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

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

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

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

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

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

Huntsman Performance Products 2. Faster curing agents

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

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

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

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

Huntsman Performance Products Modification for Faster Cure Coatings formulations

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

Huntsman Performance Products 3. Slower curing agents

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

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

Huntsman Performance Products Modification for Slower Cure

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

Huntsman Performance Products 4. New backbone

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

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

Huntsman Performance Products Modification of Backbone Structure PTMEGA-1000 Curing agent components concentrations, phr, in standard liquid resin PTMEGA PPGDA PPGDA PPGTA Properties Viscosity, cps T g, °C

Huntsman Performance Products Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin PTMEGA PPGDA PPGDA PPGTA Accelerator heatrtheatrtheatrtheatrt Flexural strength, psi Flexural modulus, psi Tensile strength, psi Elongation at break, % % Wt gain, 24 hr water boil % Wt gain, 3 hr acetone boil PTMEGA-1000

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 %

Huntsman Performance Products Modification of Backbone Structure PTMEGA-1700 Curing agent components concentrations, phr, in standard liquid resin PTMEGA PPGDA PPGDA DGA 24 MEA 14 Properties Viscosity, cps Gel time, min 4635 Tg, °C

Huntsman Performance Products Modification of Backbone Structure PTMEGA-1700 Curing agent components concentrations, phr, in standard liquid resin PTMEGA PPGDA PPGDA DGA 24 MEA 14 Accelerator Cure conditions heatrtheatrtheatrtheatrt Flexural strength, psi Flexural modulus, psi Tensile strength, psi Elongation at break, % % Wt gain, 24 hr water boil % Wt gain, 3 hr acetone boil

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