Spanning the Gulf Between Primary Amine and Hydroxyl Reactivity, New Secondary Aliphatic Amines for the

Formulators Toolbox

R OH

R1 NH R2

R NH2

Mark Posey and Ken Hillman Huntsman Advanced Technology Center

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

Polyurea Development Association 2005 Annual Conference 1 March 8-10, The Grand Casino Biloxi, Biloxi, Mississippi

The Problem
OH reaction with isocyanate is slow and usually requires catalyst. Water competes with OH for isocyanate reaction. Primary amine is fast reacting, time for leveling and good adhesion is needed. Chain extenders and aspartic esters are cost prohibitive for some applications. The need, a low-cost method to modify the cure speed of polyurea systems.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

The Technology
Proprietary Huntsman catalyst technology allows high secondary amine formation with little primary or tertiary.
O
R NH O n O NH R

R y NH O

R NH

O x

NH z

Intrinsic reactivity drops roughly a factor of 20 for secondary compared to primary amines.
Steric hindrance plays an additional role in slowing the reactivity.

Cure speed (gel time) of a formulation is dependent on concentrations and inherent reactivity. Products are stable, so there is no off-gassing of reversible blocking agents.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

Huntsmans New Secondary Polyetheramines

Secondary Version of Approximate Functionality Density, 25C, g/cm3 Kinematic Viscosity, 25C, cSt Total Amine, meq/gram Target Equivalent weight, grams/eq XTJ-584 D-230 2 0.885 7 5.3-6.3 172 XTJ-585 D-400 2 0.921 18 3.5-4.0 270 XTJ-576 D-2000 2 0.978 209 0.9-1.0 1042 XTJ-586 T-403 3 0.923 46 4.5-5.5 204

Products TSCA listed as of October 2004

Developmental quantities available now. May be available for sale in other countries due to polymer exemption rules.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

Potential Uses for Secondary Polyetheramines

Polyurea Chain Extender - Aliphatic AND Aromatic Systems
Used in conjunction with, or to replace, existing chain extenders.

Polyurethane/Polyurea hybrids When using the amine as a reactant, prevents more than one reaction at each amine site. Isocyanate Prepolymers / Quasi Pre-polymers
Reduced viscosity compared to primary amines. Viscosity in the neighborhood of polyol prepolymers. Prepolymers possible that form gels with primary amines. Valuable in PU, polyurea and other iso/amine applications
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

Viscosity Reduction in Isocyanate Prepolymers

Hydrogen Bonding in Ureas from Primary Amines
O R N H C N H R

Hydrogen Bonding in Ureas from Secondary Amines

O R N H C N R2 O R

O R N H C N H R

R N H

C N R2

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

IPDI Quasi-prepolymer Viscosity

9000 8000 IPDI/D-2000 7000 Kinematic Viscosity at 25C, cSt IPDI / XTJ-576 IPDI / D-2000 / 10% PC 6000

5000

4000

3000

2000

1000

0 40 45 50 Wt% IPDI in Prepolymer Formation

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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60

H12MDI Quasi-prepolymer Viscosity

7000 H12MDI / D-2000 H12MDI / XTJ-576 6000

Kinematic Viscosity at 25C, cSt

5000

4000

3000

2000

1000

0 40 45 50 55 60 65 Wt% H12MDI in Prepolymer Formation

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

Aliphatic Coatings Formulations

Both Formulations 1:1 Volume Ratio at ~14.5% NCO
Reference No. A Side IPDI JEFFAMINE D-2000 amine XTJ-576 B Side JEFFAMINE D-2000 amine JEFFAMINE T-5000 amine JEFFLINK 754 chain extender TiO2 Tensile Strength, psi Max Elongation, % 100% Modulus, psi 300% Modulus, psi Tear Strength, pli Shore D, 0 sec / 10 sec A/B Delta P, psi 8276-63-1 45 55 0 50.4 8.6 34 7 2157 1074 561 740 291 40/28 700 8349-96 45 0 55 49 10 36 5 2066 892 561 799 297 44/28 250

Allows the efficient formation of low viscosity prepolymers from polyetheramines with equivalent properties.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

High Hardness Aliphatic Formulations

All Formulations 1:1 Volume Ratio HDI trimer (~21.7% NCO)
Reference No. D-2000 D-400 XTJ-585 Secondary Amine X JEFFLINK 754 chain extender TiO2 Tensile Strength, psi Max Elongation, % Tear Strength, pli Shore D, 0 sec / 10 sec Spray, Gel Time, sec Tack Free, sec 8276-68 15 20 0 0 60 5 5282 14 354 73/69 1 5 8276-71 10 0 25 0 65 0 5166 13 692 78/73 2 9 8349-31 10 0 0 30 45 5 3401 96 748 73/64 3 15

Secondary amines allow the formation of an aliphatic, very high hardness coating at a reasonable cost.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Modified Aspartic Ester Formulations

HDI trimer/XTJ-576 Prepolymer (85/15 wt%), ~17.4% NCO, 1:1 Volume Ratio
Reference No. XTJ-585 DESMOPHEN NH1420 resin JEFFLINK 754 curing agent TiO2 Tensile Strength, psi Max Elongation, % 100% Modulus, psi Tear Strength, pli Shore D, 0 sec / 10 sec Spray, Gel Time, sec Tack Free, sec 8349-24 0 83 12 5 4488 17 N/A 649 70/65 120 2 hrs 8349-25 20 60 15 5 2349 152 2006 554 63/52 32 40-60 min

