Secondary Amines for Aliphatic Polyurea Polymers Mark Posey

Secondary Amines for Aliphatic Polyurea Polymers Mark Posey and Kenneth Hillman Huntsman - Austin Research Labs Thermoset Resin Formulators Association 2003 Inaugural Conference November 10 -11, The Sofitel Philadelphia Hotel, Philadelphia, Pennsylvania.

Objectives of This Presentation • Introduce JEFFLINK™ 754, Huntsman’s cycloaliphatic chain extender and provide comparisons to CLEARLINK® 1000. • Provide brief overview of aliphatic polyurea. • Provide formulation assistance to get the most out of the molecule. • Demonstrate both sprayed and static-mix coating physical properties and UV resistance. • Demonstrate the conditions at which each product will have superior properties.

Aliphatic Polyurea Overview • Aliphatic coatings do not yellow, however the raw materials are generally more expensive. • There are several aliphatic isocyanates from which to choose, however due to its lower cost and commercial prevalence, IPDI was used in this study. (see next slide) • Prepolymers with PPG-2000 or JEFFAMINE® D-2000 in the 14 -16% NCO range are ideal for spray coatings. • In the early 90’s only primary polyetheramines were available which reacted too fast to be practical. • Introduction of secondary cycloaliphatic amines made aliphatic polyurea viable, but more costly option.

Aliphatic Isocyanate Structures

Molecular Structures JEFFLINK™ 754 CLEARLINK® 1000

Chain Extender Properties Comparisons JEFFLINK™ 754 CLEARLINK® 1000 Molecular Weight 254 322 Equivalent wt, meq/g 7. 87 6. 21 Grams/equivalent 127 161 Pvap @ 25ºC, mm. Hg 0. 02 < 0. 02 Viscosity @ 25ºC, c. P 13 Density @ 25ºC, g/m. L 0. 855 110 @ 16 C 0. 89

Summary of Chemical Sources Chemical Manufacturer JEFFAMINE® D-2000 JEFFAMINE® T-5000 TIOXIDE® Ti. O 2 JEFFLINK™ 754 CLEARLINK® 1000 VESTANAT® IPDI HUNTSMAN LLC HUNTSMAN TIOXIDE HUNTSMAN LLC UOP (now Dorf Ketal) CREANOVA

Summary of ASTM Methods Used • • • Tensile Strength, psi Modulus, psi Percent Elongation, % Tear Strength, pli Hardness, Shore A/D Taber Abrasion - H 18 wheel 1000 grams, 1000 rev. • Gloss ASTM D 638 - Type IV ASTM D 624 - Die C ASTM D 2240 -81 ASTM D 4060 ASTM D 523

Pneumatic Static Mix Equipment Dual-Cartridge 200 m. L Each Side Speed Adjustment

Comparison of Equal Wt% Formulations

Equal Wt% Results (Static-Mix)

45/55 Static Mixed Formulations

45/55 Static Mix Results

50/50 Static Mixed Formulations

50/50 Static Mixed Results

Typical Spray Conditions • Gusmer GX-7 400 Gun, with 212 Pattern Control Disk and 453 Mixing Module. • Feed preheat and hose heat set at 160 F. • Due to high isocyanate viscosity, the pressure differential could be up to 500 psig. Typical pressures 2300 psig Iso. / 2000 psig Resin. • Coatings sprayed onto metal/plastic sheets with mold release to obtain free films. Also sprayed directly onto QUV panels.

Comparison of Equal Wt% Formulations

Equal Wt% Results (Spray)

45/55 Sprayed Formulations

45/55 Spray Results

50/50 Sprayed Formulations

50/50 Spray Results

QUV Testing of Samples • Coating samples were placed in a QUV cabinet with QUVB-313 bulbs for 2012 hours of continuous exposure at 35 C Panel Temp. • No UV stabilizers were used and surface cracks formed in all samples within 200 hours exposure. • Surface cracks made gloss measurement difficult. • Retested sprayed samples after 2012 hours QUV exposure for physical properties.

Yellowness Index (YI) Results Hours Sample 0 1458 2012 8276 -63 -1 4. 51 4. 23 4. 10 (45/55 JL 754) 8276 -64 -1 4. 19 2. 21 2. 19 (45/55 CL 1000) 8276 -66 -1 3. 88 2. 37 2. 42 (50/50 JL 754) Aromatic Comparison 0 8276 -72 1 24 8. 11 23. 7 49. 4

Properties After QUV Exposure

QUV Testing Conclusions • Due to lack of UV Stabilizer, all samples showed surface cracking by 200 hrs. It is recommended that all IPDI formulations utilize a UV stabilizer. • All samples showed essentially no increase in color, and some slightly decreased their Yellowness Index at 2012 hours. • Samples lost some elongation, but gained strength in the 100% and 300% stress values. • Based upon QUV results, we conclude that JEFFLINK™ 754 and CLEARLINK® 1000 have similar color behavior in aliphatic coating systems.

Conclusions • JEFFLINK™ 754 is faster reacting than CLEARLINK® 1000, but not always significantly so. • Neither chain extender can claim to be better at all sets of conditions. Both have good UV stability. • JEFFLINK™ 754 can replace CLEARLINK ® 1000, but reformulation and testing is necessary. • Clearlink® 1000 produces coatings that are harder and less flexible than JEFFLINK™ 754 at equivalent conditions. • When high NCO requires high chain extender content, 754 can provide a more flexible, cost effective coating.

Wrap-up / More Information • Huntsman is working hard to bring to market new molecules that will further enhance the formulator’s “toolbox”. Please stay tuned to our website and your local salesman for more details. • A paper based upon this data can be obtained from our website. • For more information on our products, please visit: www. huntsman. com, JEFFAMINE. COM, huntsmanpolyurea. com, huntsmanepoxy. com, huntsmanchainextenders. com • A portion of this presentation was delivered at the August 2003 Polyurea Development Association conference in Reno, Nevada.