Slideshare Royce Epoxy Accelerators 2010 TRFA
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Slideshare Royce Epoxy Accelerators 2010 TRFA Slideshare Royce Epoxy Accelerators 2010 TRFA Presentation Transcript

  • Evaluating the Use of Accelerators in Phenalkamines for Improving the Low Temperature Cure Properties Dr. Frank Cheng Royce International
  • HOW LOW CAN WE GO? ROYCE INTERNATIONAL
  • Phenols: Accelerator for Epoxy – Amine System Mechanism: ROYCE INTERNATIONAL
  • Tertiary Amine: Accelerator for Epoxy – Amine System Mechanism: ROYCE INTERNATIONAL ROYCE INTERNATIONAL
  • Tertiary Amines: Reactivity with DGEBA* *Barusch & Payne, J. Am. Chem. Soc. 65:2196 (1943) Amine Ionization Constant, Kb Geltime, hrs 25 C Triethylamine 6.4 X 10(-4) 11.2 Tripropylamine 5.5 x 10(-4) 29 Benzyldiethylamine 3.6 x 10(-5) >300 Benzyldimethylamine (BDMA) 8.5 x 10(-6) 5.3 Pyridine 2.3 x 10(-9) 54 ROYCE INTERNATIONAL
  • DMP: (Dimethylaminomethyl)phenol as Accelerator BDMA, DMP-10 and DMP-30 BDMA DMP - 10 DMP - 30 ROYCE INTERNATIONAL
  • Mannich Reaction and Mannich Base Mannich Reaction: (amino-alkylation of acidic proton named after chemist Carl Mannich ) Mannich Bases: ( for Example: I & II ) ROYCE INTERNATIONAL
  • Phenalkamines Mannich Base based on Phenols: Phenol, Cresol, tButylphenol, Nonylphenol etc…. Drawback: Solid at RT (liquid product may contain more than 30% of free phenol). Phenalkamines: Based on CNSL MW = 300 ( R = C15H27 ) ROYCE INTERNATIONAL
  • Advantage of Phenalkamines as Hardeners for Epoxy Fast Curing: Especially at low temperature (i.e. 5 C & 0 C) 25 C: Full Cure: ~ 9 - 12 hrs 5 C: Full Cure: ~17 - 22 hrs 0 C: Full Cure: ~30 - 40 hrs Excellent Cure under Damp Conditions Good for Marine and Maintainence Coatings. Low Blushing Low Color / Low Viscosity products are available Good for Flooring Applications ROYCE INTERNATIONAL
  • Reactivity Study - Gelation Techne Gelation Timer” 100gram scale 1) Epoxy Resin: DGEBA (BLR: Basic Liquid Resin based on BisphenolA) WPE: 190 (RoyOxy RA-928) 2)Phenalkamines: RoyOxy RA-951, RoyOxy RA-950 RoyOxy RA-59 3)Accelerators: a) Nonylphenol : M.W. : 220 (RoyOxy RA-444) b) DMP-30: : M.W. : 265 (RoyOxy RA-3054) c) OTBP:2-tert-butylphenol: M.W. : 150 d) CNSL: Cashew Nut Shell Liquid: M.W. : 300 ROYCE INTERNATIONAL
  • Phenalkamines selected in this Study I) EDA Phenalkamine: i.e. RoyOxy™ RA-951 Fast Cure, Low Blushing, Excellent Corrosion Resistance, High Viscosity II) DETA Phenalkamine: i.e. RoyOxy™ RA-950 Fast Cure, Low Viscosity, Some Blushing III) Mixed (EDA/DETA) Phenalkamine: i.e. RoyOxy™ RA-59, RoyOxy™ RA-59 LC Low Viscosity, Low Blushing, Excellent for Flooring Application ROYCE INTERNATIONAL
