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Catalysis of Isocyanates Werner J. Blank
[email protected] www.kingindustries.com www.wernerblank.com
SL2195
Contributors to this Work Mike Emmet John Florio Z. A. He Ed Hessell Marie E. Picci Mike Thomas Jason Poff
CATALYSIS OF ISOCYANATES HYDROXYL-ISOCYANATE REACTION DIFFERENT CATALYSTS DBTDL, Al, Bi, Zr HOW TO SELECT A CATALYST REACTION RATES WITH HYDROXYL SELECTIVITY OF OH vs WATER FORMULATION GUIDE LINES BLOCKED ISOCYANATES
ISOCYANATE REACTIONS R-OH
R-NCO R-NH2
HOH
EPOXY
R-COOH
TRIMER
R-NHCONH-R
DIMER
R-NHCOO-R R-CH2 act.
CARBODIIMIDE SL2196
CATALYSIS PROBLEMS HIGH SOLIDS COATINGS
WATERBORNE
POTLIFE/REACTIVITY MOISTURE REACTION SOLUBILITY NETWORK STABILITY
WATER REACTION POTLIFE GASSING STABILITY GLOSS
Objectives of this Study ENVIRONMETALLY ACCEPTABLE CATALYSTS REACTION RATE OF CATALYSTS WITH OH SELECTIVE CATALYSTS FOR OH IMPROVED POTLIFE/REACTIVITY REDUCED WATER REACTION
CATALYSTS USED DIBUTYLTIN DILAURATE / DIACETATE DIBUTYLTIN OXIDE MERCURY COMPOUNDS LEAD COMPOUNDS AMINES ZINC SALTS MANGANESE SALTS
CATALYST PROPERTIES POTLIFE / REACTIVITY SELECTIVITY DELAYED ACTION LOW TEMPERATURE HIGH TEMPERATURE WATER HIGH RATE (RIM) EXTERIOR DURABILITY RESISTANCE PROPERTIES ENVIRONMENT - TOXICITY
SL2197
Isocyanate-Hydroxyl Reactions ROH + R’NCO
R’NHCOOR CO 2
R’NCO + H2 O
R’-NHCOOH
R’NH 2 + R’NCO
R’-NH2
R’NHCONHR’ SL2198
ADDITIONAL REACTIONS R’NHCOOR + R’NCO
R’NCOOR R’NHCO
R’NHCONHR’ + R’NCO
R’NCONHR’ R’HNCO SL2199
SCREENING OF CATALYSTS APPLICATION TESTS FORMULATION POTLIFE (2X VISC.) GEL TIME TACK FREE DRY-THROUGH MODEL SYSTEMS (ANALYTICAL) DISAPPEARANCE OF NCO FORMATION OF URETHANE / UREA MW
HDI-TRIMER R-NCO O
O
N
N
N R-NCO
OCN-R O
Catalyst Study (HDI TRIMER) Metal (0.0065% on Solids) 30
600
25
480 420
20
360 300
15
240 10
180 120
5
60 0
A
B
C
D
E
F
G
H
I
J
K
L
M N
O
P
Q
0
Tack Free (hrs @ 25°C)
Viscosity (min @ 25°C)
540
A: DBTDL B: DBTDA C: Mn Naph/PD D: Mn Oct E: Sn Oct/PD F: Vn acac/PD G: Vn acac H: Bi Oct I: Bi Naph J: Zn acac/PD K: Zn Oct L: Co Oct M: Zr acac N: Zr acac/PD O: Zr Oct P: Al acac Q:Al chelate/PD
Catalyst VISC. 2X
Tack Free (hrs)
SL2242
400
100
350
98
300
96
250
94
200
92
150
90
0
100
200 300 400 Minutes @ 25°C % NCO
VISCOSITY
500
600 SL2017
Unreacted NCO
Viscosity (cps)
PE/HDI-TRIMER No Catalyst
PE/HDI-TRIMER CATALYST REACTION RATE
TIME. minute
