Transcript New Secondary Amine Chain Extenders for Aliphatic Polyurea

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
NCO
NCO
OCN
NCO
H3C
CH3
Hexamethylene diisocyanate (HDI)
CH3
IPDI
O
OCN---6(H2C)
N
N
C
O
OCN
NCO
H12MDI
(CH2)6 ---NCO
C
C
N
O
(CH2)6 -----NCO
Hexamethylene diisocyanate (HDI) Trimer
Molecular Structures
NH
HN
NH
JEFFLINK™ 754
CLEARLINK® 1000
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
Density @ 25ºC, g/mL
0.855
110 @ 16C
0.89
Summary of Chemical Sources
Chemical
JEFFAMINE® D-2000
JEFFAMINE® T-5000
TIOXIDE® TiO2
JEFFLINK™ 754
CLEARLINK® 1000
VESTANAT® IPDI
Manufacturer
HUNTSMAN LLC
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 - H18 wheel
1000 grams, 1000 rev.
• Gloss
ASTM D638 - Type IV
ASTM D638 - Type IV
ASTM D638 - Type IV
ASTM D624 - Die C
ASTM D2240-81
ASTM D4060
ASTM D523
Pneumatic Static Mix Equipment
Dual-Cartridge
200 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%
39
10
44
0
7
36.9
8.6
0.0
47.5
7.0
1.06
1.0
1.036
1.062
1.0
1.021
JEFFAMINE® D-2000
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
Equal Wt% Results (Static-Mix)
8276-30
JL754
8276-48
CL1000
35
64
47
73
Shore Hardness (0 sec)
(10 sec)
62D
53D
61D
50D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
2657
819
1229
1335
623
2855
778
1159
1386
601
60
84
63
84
String Gel Time (sec)
Tack-Free Time (sec)
Gloss
20 deg
60 deg
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
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
48.4
8.6
36.0
0.0
7.0
36.9
8.6
0.0
47.5
7.0
50.4
8.6
34.0
0.0
7.0
1.062
1.0
1.021
1.062
1.0
1.021
1.104
1.0
1.018
45/55 Static Mix Results
8276-47
JL754
8276-48
CL1000
8276-63-2
JL754
42
67
47
73
32
72
Shore Hardness (0 sec)
(10 sec)
52D
41D
61D
50D
46D
33D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
2700
1090
770
952
405
2855
778
1159
1386
601
1997
953
647
837
385
Coating Density (g/cc)
1.031
1.045
0.983
String Gel Time (sec)
Tack-Free Time (sec)
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%
39
10
44
0
7
25
10
0
58
7
42.8
8.6
41.6
0
7
1.06
1.0
1.036
1.061
1
1.036
1.101
1.0
1.032
JEFFAMINE® D-2000
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
50/50 Static Mixed Results
8276-30
JL754
8276-31
CL1000
8276-66-2
JL754
35
64
49
75
36
57
Shore Hardness (0 sec)
(10 sec)
62D
53D
57D
45D
61D
50D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
2657
819
1229
1335
623
Too
Brittle
To get
Data
N/A
2246
721
1096
1239
566
Coating Density (g/cc)
1.039
1.02
1.036
String Gel Time (sec)
Tack-Free Time (sec)
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
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
42.8
8.6
41.6
0
7
39.4
8.6
0
45
7
1.101
1.0
1.032
1.101
1.0
1.018
Equal Wt% Results (Spray)
8276-66-1
JL754
8276-64-1
CL1000
7
21
14
40
Shore Hardness (0 sec)
(10 sec)
58D
46D
51D
39D
Tensile Strength (psi)
Elongation (%)
Modulus (100%)
Modulus (300%)
Tear Strength (pli)
2236
834
889
1047
440
1593
737
757
915
397
Abrasion (mg lost)
Gloss
20 deg
60 deg
459
22.2
62.7
497
34.2
70.7
Gel Time (sec)
Tack-Free Time (sec)
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
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
48.4
8.6
36
0
7
36.9
8.6
0
47.5
7
50.4
8.6
34
0
7
39.4
8.6
0
45
7
1.062
1.0
1.021
1.062
1.0
1.021
1.104
1.0
1.018
1.101
1.0
1.018
45/55 Spray Results
8276-62
JL754
8276-61
CL1000
8276-63-1
JL754
8276-64-1
CL1000
10
67
10
40
11
47
14
40
Shore Hardness (0 sec)
(10 sec)
40D
27D
51D
39D
40D
28D
51D
39D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
1186
815
518
634
309
1038
419
786
879
349
2157
1074
561
740
291
1593
737
757
915
397
Abrasion (mg lost)
Gloss
20 deg
60 deg
476
13.5
44.5
569
45.3
79.9
452
16.8
54.7
497
34.2
70.7
Gel Time (sec)
Tack-Free Time (sec)
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
JEFFAMINE® T-5000
JEFFLINK® 754
CLEARLINK® 1000
TiO2
Processing
Index
Iso/Resin Volume Ratio
Iso/Resin Weight Ratio
42.8
8.6
41.6
0
7
39
10
44
0
7
25
10
0
58
7
1.101
1.0
1.032
1.06
1.0
1.036
1.061
1.0
1.036
50/50 Spray Results
8276-66-1
JL754
8276-59
JL754
8276-60
CL1000
7
21
5
22
8
27
Shore Hardness (0 sec)
(10 sec)
58D
46D
55D
45D
65D
55D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
2236
834
889
1047
440
2672
875
1003
1120
526
2121
493
1434
1550
530
Abrasion (mg lost)
Gloss
20 deg
60 deg
459
22.2
62.7
514
47.0
83.0
331
55.7
85.3
Gel Time (sec)
Tack-Free Time (sec)
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)
0
1
24
8.11
23.7
49.4
Aromatic Comparison
8276-72
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)
(10 sec)
51D
39D
49D
39D
58D
46D
55D
46D
Tensile Strength (psi)
Elongation (%)
Modulus (100%) (psi)
Modulus (300%) (psi)
Tear Strength (pli)
1593
737
757
915
397
1558
669
820
999
373
2236
834
889
1047
440
1555
514
975
1178
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.