New Developments in Polyetheramine Curing Agents David Alexander

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

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

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

Polyetheramine Structural Elements 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 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 Faster polyetheramines TEGDA BAPEG BAPDEG PTMEGA-1700 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 Huntsman Performance Products

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

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 Huntsman Performance Products

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

Modification for Slower Cure 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

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 New PTMEG-based amines · PTMEGA-1000 § PPG/PTMEG mix § 2. 0 functionality Huntsman Performance Products

PTMEGA-1000 Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin PTMEGA-1000 PPGDA-2000 22 PPGDA-400 PPGTA-400 Properties Viscosity, cps Tg, °C 40 25 44 50 33 40 33 700 600 450 1800 35 33 25 43 Huntsman Performance Products

PTMEGA-1000 Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin 22 PTMEGA-1000 PPGDA-2000 22 PPGTA-400 Accelerator 399 44 PPGDA-400 44 25 25 50 50 10 40 10 5500 -- -- Flexural modulus, psi 195000 -- -- -- 3500 2400 1700 115 125 2. 7 23 % Wt gain, 3 hr acetone boil heat rt 33 Flexural strength, psi % Wt gain, 24 hr water boil 40 33 heat Elongation at break, % rt 40 10 heat Tensile strength, psi rt 40 33 5 heat rt -- 11500 7600 -- -- 337000 230000 1700 1250 570 6500 4100 86 73 145 95 12 48 2. 6 1. 2 2. 4 2. 6 2. 5 4. 3 25 30 33 33 27 15 20 Huntsman Performance Products

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

PTMEGA-1700 Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin 26 PTMEGA-1700 PPGDA-2000 52 PPGDA-400 DGA MEA Properties Viscosity, cps Gel time, min Tg, °C 35 35 25 50 24 14 800 600 950 1800 46 35 22 40 28 33 Huntsman Performance Products

PTMEGA-1700 Modification of Backbone Structure Curing agent components concentrations, phr, in standard liquid resin 26 PTMEGA-1700 PPGDA-2000 26 52 PPGDA-400 52 35 35 35 25 25 50 50 24 DGA MEA Accelerator 399 5 heat rt Cure conditions 35 24 heat 10 rt 14 heat rt Flexural strength, psi -- -- 6600 -- Flexural modulus, psi -- -- -- 180000 -- Tensile strength, psi 2150 2000 1700 -- 2150 5150 4300 Elongation at break, % 100 150 86 73 -- 300 150 136 % Wt gain, 24 hr water boil 2. 2 3. 9 2. 6 1. 2 6. 4 5. 5 5. 7 29 28 30 33 42 42 27 31 % 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 Huntsman Performance Products