Secondary Amines for Aliphatic Polyurea Polymers

Mark Posey and Kenneth Hillman

Huntsman - Austin Research Labs

Thermoset Resin Formulators Association 2003 Inaugural ConferenceNovember 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

H3CCH3 CH3

NCO

NCO

IPDI

NCOOCN

Hexamethylene diisocyanate (HDI)

OCN NCO

H12MDI

N

CN

C

NC (CH2)6 ---NCOOCN---

6(H2C)

(CH2)6 -----NCO

O

OO

Hexamethylene diisocyanate (HDI) Trimer

Molecular Structures

HN NH

JEFFLINK™ 754 CLEARLINK® 1000

NH

NH

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, mmHg 0.02 < 0.02

Viscosity @ 25ºC, cP 13 110 @ 16C

Density @ 25ºC, g/mL 0.855 0.89

Summary of Chemical Sources

Chemical Manufacturer

JEFFAMINE® D-2000 HUNTSMAN LLC

JEFFAMINE® T-5000 HUNTSMAN LLC

TIOXIDE® TiO2 HUNTSMAN TIOXIDE

JEFFLINK™ 754 HUNTSMAN LLC

CLEARLINK® 1000 UOP (now Dorf Ketal)

VESTANAT® IPDI CREANOVA

Summary of ASTM Methods Used

• Tensile Strength, psi ASTM D638 - Type IV

• Modulus, psi ASTM D638 - Type IV

• Percent Elongation, % ASTM D638 - Type IV

• Tear Strength, pli ASTM D624 - Die C

• Hardness, Shore A/D ASTM D2240-81

• Taber Abrasion - H18 wheel ASTM D4060

1000 grams, 1000 rev.

• Gloss ASTM D523

Pneumatic Static Mix Equipment

Dual-Cartridge200 mL Each Side Speed Adjustment

Comparison of Equal Wt% Formulations

IPDI/D-2000 Prepolymer

8276-30 8276-48

% NCO 16.82 14.72

Resin Blend Wt% Wt%

JEFFAMINE® D-2000 39 36.9JEFFAMINE® T-5000 10 8.6JEFFLINK® 754 44 0.0CLEARLINK® 1000 0 47.5TiO2 7 7.0ProcessingIndex 1.06 1.062Iso/Resin Volume Ratio 1.0 1.0Iso/Resin Weight Ratio 1.036 1.021

Equal Wt% Results (Static-Mix)

8276-30 JL754

8276-48 CL1000

String Gel Time (sec) 35 47Tack-Free Time (sec) 64 73

Shore Hardness (0 sec) 62D 61D (10 sec) 53D 50D

Tensile Strength (psi) 2657 2855Elongation (%) 819 778Modulus (100%) (psi) 1229 1159Modulus (300%) (psi) 1335 1386Tear Strength (pli) 623 601

Gloss 20 deg 60 63 60 deg 84 84

45/55 Static Mixed Formulations

IPDI/D-2000 8276-47 8276-48 8276-63-2

45 / 55 wt% Prepolymer% NCO 14.72 14.72 14.72

Resin Blend Wt% Wt% Wt%

JEFFAMINE® D-2000 48.4 36.9 50.4JEFFAMINE® T-5000 8.6 8.6 8.6JEFFLINK® 754 36.0 0.0 34.0CLEARLINK® 1000 0.0 47.5 0.0TiO2 7.0 7.0 7.0ProcessingIndex 1.062 1.062 1.104Iso/Resin Volume Ratio 1.0 1.0 1.0Iso/Resin Weight Ratio 1.021 1.021 1.018

45/55 Static Mix Results

8276-47 JL754

8276-48 CL1000

8276-63-2 JL754

String Gel Time (sec) 42 47 32Tack-Free Time (sec) 67 73 72

Shore Hardness (0 sec) 52D 61D 46D (10 sec) 41D 50D 33D

Tensile Strength (psi) 2700 2855 1997Elongation (%) 1090 778 953Modulus (100%) (psi) 770 1159 647Modulus (300%) (psi) 952 1386 837Tear Strength (pli) 405 601 385

Coating Density (g/cc) 1.031 1.045 0.983

50/50 Static Mixed Formulations

IPDI/D-2000 8276-30 8276-31 8276-66-2

50 / 50 wt% Prepolymer% NCO 16.82 16.82 16.82

Resin Blend Wt% Wt% Wt%

JEFFAMINE® D-2000 39 25 42.8JEFFAMINE® T-5000 10 10 8.6JEFFLINK® 754 44 0 41.6CLEARLINK® 1000 0 58 0TiO2 7 7 7ProcessingIndex 1.06 1.061 1.101Iso/Resin Volume Ratio 1.0 1 1.0Iso/Resin Weight Ratio 1.036 1.036 1.032

50/50 Static Mixed Results

8276-30 JL754

8276-31 CL1000

8276-66-2 JL754

String Gel Time (sec) 35 49 36Tack-Free Time (sec) 64 75 57

Shore Hardness (0 sec) 62D 57D 61D (10 sec) 53D 45D 50D

Tensile Strength (psi) 2657 Too 2246Elongation (%) 819 Brittle 721Modulus (100%) (psi) 1229 To get 1096Modulus (300%) (psi) 1335 Data 1239Tear Strength (pli) 623 N/A 566

Coating Density (g/cc) 1.039 1.02 1.036

Typical Spray Conditions

• Gusmer GX-7 400 Gun, with 212 Pattern Control Disk and 453 Mixing Module.