  • Geltime Study @ 25 C EDA Phenalkamine (RoyOxy™ RA-951) A.N. : AHEW : Vis. @25 C : Geltime : 316 mgKOH/g 130 27,200 cP (45g/55g BLR) 71 min. Nonylphenol MW: 220 DMP-30 MW: 265 2.0% (0.9 g) 65.1 min. 2.4% (1.08 g) 69.0 min 4.0% (1.8 g) 57.5 min. 4.8% (2.16 g) 63.6 min. 8.0% (3.6 g) 46.5 min. 9.6% (4.32 g) 57.1 min. ROYCE INTERNATIONAL
  • Geltime Study @ 25 C EDA Phenalkamine (RoyOxy™ RA-951) Nonylphenol MW: 220 A.N. AHEW Vis. @25 C Geltime DMP-30 MW: 265 : 316 mgKOH/g : 130 : 27,200 cP : (45g/55g BLR) 71 min. OTBP MW: 150 CNSL MW: 300 2.0% (0.9 g) 65.1 min. 2.4% (1.08 g) 69.0 min. 1.36% (0.61 g) 62.1 min. 2.72% (1.22 g) 66.3 min. 4.0% (1.8 g) 57.5 min. 4.8% (2.16 g) 63.6 min. 2.72% (1.22 g) 56.2 min. 5.44% (2.44 g) 55.2 min. 8.0% (3.6 g) 46.5 min. 9.6% (4.32 g) 57.1 min. 5.44% (2.44 g) 45.6 min. 10.9% (4.88 g) 46.8 min. ROYCE INTERNATIONAL
  • Geltime Study @ 5 C EDA Phenalkamine (RoyOxy™ RA-951) Nonylphenol MW: 220 A.N. : 316 mgKOH/g AHEW : 130 Vis. @25 C : 27,200 cP Geltime : (45g/55g BLR) 77.9 min. DMP-30 MW: 265 OTBP MW: 150 CNSL MW: 300 2.0% (0.9 g) 71.9 min. 2.4% (1.08 g) 75.5 min. 1.36% (0.61 g) 69.3 min. 2.72% (1.22 g) 72.4 min. 4.0% (1.8 g) 66.6 min. 4.8% (2.16 g) 75.9 min. 2.72% (1.22 g) 67.1 min. 5.44% (2.44 g) 71.2 min. 8.0% (3.6 g) 57.8 min. 9.6% (4.32 g) 73.2 min. 5.44% (2.44 g) 61.5 min. 10.9% (4.88 g) 65.6 min. ROYCE INTERNATIONAL
  • Geltime Study @ 25 C DETA Phenalkamine: (RoyOxy™ RA-950) Nonylphenol MW: 220 A.N. AHEW Vis.@25 C Geltime DMP-30 MW: 265 : : : : 518 mgKOH/g 81 1280 cP (30g/70g BLR) 37.8 min. OTBP MW: 150 CNSL: MW: 300 2.0% (0.60 g) 37.0 min. 2.4% (0.72 g) 40.7 min. 1.36% (0.41 g) 35.2 min. 2.72% (0.82 g) 36.4 min. 4.0% (1.2 g) 33.7 min. 4.8% (1.44 g) 40.5 min. 2.72% (0.82 g) 31.8 min. 5.44% (1.64 g) 34.5 min. 8.0% (2.4 g) 30.6 min. 9.6% (2.88 g) 39.6 min. 5.44% (1.64 g) 27.2 min. 10.88% (3.27 g) 29.3 min. ROYCE INTERNATIONAL
  • Geltime Study @ 5 C DETA Phenalkamine: (RoyOxy™ RA-950) Nonylphenol MW: 220 A.N. AHEW Vis.@25 C Geltime DMP-30 MW: 265 : : : : 518 mgKOH/g 81 1280 cP (30g/70g BLR) 114.7 min. OTBP MW: 150 CNSL: MW: 300 2.0% (0.60 g) 90.7 min. 2.4% (0.72 g) 108.1 min. 1.36% (0.41 g) 84.2 min. 2.72% (0.82 g) 88.1 min. 4.0% (1.2 g) 60.5 min. 4.8% (1.44 g) 112.1 min. 2.72% (0.82 g) 55.2 min. 5.44% (1.64 g) 56.5 min. 8.0% (2.4 g) 46.4 min. 9.6% (2.88 g) 107.1 min. 5.44% (1.64 g) 36.4 min. 10.88% (3.27 g) 41.6 min. ROYCE INTERNATIONAL
  • Geltime Study @ 25 C Mixed Phenalkamine: (RoyOxy RA-59 & RoyOxy RA-59LC) Nonylphenol MW: 220 A.N. AHEW Vis. @25 C Geltime DMP-30 MW: 265 : : : : 343mgKOH/g 95 1317 cP (34g/66g BLR) 38.3 min OTBP MW: 150 CNSL: MW: 300 2.0% (0.68 g) 37.2 min. 2.4% (0.82 g) 38.0 min. 1.36% (0.46 g) 37.3 min. 2.72% (0.93 g) 37.5 min. 4.0% (1.36 g) 34.0 min. 4.8% (1.63 g) 35.2 min. 2.72% (0.93g) 35.1 min. 5.44% (1.85 g) 35.0 min. 8.0% (2.72 g) 32.5 min. 9.6% (3.26 g) 33.9 min. 5.44% (1.85 g) 32.3 min. 10.88% (3.70g) 31.1 min. ROYCE INTERNATIONAL
