Catalysis of IsocyanatesWerner J. Blank

SL2195

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Mike Emmet John FlorioZ. A. He Ed HessellMarie E. PicciMike ThomasJason Poff

Contributors to this Work

CATALYSIS OF ISOCYANATES

HYDROXYL-ISOCYANATE REACTIONDIFFERENT CATALYSTS DBTDL, Al, Bi, ZrHOW TO SELECT A CATALYSTREACTION RATES WITH HYDROXYLSELECTIVITY OF OH vs WATERFORMULATION GUIDE LINES

BLOCKED ISOCYANATES

ISOCYANATE REACTIONS

R-OH

R-COOHR-NHCONH-RR-NHCOO-R

TRIMERDIMER

EPOXYR-NH2

HOH

CARBODIIMIDE

R-NCO

SL2196R-CH2 act.

CATALYSIS PROBLEMS

HIGH SOLIDS COATINGS

POTLIFE/REACTIVITYMOISTURE REACTIONSOLUBILITYNETWORK STABILITY

WATERBORNE

WATER REACTIONPOTLIFEGASSINGSTABILITYGLOSS

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 / DIACETATEDIBUTYLTIN OXIDE MERCURY COMPOUNDS LEAD COMPOUNDSAMINESZINC SALTSMANGANESE SALTS

CATALYST PROPERTIESPOTLIFE / REACTIVITYSELECTIVITYDELAYED ACTIONLOW TEMPERATUREHIGH TEMPERATUREWATERHIGH RATE (RIM)EXTERIOR DURABILITYRESISTANCE PROPERTIESENVIRONMENT - TOXICITY

SL2197

Isocyanate-Hydroxyl Reactions

ROH + R’NCO R’NHCOOR

CO CO 22

R’NH +2 R’NCO R’NHCONHR’

R’NCO + H2 O R’-NHCOOH R’-NH2

SL2198

R’NCOR’NHCOOR + R’NCOOR

R’NHCO

R’NCOR’NHCONHR’ + R’NCONHR’

R’HNCO

ADDITIONAL REACTIONS

SL2199

SCREENING OF CATALYSTS

APPLICATION TESTS FORMULATIONPOTLIFE (2X VISC.)GEL TIMETACK FREEDRY-THROUGH

MODEL SYSTEMS (ANALYTICAL)DISAPPEARANCE OF NCOFORMATION OF URETHANE / UREAMW

NR-NCO

O

N

N OO

R-NCO

OCN-R

HDI-TRIMER

0

60

120

180

240

300

360

420

480

540

600

Visc

osity

(min

@ 2

5°C

)

0

5

10

15

20

25

30

Tack

Fre

e (h

rs @

25°

C)

A B C D E F G H I J K L M N O P Q

Catalyst

VISC. 2X Tack Free (hrs)

Catalyst Study (HDI TRIMER)Metal (0.0065% on Solids)

A: DBTDLB: DBTDAC: Mn Naph/PDD: Mn OctE: Sn Oct/PDF: Vn acac/PDG: Vn acacH: Bi OctI: Bi NaphJ: Zn acac/PDK: Zn OctL: Co OctM: Zr acacN: Zr acac/PDO: Zr OctP: Al acacQ:Al chelate/PD

SL2242

150

200

250

300

350

400

Visc

osity

(cps

)

90

92

94

96

98

100

Unr

eact

ed N

CO

0 100 200 300 400 500 600 Minutes @ 25°C

% NCO VISCOSITY

PE/HDI-TRIMERNo Catalyst

SL2017

1E0

1E1

1E2

1E3

1E4

TIM

E. m

inut

e

0.0001 0.001 0.01 0.1 DBTDL, Sn %

Potlife TACK FREE

PE/HDI-TRIMERCATALYST REACTION RATE

SL2245

NETWORK FORMATIONA4 + B2

0

2

4

6

8

10

0 0.2 0.4 0.6 0.8 1

CONVERSION

DE

GR

EE

OF

P

OL

YM

ER

IZA

TIO

N

00.20.40.60.811.21.41.61.82

FR

AC

TIO

N

Mw

Mn

Ws

P(X3)