1E4
1E3
1E2
1E1
1E0 0.0001
0.001
0.01
0.1
DBTDL, Sn % Potlife
TACK FREE
SL2245
DEGREE OF POLYMERIZATION
10
2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0
Mw
8 Ws P(X4)
6 4
P(X3) Mn
2 0 0
0.2
0.4
0.6
CONVERSION
0.8
1
FRACTION
NETWORK FORMATION A4 + B2
CATALYSTS Zr ChA……….XC-4205…….ZrAcAc Zr ChB……….XC-6212…….Zr Dionate Al Ch1………..XC-5218…….Al Dionate Bi carb……….K-348………..Bi Oct. DBTDL………………………..Dibutyltin C12 DBTDA……………………….Dibutyltin Ac
Metal Chelate with 2,4-PD
-
CH 3 C
O +
M
CH C CH3
O n SL2202
Isocyanate Peak Decay
0.60 0.50
Wavenumber
2268
2228
1500
2308
1980
0.00 2348
2460
539
0.10
1020
0.20
58.5
0.30
2940
Abs
0.40
Time (sec)
REACTIVITY WITH DIFFERENT HYDROXYL GROUPS O
OH OH N H
N-BUTANOL
O
HEC
OH
O
OH
ISOBUTANOL
O
OH
BUCELL
O
HEE O O
2-BUTANOL OH
OH O
METRIPOP
HDI TRIMER / HYDROXYL DBTDL 0.0140% Sn n-BUTANOL
NCO NORMALIZED
1.2 1.0 DBTDL 0.014 % Sn
0.8
Zr CHEL. 0.014 % Zr Bi CARB. 0.014 % Bi
0.6
DABCO 1 %
0.4
Zn OCT. 0.014 % Zn
0.2 0.0 0
1000
2000
3000 TIME, sec
4000
5000
6000
HDI-TRIMER/HYROXYL PRIMARY HYDROXL NCO NORMALIZED 3000 sec.
0.8 0.134 %
0.0134 %
0.0134 %
10%
0.268 %
0.6
n-BUTANOL 2BUCEL
0.4 HEE HEC
0.2
0
SL2337
Bi
Dabco
DBTDL Zn Oct. Zr Chel
CATALYST
HDI-TRIMER/HYROXYL pri, sec BUTANOL NCO NORMALIZED 3000 sec.
1 0.134 %
0.0134 %
0.0134 %
10%
0.268 %
0.8
n-BUTANOL
0.6 2-BUTANOL
0.4
ISOBUTANOL
0.2 0
SL2338
Bi
Dabco
DBTDL Zn Oct. Zr Chel
CATALYST
HDI-TRIMER/HYROXYL pri, sec BUTANOL, ETHER NCO NORMALIZED 3000 sec.
1 0.134 %
0.0134 %
0.0134 %
10%
0.268 %
0.8 n-BUTANOL
0.6
2-BUTANOL 2-BUCELL
0.4
METRIPROP
0.2 0
SL2339
Bi
Dabco
DBTDL Zn Oct. Zr Chel
CATALYST
Polyether MDI Elastomer Bi Oct. 1/5 mol WATER Viscosity, cP
250000 200000 150000 100000 50000 0
0
20
40
60
80
Time, minutes Bi Oct. Initial
Bi Oct. 2 days
Bi Oct. 7 days
100
CATALYSTS Zr ChA……….XC-4205…….ZrAcAc Zr ChB……….XC-6212…….Zr Dionate XC-9213…….Zr Dionate Al Ch1………..XC-5218…….Al Dionate Bi carb……….K-348………..Bi Oct. Bi carb……….XC-8203...…..Bi Carb. DBTDL………………………..Dibutyltin C12 DBTDA………………………..Dibutyltin Ac
GEL TIME ACRYLIC/HDI-TIMER
GEL TIME (min)
200
150
100
50
0 0
0.01 0.02 CATALYST CONCENTRATION (Me, %) Zr B
Zr A
DBTDL
0.03
SL2073
Tack Free time Acrylic HDI-Trimer
300
Time (min.)
250 200 150 100 50 0 0
0.005 0.01 0.015 CATALYST CONC. Me % Zr B
Zr A
DBTDL
0.02
SL2077
DRY THROUGH TIME ACRYLIC/HDI-TRIMER, 30 µ,RT, 66 % RH
Time ( min.)
