New Eco-Sustainable Polyamide-Based Polymers for Multipurpose Applications

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Nicolangelo Peduto - R&D manager at Radici Chimica & Radici Plastics
Anna De Sio - R&D and Technical Marketing at Radici Chimica
11th China International Polyamide & Intermediates Forum in Shanghai, 5-6 /12/2013

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New Eco-Sustainable Polyamide-Based Polymers for Multipurpose Applications

  1. 1. New Eco-Sustainable Polyamide-Based Polymers for Multipurpose Applications Nicolangelo Peduto Radici Chimica & Radici Plastics Anna De Sio Radici Chimica 11th China International Polyamide & Intermediates Forum Shanghai, 5-6 /12/2013 1
  2. 2. RADICIGROUP & SUSTAINABILITY LCA studies GRI Certified Sustainability Report sustainability R&D for sustainable products PCR-EPD approach 2
  3. 3. R&D for sustainable products Bio-sourced polymers Radilon® A HS144 “Green like” performances Ecosustainable approach of product development Heramid® Post industrial recycled polymers 3
  4. 4. Pyramidal organization of RadiciGroup bio–sourced polyamides Renewable source content 100% Radici Chimica polymerization know how and flexibility + Radici Plastics compound technology 60% to design high performance polymers and polymer blends 0% Costs 4
  5. 5. Bio- polyamides – Main manufacturing routes Castor oil seeds Undecilenic acid Decanodiamine Ricinoleic acid 11-amino-undecanoic acid PA 1010 HMDA Sebacic acid PA 610 PA 11 PA 410 5
  6. 6. RADIPOL® DC : PRODUCTION CHAIN A new family of semi-crystalline polyamides 6.10 obtained from the polycondensation of 1,6–hexamethylenediamine and 1,10-decanedioic acid (sebacic acid). 6
  7. 7. RADIPOL® DC PA6.10: environmental benefit, reduced carbon footprint Global Warming Potential (Kg CO2 Eqv/Kg Polymer) 10 9 8 7 PA6.10 PA6 5 PA12 4 GWP 6 PC Epoxy Resin 3 PA66 2 PA11 1 0 PA6.10 PA6 PA12 PC Epoxy Resin PA66 PA11 PA6.10: GWP much lower than technical polymers like PC, PA6, PA66 …. Comparable to PA11 (Data collected from literature) 7
  8. 8. PA property comparison according to the fundamental parameter 4 5 5 7 8 9 10 11  CH 2  CO  NH 8
  9. 9. PA property comparison according to the fundamental parameter 4 5 5 7 8 9 10 11  CH 2  CO  NH 9
  10. 10. RADIPOL DC PA6.10 KEY FEATURES: TENSILE MODULUS Tensile Modulus Comparison (ISO 527) 1100 1300 PA11 1100 PA12 1500 1100 PA6.10 2200 1200 PA6.12 Tensile Modulus (RH50)) 2100 Tensile Modulus (DAM) 1700 PA66 3150 1100 PA6 3100 0 1000 2000 3000 4000 Tensile Modulus (MPa) PA6.10 shows a lower tensile modulus variation caused by moisture absorption than PA6 and PA66 10
  11. 11. RADIPOL DC PA6.10 KEY FEATURES: TENSILE STRENGTH Tensile Stress at Yield (ISO 527) 45 PA11 50 38 PA12 42 50 PA6.10 65 Tensile Stress at Yield (RH50) 50 PA6.12 60 Tensile Stress at Yield (DAM) 58 PA66 82 35 PA6 80 0 20 40 60 80 100 Tensile Stress at Yield (Mpa) PA6.10 shows higher tensile strength at break than PA11 & PA12 and better tensile strength retention after conditioning versus PA6 and PA66 11
  12. 12. RADIPOL® DC PA6.10 KEY FEATURES: IMPACT RESISTANCE Charpy Notched Impact (ISO 179, conditioned) 11 PA11 14 5 PA12 9 6 PA6.10 10 Charpy Notched Impact (- 30 °C) 6 PA6.12 7 Charpy Notched Impact 4 PA66 12 3 PA6 20 0 5 10 15 20 Charpy Notched Impact (KJ/m² PA6.10 shows an impact resistance higher than PA6 and PA66 at -30°C and slightly higher than PA12 12