P(X4)

CATALYSTS

Zr ChA……….XC-4205…….ZrAcAcZr ChB……….XC-6212…….Zr DionateAl Ch1………..XC-5218…….Al DionateBi carb……….K-348………..Bi Oct.DBTDL………………………..Dibutyltin C12DBTDA……………………….Dibutyltin Ac

Metal Chelate with 2,4-PD

CH3

CH3

CHC

C

O

O

n

-

M+

SL2202

23482308

22682228

2940 2460 1980 1500 1020 5

39 58.5

0.00

0.10

0.20

0.30

0.40

0.50

0.60

Ab

s

Wavenumber

Time (sec)

Isocyanate Peak Decay

REACTIVITY WITH DIFFERENT HYDROXYL GROUPS

OH

OH

OH

OOH

O

NH

OOH

O

OOH

OO

OHO

N-BUTANOL

ISOBUTANOL

2-BUTANOL

HEC

BUCELL

METRIPOP

HEE

HDI TRIMER / HYDROXYLDBTDL 0.0140% Sn

n-BUTANOL

0.0

0.2

0.4

0.6

0.8

1.0

1.2

0 1000 2000 3000 4000 5000 6000

TIME, sec

NC

O N

OR

MA

LIZE

D DBTDL 0.014 % Sn

Zr CHEL. 0.014 % Zr

Bi CARB. 0.014 % Bi

DABCO 1 %

Zn OCT. 0.014 % Zn

0

0.2

0.4

0.6

0.8

NC

O N

OR

MAL

IZED

300

0 se

c.

Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST

n-BUTANOL

2BUCEL

HEE

HEC

HDI-TRIMER/HYROXYLPRIMARY HYDROXL

0.134 % 10% 0.0134 %

0.268 %

0.0134 %

SL2337

0

0.2

0.4

0.6

0.8

1

NC

O N

OR

MA

LIZE

D 3

000

sec.

Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST

n-BUTANOL

2-BUTANOL

ISOBUTANOL

HDI-TRIMER/HYROXYLpri, sec BUTANOL

0.134 % 10% 0.0134 %

0.268 %

0.0134 %

SL2338

0

0.2

0.4

0.6

0.8

1

NC

O N

OR

MA

LIZE

D 3

000

sec.

Bi Dabco DBTDL Zn Oct. Zr ChelCATALYST

n-BUTANOL

2-BUTANOL

2-BUCELL

METRIPROP

HDI-TRIMER/HYROXYLpri, sec BUTANOL, ETHER

0.134 % 10% 0.0134 %

0.268 %

0.0134 %

SL2339

Polyether MDI Elastomer Bi Oct. 1/5 mol WATER

0

50000

100000

150000

200000

250000

0 20 40 60 80 100

Time, minutes

Vis

cosi

ty, c

P

Bi Oct. Initial Bi Oct. 2 days Bi Oct. 7 days

CATALYSTS

Zr ChA……….XC-4205…….ZrAcAcZr ChB……….XC-6212…….Zr Dionate

XC-9213…….Zr DionateAl Ch1………..XC-5218…….Al DionateBi carb……….K-348………..Bi Oct.Bi carb……….XC-8203...…..Bi Carb.DBTDL………………………..Dibutyltin C12DBTDA………………………..Dibutyltin Ac

0

50

100

150

200 G

EL T

IME

(min

)

0 0.01 0.02 0.03 CATALYST CONCENTRATION (Me, %)

Zr B Zr A DBTDL

GEL TIMEACRYLIC/HDI-TIMER

SL2073

0

50

100

150

200

250

300 Ti

me

(min

.)

0 0.005 0.01 0.015 0.02 CATALYST CONC. Me %

Zr B Zr A DBTDL

Tack Free time Acrylic HDI-Trimer

SL2077

0

100

200

300

400

Tim

e ( m

in.)