Secondary amines reduce cure speed by reducing % NCO. Secondary polyetheramines expand formulation capabilities of aspartic esters at a much lower cost.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Partial Replacement of Aromatic Chain Extenders

Aliphatic amines react too fast to replace aromatic amines in aromatic formulations, right? Wrong. The following tables shows the effect of replacing aromatic amines with secondary aliphatic amines (in small amounts). Can improve flexibility and/or reduce cost of aromatic systems. Conclusion - Aliphatic amines are not just for aliphatic formulations!
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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High Hardness Aromatic Formulations

All Formulations 1:1 Volume Ratio with SUPRASEC 9549 isocyanate (~19.4%NCO)
Reference No. D-2000 T-5000 ETHACURE 100 curing agent XTJ-584 XTJ-585 XTJ-586 UNILINK 4200 additive TiO2 Tensile Strength, psi Max Elongation, % 100% Modulus, psi Tear Strength, pli Shore D, 0 sec / 10 sec Spray, Gel Time, sec Tack Free, sec 8314-9 23 9 18 0 18 0 27 5 2477 231 1984 605 61/54 6 16 8314-10 27 9 18 0 0 18 23 5 2546 100 2190 583 69/63 4.5 9 8314-11 25 9 17 17 0 17 10 5 2669 118 1891 624 68/60 4.5 10

Secondary polyetheramines allow high hardness aromatic formulations while maintaining flexibility and good cure speed at a reasonable cost.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Replacement of UNILINK 4200 additive with Secondary Amines in Aromatics

All Formulations with RUBINATE 9480 Aromatic Isocyanate (~15.5%NCO)
Reference No. JEFFAMINE D-2000 amine JEFFAMINE T-5000 amine ETHACURE 100 curing agent XTJ-584 XTJ-586 JEFFLINK 754 curing agent UNILINK 4200 additive TiO2 Tensile Strength, psi Max Elongation, % 100% Modulus, psi 300% Modulus, psi Tear Strength, pli Shore D, 0 sec / 10 sec Spray, Gel Time, sec Tack Free, sec 8276-72 53 10 22 0 0 0 10 5 2902 637 1116 1639 506 50/41 6 12 8314-12 55 10 22 0 0 8 0 5 2664 606 1064 1569 476 51/43 7 11 8276-93 48 10 22 0 15 0 0 5 2642 492 1168 1767 423 53/44 6 10 8276-92 53 10 22 10 0 0 0 5 2569 653 1007 1454 478 52/41 7 11.5

Secondary aliphatic amines can partially replace 4200. Reduces cost and improves the initial coating color.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Summary
Secondary polyetheramines allow the efficient formation of low viscosity prepolymers with properties equivalent to primary polyetheramines or polyols. Secondary amines allow the formation of high hardness coatings, with good flexibility, at a reasonable cost. Secondary polyetheramines can expand formulation capabilities of aspartic esters, and at a much lower cost. Secondary aliphatic amines can partially replace UNILINK 4200 additive in aromatic formulations with equivalent properties and cure speed. Cure speed (gel time) is dependent on both intrinsic kinetics and concentration of the reactants.
2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Commercial Availability
Developmental quantity samples available now of XTJ-584, XTJ-585, XTJ-586, XTJ-576. Patent applications have been filed on the production method and use of these products. Technical Data Sheets are available at www.huntsmanpolyurea.com. Opportunities unlimited, go formulate!

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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Formulations Disclaimer
All information contained herein is provided "as is" without any warranties, express or implied, and under no circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or reliance upon such information. Nothing contain in this publication should be construed as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any patent. The term "Huntsman" is used herein for convenience only, and refers to Huntsman Corporation, its direct and indirect affiliates, and their employees, officers, and directors. Typical properties, where stated, are to be considered as representative of current production and should not be treated as specifications. While all the information presented in this document is believed to be reliable and to represent the best available data on these products, NO GUARANTEE, WARRANTY, OR REPRESENTATION IS MADE, INTENDED, OR IMPLIED AS TO THE CORRECTNESS OR SUFFICIENCY OF ANY INFORMATION, OR AS TO THE SUITABILITY OF ANY CHEMICAL COMPOUNDS FOR ANY PARTICULAR USE, OR THAT ANY CHEMICAL COMPOUNDS OR USE THEREOF ARE NOT SUBJECT TO A CLAIM BY A THIRD PARTY FOR INFRINGEMENT OF ANY PATENT OR OTHER INTELLECTUAL PROPERTY RIGHT. EACH USER SHOULD CONDUCT A SUFFICIENT INVESTIGATION TO ESTABLISH THE SUITABILITY OF ANY PRODUCT FOR ITS INTENDED USE. Products may be toxic and require special precautions in handling. For all products listed, user should obtain detailed information on toxicity, together with proper shipping, handling, and storage procedures, and comply with all applicable safety and environmental standards. JEFFAMINE, JEFFLINK, SUPRASEC, and RUBINATE are registered trademark of Huntsman Corporation or an affiliate thereof in one or more, but not all countries. DESMOPHEN is a trademark of Bayer. UNILINK is a trademark of Dorf Ketal. ETHACURE is a trademark of Albemarle.

2005 PDA Annual Conference, March 8-10, 2005, Biloxi, MS

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