  • Geltime Study @ 5 C Mixed Phenalkamine: (RoyOxy™ RA-59 & RoyOxy™ RA-59LC) Nonylphenol MW: 220 A.N. AHEW Vis.@25 C Geltime DMP-30 MW: 265 : 343mgKOH/g : 95 : 1317 cP : (34g/66g BLR) 105.3 min. OTBP MW: 150 CNSL: MW: 300 2.0% (0.68 g) 82.8 min. 2.4% (0.82 g) 88.1 min. 1.36% (0.46 g) 95.1 min. 2.72% (0.93 g) 100.3 min. 4.0% (1.36 g) 76.3 min. 4.8% (1.63 g) 89.0 min. 2.72% (0.93g) 85.5 min. 5.44% (1.85 g) 86.2 min. 8.0% (2.72 g) 69.1 min. 9.6% (3.26 g) 87.5 min. 5.44% (1.85 g) 78.5 min. 10.88% (3.70g) 81.8 min. ROYCE INTERNATIONAL
  • DGEBA / EDA Phenalkamine (RoyOxy™ RA-951) Water Intake Data Thickness of Cured Bar: 10mm Cured @ 25 C for 24 hrs. , then immersed in 20 C Water for 10 days Catalyst Level None (Neat) Nonyl-Phenol 4.0% 1.80 phr Nonyl-Phenol 8.0% 3.60 phr % of Water Intake 0.291 % 0.291% 0.295% 0.417% 0.601% N/A None (0) 0.04% 0.126% 0.310% Extra Water Intake DMP-30 DMP-30 4.8% 9.6% 2.16 phr 4.32 phr ROYCE INTERNATIONAL
  • Gelation with DGEBA - Geltime @25 C Nonylphenol MW: 220 DMP-30 MW: 265 4.0% (w/w) Stable 4.0%(w/w) Geltime: 119 min 10.0% (w/w) Stable 10.0% (w/w) Geltime: 48 min. ROYCE INTERNATIONAL
  • CONCLUSION - I I) I) In Phenalkamine / Epoxy System: “Phenol Moiety” Alone is better than DMP-30 (Combination of “Phenol” and “BDMA-Tertiary Amine”) II) At 25 C: Similar Acceleration Effect for all phenols disregard whether it is a) Ortho / Para / Meta- substitutions b) Linear Alkyl/Bulky Alkyl/ Linear Alkenyl c) Molecular Weight ROYCE INTERNATIONAL
  • CONCLUSION - II III) At 5 C: Nonylphenol performs best may contribute from: a) Lower Molecular Weight (vs. CNSL) b) Linear alkyl substitution at “Para” position versus Bulky alkyl at “Ortho” position (vs. OTBP) IV) Nonylphenol will not cause extra water intake up to 3.6 phr level, however, DMP-30 causes significant water intake even at 2.16 phr (40% more) and at 4.32 phr (100% more). It might due to the presence of “BDMA Tertiary amine moiety”. ROYCE INTERNATIONAL
  • CONCLUSION - III V) DMP-30 shows no accelerating effect for DETA Phenalkamine (i.e. RoyOxy RA-950) both at 25 and 5 C. This is also true for mixed Phenalkamine (i.e. RoyOxy RA-59) at 5⁰C. VI) In the mixed Phenalkamine / Epoxy System: For All Phenols: The Accelerators behave more closer to EDA Phenalkamine / Epoxy System at both 25 and 5⁰C. ROYCE INTERNATIONAL
  • www.royceintl.com info@royceint.com 941-894-1228 ROYCE INTERNATIONAL 3400 South Tamiami Trail Sarasota, FL 34239 ROYCE INTERNATIONAL