400
300
200
100
0 0
0.005 0.01 0.015 CATALYST, CONC Me % Zr B
Zr A
DBTDL
0.02
SL2075
1698
1461
1568 1647
urethane + urea
1647 1570
1461
A
urea
1698 1462 1539
urethane 1900.0
1800
1700
1600
1/CM
1500
1400
SELECTIVITY OF CATALYSIS DBTDL & Zr CHELATE 0.6
UREA
ABSORBANCE
0.5 0.4 0.3 0.2 0.1 0 -0.1 1800
1700
1600
WAVENUMBER CM-1 ZIRC A
DBTDL
1500 SL2183
Zr diketonate
A urea
DBTDL
urea
/
\
urethane
urethane
\
/ Zn octoate 1900.0
1800
1700
1600
1/cm
1500
1400.0
SELECTIVITY HYDROXYL / WATER Co oct
NCO/OH/WATER 1/1/2
CATALYST
Zn oct K-348 DBTDAC K-5218 DBTDL
Uncatalyzed XC-6212
0
1
2
3
4
5
6
7
RELATIVE SELECTIVITY URETH/UREA
WATERBORNE TWO COMPONENT 100
WEIGHT,%
80 WATER
60
HDI-TRI 40 POLYMER 20
0
Sn 0.0074%
Zr 0.008 %
SL2192
WATERBORNE TWO COMPONENT 8
TIME, HOURS
6 4 2 0
No catalyst
DBTDL
Zr CH
CATALYST TACK FREE
THROUGH DRY SL2193
WATERBORNE TWO COMPONENT 5
80
4
60
3
40
2
20
1
0
0
GLOSS, %
100
No catalyst GLOSS 20°
DBTDL
Zr CH
GLOSS 60°
POTLIFE
MAXIMUM POTLIFE, HRS
CATALYST SELECTION
SL2194
LEWIS ACID CATALYSIS
+ R-N=C=O + R”2 SnX 2
R”2 Sn X2
R - N=C=O
-
+ R’OH
R -N=C=O R-NHCOOR’ + R” SnX 2
R”2 Sn X2
O
2
+
H
R’
SL2200
AMINE CATALYSIS R”3N + H- O- R’ R”3N….H….O-
R”3N….H….O- R’
R’ + R-N=C=O
…. ….
R-N C O
R”3N….H….O- R’
+
O R-N-C + R”3N O-R’ H
SL2201
ZIRCONIUM CHELATE CATALYSIS
R
+ROH (AcAc) 4 Zr
0
(AcAc)4 Zr
H
- ROH (fast)
+AcAc
-AcAc
(slow)
(AcAc) 3 Zr-OR
SL2203
ZIRCONIUM CHELATE CATALYSIS (AcAc) 3 Zr-OR O || R’NH-C-OR
ROH
R’-NCO
(AcAc) 3 Zr-OR
O R’N=C=O || (AcAc) 3 Zr-N-C-OR | R’ SL2204
HYDROLYSIS OF Zr CHELATE Zr(AcAc)4 + H 2O
(AcAc) 3 ZrOH
(AcAc)3 ZrOH+AcAc
(AcAc) 3 ZrOZr(AcAc)3
SL2205
DELAYED ACTION OF Bi CARBOXYLATE DEACTIVATION
Bi (RCOO)3 + H2O
Bi2O3 + RCOOH
ACTIVATION
Bi2O3 + RCOOH H2O + RNCO R-NHCOOH + Bi2O3
Bi (RCOO)3 + H2O R-NHCOOH
R-NH2 + C02
Bi (RNHCOO)3
WHY REPLACE DBTDL ENVIRONMENTAL POTLIFE - REACTIVITY PIGMENT ABSORPTION SELECTIVITY - HYDROXYL vs WATER LOW GLOSS HIGH HUMIDITY GASSING WATERBORNE DELAYED REACTION SIDE REACTIONS HYDROLYSIS OF ESTER GROUPS DURABILITY
Al, Bi, Zr Al Al Zr Zr Zr Zr Bi Zr Al, Bi, Zr Al, Bi, Zr
FORMULATION GUIDE LINES HIGH SOLIDS POTLIFE - REACTIVITY SOLUBILITY
WATERBORNE GASING CATALYST HYDROLYSIS
CATALYST INHIBITION - DEACTIVATION PIGMENT ABSORPTION WATER ACID NUMBER AMINE
K-KAT CATALYST CONCENTRATION DBTDL REPLACEMENT LEVEL
K-KAT % ON BINDER