  13. 13. RADIPOL® DC PA6.10 KEY FEATURES: MELTING TEMPERATURE, HDT Melting Temperature, HDT PA11 145 189 135 PA12 178 165 PA6.10 218 140 PA6.12 225 PA66 PA6 HDT (0,45 Mpa) 215 260 170 Melting Temperature 220 0 100 200 Melting Temperature (°C), HDT (0,45 MPa, °C) 300 PA6.10 shows higher melting point and HDT than PA12 and PA11 leading to an improved thermal resistance 13
  14. 14. RADIPOL® DC PA6.10 KEY FEATURES: SPECIFIC GRAVITY PA6.10 specific gravity : intermediate between PA6 & 66 and PA11 & 12 14
  15. 15. PA 610 COPOLYMERS RADIPOL® Dcopo  50% bio-based  Superior transaparency and gloss  Good flexibility and tougheness  Good termoforming and shrink 15
  16. 16. RADIPOL® DC PA6.10 KEY FEATURES  Best compromise between properties/costs/eco content  Greater dimensional stability compared to PA6 and PA66, due to less water and moisture uptake that lead to a superior hydrolysis resistance  Higher chemical resistance compared to PA6 and PA66  Grater resistance at high temperature than PA11&PA12  Superior resistance to peroxides  Excellent elastic memory, superior to traditional polyamides, i.e. better bending 16
  17. 17. PA 6.10 vs. PA 66 – Hydrolysis resistance of compounds with 30% GF *PA 6.10 *PA 6.6 *Courtesy of RadiciNovacips 17
  18. 18. Stress-cracking mechanism of PA’s in solutions of road salts When in contact with PA, ZnCl2 makes a complex compound with the amide groups and the reaction takes place easily. The ultimate effect is the scission of the amide groups and the degradation of molecular weight and therefore mechanical properties. One of the key parameter is then the amide groups concentration. Such a complex increases the stiffness of the polymer that overcomes a stress concentration, ultimate responsible for the stress cracking phenomena. Modulus is the other key parameter. Water plays a positive rule because it acts as a stress relief. Stress cracking usually happens during the firsts hours of the test. Halide ions are very important to create this complex. In fact other types of salts such as Zn acetate do not cause stress cracking in PA. For ZnCl2 salt solution, the pH of the mixture is < 2, at 50 % concentration. The solution is therefore acid and the PA parts in contact with the solution show an extensive whitening phenomenon. 18
  19. 19. Effect of salts on Polyamide Glass Transition Temperature 100 microns film plunged into water solution of ZnCl2 at different T Tg variation Material 20°C 40°C 60°C PA 6 72 77 89 PA 66 70 75 90 PA 6.10 65 63 65 19
  20. 20. Radilon® D PA6.10 Approvals  Pneumatic Pipes  Truck Air Brake Pipes  Fuel Line Connectors  Several parts requiring dimensional stability and superior chemical resistance 20
  21. 21. PA 6.10 – Case History Radilon® D PA6.10 Key Features: Chemical Resistance  Two special grades that pass the most severe zinc-chloride test : Radilon® D E35ZW (flexible) (dilution of amide groups + stress relief) Radilon® D E50ZW (semi-flexible) High stress fastening area PA 6 * PA6.10 Radilon® D E35ZW and Radilon® D E50ZW special grades : no damages after immersion in zinc-chloride/water 50/50 solution for 200 h. Right side picture shows a typical stress cracking damage on high stressed fastening area 21
