1. New Developments in Polyetheramine Curing Agents David Alexander, Bruce Burton, Howard Klein Huntsman Performance Products The Woodlands, TX 77381 Thermoset Resin Formulators Association Fall 2005 Meeting Ft. Lauderdale, FL November 14, 2005

2. Huntsman Performance Products Outline 1.Introduction – polyetheramine products, changes 2.Products for faster curing 3.Products for slower curing 4.Products with new backbones 5.Summary

3. Huntsman Performance Products  Monoamines, diamines, and triamines  Flexible polyether backbone  Polypropylene glycol, polyethylene glycol-based  Wide molecular weight range – 150 to 5000 JEFFAMINE® Polyetheramines

4. Huntsman Performance Products Polyetheramines as Epoxy Curing Agents  Have been commercial for more than 30 years  Variety of advantages in epoxy curing  Low viscosity, low color, low vapor pressure  Moderate reaction rate  Flexible backbone – good cured resin properties – relatively high elongation  Variety of applications as curing agents  Coatings, adhesives, composites  Flexibility, impact resistance key properties

5. Huntsman Performance Products Polyetheramine Structural Elements Amine end groups  In PPG-based amines, primary amine next to methyl group  Hindrance means slower reaction  Slower is better in some applications  Most PEG-based diamines capped with PO, giving same type of amine group as PPG- based amines

6. Huntsman Performance Products Polyether backbones  Polypropylene glycol – most common; relatively hydrophobic; good mechanical properties  Polyethylene glycol – not so common in curing agents; hydrophilic; important in some other applications Polyetheramine Structural Elements

7. Huntsman Performance Products 2. Faster curing agents

8. Huntsman Performance Products Modification of Amine Environment For faster cure -  Aminoethyl, 3-aminopropyl end groups for more reactive amines  No adjacent methyl group  Amine more exposed

9. Huntsman Performance Products Modification for Faster Cure TEGDA BAPEG BAPDEG PTMEGA-1700 Faster polyetheramines

10. Huntsman Performance Products Modification for Faster Cure Faster polyetheramines  Formulated viscosities similar  Reactivities much higher than conventional polyetheramines  Modifcation necessary for coatings applications

11. Huntsman Performance Products Modification for Faster Cure Faster polyetheramines  Expected trend in glass transition temperatures; similar to PPGDA-230  Flexural properties similar for group  Thermal shock resistance generally superior for systems cured with low MW linear etherdiamines

12. Huntsman Performance Products Modification for Faster Cure Coatings formulations

13. Modification for Faster Cure Coatings properties  High-build, decorative-type coatings  Shorter dry times with reactive amines; MNP inhibits blushing  Adduction, Mannich base formation possible modifications

14. Huntsman Performance Products 3. Slower curing agents

15. Huntsman Performance Products Modification of Amine Environment For slower cure –  Some applications benefit from longer working times – e.g. large composite parts  2-aminobutyl groups for less reactive amines  Adjacent ethyl instead of methyl group; amine less exposed New products –  BOTDA – diamine  BOTTA – triamine

16. Modification for Slower Cure Slower polyetheramines  AHEWs similar, giving similar mix ratios  Viscosities similar, so formulations similar in behavior  Process essentially same as for existing amines, giving low color products

17. Huntsman Performance Products Modification for Slower Cure

18. Slower polyetheramines  Glass transition temperatures slightly higher than those of existing products  Cured resin properties similar; good mechanical properties

19. Huntsman Performance Products 4. New backbone

20. Huntsman Performance Products Modification of Backbone Structure PTMEG – new backbone for polyetheramines  Higher carbon/oxygen ratio means better water resistance  Better mechanical properties  Used in high-performance TPU formulations

21. Huntsman Performance Products Modification of Backbone Structure  PTMEGA-1000  PPG/PTMEG mix  2.0 functionality New PTMEG-based amines

22. Huntsman Performance Products Modification of Backbone Structure PTMEGA-1000 Curing agent components concentrations, phr, in standard liquid resin PTMEGA-100022 4033 PPGDA-2000 25 PPGDA-400445040 PPGTA-400 33 Properties Viscosity, cps7006004501800 T g, °C35332543

23. Huntsman Performance Products Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin PTMEGA-1000 22 40 33 PPGDA-2000 25 PPGDA-400 44 50 40 PPGTA-400 33 Accelerator 399 10 5 heatrtheatrtheatrtheatrt Flexural strength, psi 5500 -- 115007600 Flexural modulus, psi 195000-- 337000230000 Tensile strength, psi 350024001700 125057065004100 Elongation at break, % 1151258673145951248 % Wt gain, 24 hr water boil 2.72.82.61.22.42.62.54.3 % Wt gain, 3 hr acetone boil 23253033 271520 PTMEGA-1000

24. Huntsman Performance Products Modification of Backbone Structure PTMEGA-1700  All PTMEG means more exposed amine group  Mixture of amines; contains 2° amine also New PTMEG-based amines n = 13 x = 0, the "monomer,” [~19%] x = 1, the "dimer” [~78%]; x=2 a few %

25. Huntsman Performance Products Modification of Backbone Structure PTMEGA-1700 Curing agent components concentrations, phr, in standard liquid resin PTMEGA-1700 26 35 PPGDA-2000 25 PPGDA-400 5250 DGA 24 MEA 14 Properties Viscosity, cps 8006009501800 Gel time, min 4635 Tg, °C 28332240

26. Huntsman Performance Products Modification of Backbone Structure PTMEGA-1700 Curing agent components concentrations, phr, in standard liquid resin PTMEGA-1700 26 35 PPGDA-2000 25 PPGDA-400 52 50 DGA 24 MEA 14 Accelerator 399 5 10 Cure conditions heatrtheatrtheatrtheatrt Flexural strength, psi -- 6600-- Flexural modulus, psi -- 180000-- Tensile strength, psi 215020001700 --215051504300 Elongation at break, % 1001508673-- 300150136 % Wt gain, 24 hr water boil 2.23.92.61.26.4 5.55.7 % Wt gain, 3 hr acetone boil 2928303342 2731

27. Huntsman Performance Products Summary  Variations in polyetheramine structure lead to variations in epoxy curing properties  Amine end group environment  Backbone structure  Expanding range of polyetheramine structures, applications  Slower amines for longer working time, good properties  Faster amines for more versatility in formulating  New polymer backbones for improved properties