10 1 0.1 0.01 ALL CATALYST LEVELS AS SUPPLIED
0.001 0.0001 0.0001
0.001
0.01
0.1
1
DBTDL % ON BINDER K-348 XC-9213
XC-8203
XC-6212
K-4205, K-5218
CATALYSTS FORMULATION GUIDELINE Zr Chelate XC-6212, XC-9213 Add to isocyanate Zr Chelate 4205 Water free formulation low in acid number Bismuth carboxylate K-348, XC-8203 COOH beneficial Low water content Dehydrating agents Al Chelate K-5218 Low acid number, neutralization Low water content 2,4-pentanedione addition
STABILITY OF HDI-TRIMER 50°C K-KAT XC-6212 (4%)
ICI VISCOSITY, 25°C, Poise
17 16 15 14 13 12
initialy CONTROL
2 weeks XC-6212
SL2079
POLYESTER/HDI-TRIMER VISCOSITY, 2X (min @ 25°C)
TACK FREE TIME 3.0-4.0 HOURS 600
K-KAT 5218 1.3 % DBTDL 0.023%
540 480 420 360 300 240 180 120 60 0
1.8
1.23
0.58
0
2,4-PENTANEDIONE on SOLIDS, % K-KAT 5218
DBTDL
SL2021
POLYESTER/HDI-TRIMER CATALYST 60
12
50
10
40
8
30
6
20
4
10
2
0
0
4
TACK FREE, hours
VISCOSITY, minutes
CATALYST Me 0.0065% ON SOLIDS
376 748 1347 2,4 PENTANEDION/Zr mole ratio SL2015F
2X visc (min)
Tack Free (hrs)
CATALYST SELECTION HIGH REACTION SPEED PLURAL COMPONENT GUN……………. POT LIFE HEAT CURE……………………... EXTERIOR DURABILITY HIGH HUMIDITY………………….. WATERBORNE NCO BLOCKED PU-PREPOLYMER……………….. RIM K-348 Bi
K-4205 Zr DBTDL
K-6212 Zr K-5218 Al SL2210
ACID NUMBER
Hydrolysis of polyester in presence of catalyst (0.01%on TRS)
14 12 10 8 6 4 2 0
0
2
4
8
13
18
TIME (weeks) DBTDAc
CONTROL
K-KAT XC-6212
K-Kat 4205
K-Kat 348
K-Kat 5218
SL2072
SUMMARY ORGANO TIN FREE COATINGS POSSIBLE CHOICE OF CATALYST DEPENDS ON APPLICATION Zr CHELATE CATALYSTS SELECTIVE FOR OH HIGH REACTION RATES POSSIBLE RELATIVE REACTIVITY OF HYDROXYLS DIFFERENT CATALYSIS OF WATERBORNE COATINGS WITH Zr POTLIFE - REACTIVITY Al Bi CATALYST SIMILAR TO DBTDL
REACTION OF BLOCKED ISOCYANATE
RNHCOO-BL
k1
RNCO + R’OH
k2 k3
RNCO + BL RNHCO-OR’ k1
RNHCO-BL + R’OH
k2
RNHCO-OR’+BL
BLOCKED ISOCYANATES ROH N N H
OH
R > C=N-OH R O RO-C HCH
O
N H
RO-C O
BLOCKED ISOCYANATE + + +
K-KAT 348
+ + +
DBTDL
0
50
100 MEK
+ + + + + +
150 + °C
Phenol
Pyrazol
Oxime
Carbitol
Caprolactam
Uretdione
200
BLOCKED ISOCYANATE MEK / °C oxime phenol pyrazol carbitol caprolactam uretdione 0 K-KAT 348
50 No Cat
100
150 Temp, °C
200
ACKNOWLEDGEMENT TECHNICAL SERVICE DEPARTMENT
[email protected] www.kingindustries.com www.wernerblank.com
SL2211