• Feed preheat and hose heat set at 160F.

• 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

IPDI/D-2000 Prepolymer

8276-66-1 8276-64-1

% NCO 16.82 14.72

Resin Blend Wt% Wt%

JEFFAMINE® D-2000 42.8 39.4JEFFAMINE® T-5000 8.6 8.6JEFFLINK® 754 41.6 0CLEARLINK® 1000 0 45TiO2 7 7ProcessingIndex 1.101 1.101Iso/Resin Volume Ratio 1.0 1.0Iso/Resin Weight Ratio 1.032 1.018

Equal Wt% Results (Spray)

8276-66-1 JL754

8276-64-1 CL1000

Gel Time (sec) 7 14Tack-Free Time (sec) 21 40

Shore Hardness (0 sec) 58D 51D (10 sec) 46D 39D

Tensile Strength (psi) 2236 1593Elongation (%) 834 737Modulus (100%) 889 757Modulus (300%) 1047 915Tear Strength (pli) 440 397

Abrasion (mg lost) 459 497Gloss 20 deg 22.2 34.2 60 deg 62.7 70.7

45/55 Sprayed Formulations

IPDI/D-2000 Prepolymer

8276-62 8276-61 8276-63-1 8276-64-1

% NCO 14.72 14.72 14.72 14.72

Resin Blend Wt% Wt% Wt% Wt%

JEFFAMINE® D-2000 48.4 36.9 50.4 39.4JEFFAMINE® T-5000 8.6 8.6 8.6 8.6JEFFLINK® 754 36 0 34 0CLEARLINK® 1000 0 47.5 0 45TiO2 7 7 7 7ProcessingIndex 1.062 1.062 1.104 1.101Iso/Resin Volume Ratio 1.0 1.0 1.0 1.0Iso/Resin Weight Ratio 1.021 1.021 1.018 1.018

45/55 Spray Results

8276-62 JL754

8276-61 CL1000

8276-63-1 JL754

8276-64-1 CL1000

Gel Time (sec) 10 10 11 14Tack-Free Time (sec) 67 40 47 40

Shore Hardness (0 sec) 40D 51D 40D 51D (10 sec) 27D 39D 28D 39D

Tensile Strength (psi) 1186 1038 2157 1593Elongation (%) 815 419 1074 737Modulus (100%) (psi) 518 786 561 757Modulus (300%) (psi) 634 879 740 915Tear Strength (pli) 309 349 291 397

Abrasion (mg lost) 476 569 452 497Gloss 20 deg 13.5 45.3 16.8 34.2 60 deg 44.5 79.9 54.7 70.7

50/50 Sprayed Formulations

IPDI/D-2000 Prepolymer

8276-66-1 8276-59 8276-60

% NCO 16.82 16.82 16.82

Resin Blend Wt% Wt% Wt%

JEFFAMINE® D-2000 42.8 39 25JEFFAMINE® T-5000 8.6 10 10JEFFLINK® 754 41.6 44 0CLEARLINK® 1000 0 0 58TiO2 7 7 7ProcessingIndex 1.101 1.06 1.061Iso/Resin Volume Ratio 1.0 1.0 1.0Iso/Resin Weight Ratio 1.032 1.036 1.036

50/50 Spray Results

8276-66-1 JL754

8276-59 JL754

8276-60 CL1000

Gel Time (sec) 7 5 8Tack-Free Time (sec) 21 22 27

Shore Hardness (0 sec) 58D 55D 65D (10 sec) 46D 45D 55D

Tensile Strength (psi) 2236 2672 2121Elongation (%) 834 875 493Modulus (100%) (psi) 889 1003 1434Modulus (300%) (psi) 1047 1120 1550Tear Strength (pli) 440 526 530

Abrasion (mg lost) 459 514 331Gloss 20 deg 22.2 47.0 55.7 60 deg 62.7 83.0 85.3

QUV Testing of Samples

• Coating samples were placed in a QUV cabinet with QUVB-313 bulbs for 2012 hours of continuous exposure at 35C 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 JL754)

8276-64-1 4.19 2.21 2.19 (45/55 CL1000)

8276-66-1 3.88 2.37 2.42 (50/50 JL754)

Aromatic Comparison

0 1 24

8276-72 8.11 23.7 49.4

Properties After QUV Exposure

8276-64-1 CL1000

8276-64-1 2012 QUV

8276-66-1 JL754

8276-66-1 2012 QUV

Shore Hardness (0 sec) 51D 49D 58D 55D (10 sec) 39D 39D 46D 46D

Tensile Strength (psi) 1593 1558 2236 1555Elongation (%) 737 669 834 514Modulus (100%) (psi) 757 820 889 975Modulus (300%) (psi) 915 999 1047 1178Tear Strength (pli) 397 373 440 416

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.