  22. 22. PA 6.10 – Case History Radilon® D PA6.10 for pneumatic tubings DIN 73378 : Basic Stress Comparison 35 Basic Stress (Mpa) 30 25 PA12-PHLY PA12-PHL 20 Radilon D40EP35XK Radilon D40P50K 15 10 5 0 0 20 40 60 80 100 120 140 Spiral-shaped pneumatic tubing made of Radilon® D40P50K Temperature (°C) Norm ref DIN 73378 : basic stress comparison from 23 to 130 °C • Radilon® D 40P50K (translucent, UV resistant, semi-flexible) • Radilon® D 40EP35XK (opaque, UV resistant, semi-flexible) 22
  23. 23. PA 6.10 – Case History Radilon® D PA6.10 for truck brake air lines MAIN CTQ’S • Properties retention after ageing in air • Chemical resistance • Norms DIN 74324, FVMSS 106, ISO 7628, DIN 73378, SAE J844 One layer solution Radilon® D 40EP25ZW (flexible) Radilon® D 40EP35XK (semi-flexible) Radilon® D E35ZW (superior zinc-chloride resistance) Two layer solution Truck brake tubes made of Radilon® D E35ZW. Radilon® D E35ZW (outer layer) Radilon® D 40EP25ZW (inner layer) or Radilon® D 40EP35XK (inner layer) 23
  24. 24. PA 6.10 – Case History Radilon® D PA6.10 for fuel connectors MAIN CTQ’S •Good properties retention after fuel ageing •Good dimensional stability •Good chemical resistance Available grades Radilon® D RV300W (30% GF) Radilon® D CF150W (conductive grade) 24
  25. 25. PA 6.10 – Case history Radilon® D PA6.10 for fuel connectors Ageing in E24 Fuel at 90 °C Tensile Strength at Break (Mpa) 160 Radilon D RV300W 333 NER 140 PA12-GF30 120 100 80 60 40 20 0 0 500 1000 1500 2000 Time (h) PA6.10 change over time in tensile strength after E24 fuel immersion : similar trend as PA12-GF30, which has been used to manufacture fuel connectors up to present 25
  26. 26. PA 6.10 – Case history Radilon® D PA6.10 for fuel connectors Ageing in E24 Fuel at 90 °C Charpy Unnotched Impact (KJ/m2) 140 120 100 80 60 40 20 0 0 500 1000 Time (h) 1500 2000 Radilon D RV300W 333 NER PA12-GF30 PA6.10 change over time in Charpy unnotched impact strength after E24 fuel immersion : initial increase observed and no change from 1,500 to 1,000 h . For PA12 after 1,000 h the impact strength begins to decrease; this could be a sign of material degradation 26
  27. 27. PA 6.10 – Case history Radilon® D PA6.10 for fuel connectors Ageing in E24 Fuel at 90 °C 10,0 9,0 Weight Change (%) 8,0 7,0 6,0 5,0 Radilon D RV300W 333 NER 4,0 PA12-GF30 3,0 2,0 1,0 0,0 0 500 1000 1500 2000 2500 Time (h) The graph shows that, after 2,000 h of immersion in E24 fuel, the change in weight for PA610-GF30 is 2% lower than for PA12-GF30 27
  28. 28. PA 6.10 – Case history Radilon® D PA6.10 for fuel connectors Radilon D RV300W : Ageing in air at 130 °C 140% Property Retention (%) 120% 100% 80% 60% 40% Tensile Strength at Break Tensile Deformation at Break 20% Target 0% 0 500 1000 1500 2000 Time (h) The graph shows that, after 2,000h heat ageing in air at 130°C, PA610-GF30 shows no decline either in tensile strength at break or in deformation at break 28
  29. 29. Radilon® D PA6.10 for fuel connectors Ageing in a 50:50 Zinc-Chloride solution at 23°C and 60 °C 100 Charpy Unnotched Impact (KJ/m2) 90 80 70 60 PA12 GF30 at 23 °C 50 PA12 GF30 at 60 °C 40 Radilon D RV300W 333 Ner at 23 °C 30 Radilon D RV300W 333 Ner at 60 °C 20 10 0 0 50 100 150 200 250 Ageing Time (hours) The graph shows that, after 200 h immersion in zinc-chloride solution at 23°C and 60°C there is no significant change in the Charpy unnotched impact strength. These results confirm the excellent chemical resistance of Radilon® D RV300W (PA610-GF30) compared to PA12-GF30 29
