, or softness for hygiene applications. Nonwovens shrinkage in melt blown fabric applications will be ~ 80% less than what was previously achievable. MT www.natureworksllc.com. bioplastics MAGAZINE [05/13] Vol. 8 11
