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Fibers & Textiles % Limiting oxygen index 40 — 35 — 30 — 25 — 20 — 15 — 10 — 5 — 0 — Cotton Polyester Nylon Terryl Figure 6: Terryl is more flame retardant % Renewable Carbon Content (ASTM D6866) 50 — 45 — 40 — 35 — 30 — 25 — 20 — 15 — 10 — 5 — 0 — Nylon PTT Terryl Figure 7: Terryl renewable carbon content compared to PTT from biobased 1,3-PDO and existing nylon. Nylon has been used in carpet for its superior dyeability and wear resistance. Polyester PTT from biobased 1,3-PDO has recently gained some traction amongst carpet manufacturers for its renewability. Terryl wear resistant and lightweight like nylon and contains higher renewable content than renewable PTT. According to biobased carbon content as determined per ASTM D6866, Terryl is 45% biobased carbon, compared to 27% for PTT made from biobased 1,3-propanediol. Terryl’s elasticity, moisture wicking, comfort, antistatic, dyeability and flame retardant properties give it a potential performance advantage in numerous textile applications including carpet, hosiery, seamless underwear, and performance sportswear. Future Prospects Based on these promising initial results, Cathay Biotech has begun expansion of Terryl production. Purely focused on Industrial Biotechnology with a successful commercialization track record and an international R&D team dedicated to the industry for over ten years, Cathay Biotech is the world’s first and to date only commercial scale producer of DN5. Terryl will be the first new broad-use polyamide since the invention of nylon 66 (PA66) and nylon 6 (PA6) in the 1930s. To promote Terryl, the China Chemical Fibre Association formally announced the inauguration of the Biobased Polyamide Fibre Material Technology Innovation Industry Alliance in March 2014. Led by Cathay Biotech, the industry alliance includes academic and industry leaders and will focus on research and development of Terryl applications. Competitively viable today, Cathay Biotech’s DN5 technology still has much room for future optimization and improvement, whereas the mature chemical process for HMDA is close to theoretical yield leaving little runway for future improvement. Biobased raw materials are also expected to be more sustainable both environmentally and economically than butadiene from petroleum in the long run. Large-scale commercialization of Terryl will hopefully highlight the importance of industrial biotechnology for the chemicals industry. By: Charlie Liu Vice President Cathay Industrial Biotech Shanghai, China 14 bioplastics MAGAZINE [05/14] Vol. 9

Fibers & Textiles Applications of biopolymers for technical fibres are a niche in the world of biopolymers. Nevertheless, we see an increasing request for the development of special yarns based on biopolymers. Key issue is to develop yarns with an attractive combination of (mechanical) properties and price. Biobased polyamides In many applications PET or PA multifilament yarns are used for reinforcement. These yarns have a high tenacity (> 800 mN/tex) and a high melting point (above 200°C). For different applications it is preferred to replace these yarns by biobased analogues. Best known example is of course a yarn produced from PLA. But for several applications the thermal and chemical stability of a PLA yarn is not sufficient. In those cases biobased polyamides can be an attractive alternative. Yarns from PA11 are already known in the market. The API Institute also successfully developed a PA11 yarn, but after all practical application was hampered by the price of the polymer. For this reason biobased polyamides that are cheaper and can be converted in to technical yarns have been looked for. At the moment the best option seems to be PA10.10. Thermal and chemical properties are excellent and a tenacity of 400 mN/tex can be achieved. This is not yet the same level as for PET or PA yarns, but for many applications still sufficient. High tenacity PLA yarns Based on availability and price, PLA is the most investigated biopolymer. For technical application it is important to improve the tenacity. Compared to e.g. PET the price is higher and the tenacity lower. This makes replacement of PET yarns by PLA difficult. So there is a continuous drive to reach higher tenacities. In order to achieve this the team at API Institute focussed on the polymer quality and spinning conditions as they both play an important role. As an illustration the graph in Fig 1 shows the difference with respect to the yarn properties of a regular spinning grade PLA multifilament yarn and grades with a reduced D-isomercontent. The data shown is obtained from small scale proof-of-principle trials. Anonther result is that spinning conditions play an important role. By optimization of the spinning conditions in combination with the polymer quality, production of high tenacity yarns on an industrial scale should be possible. The author is looking for opportunities to continue these developments. Low creep PLA PLA yarns show a significant creep behaviour, especially in wet environments and at increased temperatures. This limits the possibilities to use PLA yarns in e.g. greenhouses. By investigating the structural background of this phenomenon it was possible to improve the properties considerably. The results of a time-to-failure test at extreme conditions is shown in Fig 2. At the moment tests are running in a greenhouse to investigate the long term behavior at real conditions. High tenacity fibres By: Bas Krins Director R&D API - Applied Polymer Innovations B.V. Emmem, The Netherlands Tenacitiy (mN/tex) Creep (%) 800 700 600 500 400 300 200 100 Fig. 1 Fig. 2 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 Improved polymer a Improved polymer b Improved polymer c regular spinning grade 0 5 10 15 20 25 30 35 Elongation (%) PLA multifilament Wet creep (10N/1000 dtex) at 41°C Commercial product based on PLA tape 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Time (hour) PLA multifilament special process bioplastics MAGAZINE [05/14] Vol. 9 15

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