Catalysis of Isocyanates

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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