  30. 30. PA 6.10 & Fibers –Property comparison PROPERTIES UNIT PA6 PA66 PA6.10 POLYESTER COTTON MELTING POINT °C 220 260 223 255 - WATER ABS, SATURATION % 9,4 8.2 3,0 0,2 20 DENSITY g/cm3 1,13 1.14 1,06 1.39 1.5 DIMENSIONAL STABILITY XX XX XXX XXX x RENEWABLE SOURCE - - XXX - XXXX MECHANICAL RESISTANCE XXX XXX XXX XX X THERMAL RESISTANCE XXX XX XXX XXX X DRYING SPEED DUE TO LOW WATER PICK UP XX XX XXX XXXX X CHEMICAL RESISTANCE XX XX XXX XX XXX Source: RADICIGROUP AND EXISTING LITERATURE 30
  31. 31. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY WHAT Development of a «New Concept» Floor Covering Product …… made in “Bio-Sourced Polyamide Fibre” WHO Partners : Radici Chimica as Polymer Developer Radici Yarn – Radici Chemiefaser as Fibre Developer Findeisen GmbH as Floor Covering Developer European Leader in the Production of «Needled Floor Coverings» 31
  32. 32. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products … Comparison LIVE –Test (six months) PA610 PA6 PP  Internal at Findeisen’s  External at Customer’s The Best Test ??? 32
  33. 33. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products …  Achieved Result : 33 Abrasion Resistance (EN 1470)  Best Class for Commercial (similar to PA6, better than PP)  Achieved Result : 3.8 – 4.5 Castor Chair (EN 985)  Best Result (similar to PA6, better than PP) 33
  34. 34. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products … Wolff -Test (internal test for evaluating the abrasion resistance)  Achieved Result : Good  Similar to PA6, better then PP (250 h of PA6 vs 100 h of PP) 34
  35. 35. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products … Fire Behaviour (ISO 9239-1)  Textile Flooring  Residential Flooring Achieved result : Bfl – S 1 Comments: best possible result for Textile Floor Covering (similar to PA6) 35
  36. 36. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products …  Important for installation of floor coverings Dimensional Stability (EN 986)  The Limits are: • - 1.2% for Shrinkage • + 0.5% for Elongation Typical values PA6.10 PA6 PP Shrinkage - 0.5% - 1.0% - 0.3% Elongation + 0.2% + 0.4% + 0.1% PA6.10 very close to PP : a CRUCIAL characteristic (In particular for installation of rolls --> easier installation, no influence of climate conditions) Potential development for TILES : 100% PA6.10 (today PA6 blend with PP) 36
  37. 37. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products … Tot VOC = 27 µg/m^3 Tot VOC = 13 µg/m^3 PA6.10 : NO emission of Caprolactam ! 37
  38. 38. FINDEISEN GmbH DORIX® 6.10 CASE HISTORY Evaluation of the Main Performances vs Regular Products … Comparison PA610 PA6 PP LIVE-Test Good Good Good Abrasion resistance *** *** * Castor Chair *** *** * Fire Behaviour *** (Bfl-S1) *** (Bfl-S1) ** (Cfl-S1) Dimensional Stability *** * *** Eco- Friendly *** ** ** Soiling and Staining Test: to be checked (pontentially better than PA6) Low Water Pickup and Better Chemical Resistance 38
  39. 39. Acknowledgements • Special thanks to: – Findeisen GmbH – A. Pezzoni & the polymerisation team of Radici Chimica – E. Spini of Radici Plastics – R&D of Radici Chimica/Radici Plastics/Radici Yarn – Corporate Marketing of RadiciGroup – Maria Teresa Betti for revising this document 39
  40. 40. Thank You for your attention Contact: sustainability@radicigroup.com 40

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