Secondary Amines for Aliphatic Polyurea Polymers

1
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.
2
Objectives of This Presentation

• Introduce JEFFLINK 754, Huntsmans
  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.

3
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 90s 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.

4
Aliphatic Isocyanate Structures
5
Molecular Structures
JEFFLINK 754
CLEARLINK 1000
6
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
_at_ 25ºC, mmHg 0.02 lt 0.02 Viscosity _at_ 25ºC,
cP 13 110 _at_ 16C Density _at_ 25ºC,
g/mL 0.855 0.89
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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

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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

9
Pneumatic Static Mix Equipment
Dual-Cartridge 200 mL Each Side
Speed Adjustment
10
Comparison of Equal Wt Formulations
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Equal Wt Results (Static-Mix)
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45/55 Static Mixed Formulations
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45/55 Static Mix Results
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50/50 Static Mixed Formulations
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50/50 Static Mixed Results
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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.

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Comparison of Equal Wt Formulations
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Equal Wt Results (Spray)
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45/55 Sprayed Formulations
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45/55 Spray Results
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50/50 Sprayed Formulations
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50/50 Spray Results
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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.

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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

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Properties After QUV Exposure
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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.

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Conclusions

• JEFFLINK 754 is faster reacting than
  CLEARLINK1000, 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.
• Clearlink1000 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.

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Wrap-up / More Information

• Huntsman is working hard to bring to market new
  molecules that will further enhance the
  formulators 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.