0 0.005 0.01 0.015 0.02 CATALYST, CONC Me %

Zr B Zr A DBTDL

DRY THROUGH TIMEACRYLIC/HDI-TRIMER, 30 µ,RT, 66 % RH

SL2075

1900.0 1800 1700 1600 1500 1400

1/CM

A

urea

urethane

urethane + urea

1698

1698

1647

1647

1568

1461

1539

1570

1462

1461

-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6 A

BSO

RB

AN

CE

1500 1600 1700 1800 WAVENUMBER CM-1

ZIRC A DBTDL

SELECTIVITY OF CATALYSISDBTDL & Zr CHELATE

UREA

SL2183

1900.0 1800 1700 1600 1500 1400.0

1/cm

A

urea

urethane

Zr diketonate

DBTDL

Zn octoate

urea

urethane

/

\

\

/

0 1 2 3 4 5 6 7 RELATIVE SELECTIVITY URETH/UREA

XC-6212

Uncatalyzed

DBTDL

K-5218

DBTDAC

K-348

Zn oct

Co octC

ATA

LYST

SELECTIVITY HYDROXYL / WATER

NCO/OH/WATER 1/1/2

0

20

40

60

80

100 W

EIG

HT,

%

Sn 0.0074% Zr 0.008 %

WATER

HDI-TRI

POLYMER

WATERBORNE TWO COMPONENT

SL2192

0

2

4

6

8

TIM

E, H

OU

RS

No catalyst DBTDL Zr CHCATALYST

TACK FREE THROUGH DRY

WATERBORNE TWO COMPONENT

SL2193

0

20

40

60

80

100 G

LOSS

, %

0

1

2

3

4

5

MA

XIM

UM

PO

TLIF

E, H

RS

No catalyst DBTDL Zr CHGLOSS 20° GLOSS 60° POTLIFE

WATERBORNE TWO COMPONENTCATALYST SELECTION

SL2194

LEWIS ACID CATALYSIS

R-N=C=O + R” SnX22

+ R’OH

R - N=C=O2R”

Sn

2X

-+

R -N=C=O2R”

Sn2X

-

O H R’+

R-NHCOOR’ + R” SnX 22SL2200

AMINE CATALYSIS

OR-N-C

O-R’H

+ R”3N

R”3N + H- O- R’ R”3N….H….O- R’

+

R”3N….H….O- R’ + R-N=C=O R-N….C….O

R”3N….H….O- R’

-

SL2201

3(AcAc) Zr-OR

4(AcAc) Zr 4(AcAc) Zr R

0H

+ROH

- ROH

-AcAc+AcAc(slow)

(fast)

ZIRCONIUM CHELATE CATALYSIS

SL2203

3(AcAc) Zr-OR R’-NCO

3(AcAc) Zr-OR

R’N=C=O

3

O ||

(AcAc) Zr-N-C-OR| R’

ROH

O||

R’NH-C-OR

ZIRCONIUM CHELATE CATALYSIS

SL2204

3(AcAc) ZrOH 3(AcAc) ZrOZr(AcAc)3

Zr(AcAc) + H O4 2 3

(AcAc) ZrOH+AcAc

HYDROLYSIS OF Zr CHELATE

SL2205

DELAYED ACTION OF Bi CARBOXYLATE

Bi (RCOO)3 + H2O Bi2O3 + RCOOH

Bi2O3 + RCOOH Bi (RCOO)3 + H2O

R-NHCOOH + Bi2O3 Bi (RNHCOO)3

DEACTIVATION

ACTIVATION

H2O + RNCO R-NHCOOH R-NH2 + C02

WHY REPLACE DBTDL

ENVIRONMENTAL Al, Bi, ZrPOTLIFE - REACTIVITY AlPIGMENT ABSORPTION AlSELECTIVITY - HYDROXYL vs WATER Zr

LOW GLOSS HIGH HUMIDITY ZrGASSING Zr

WATERBORNE ZrDELAYED REACTION BiSIDE REACTIONS ZrHYDROLYSIS OF ESTER GROUPS Al, Bi, ZrDURABILITY Al, Bi, Zr

FORMULATION GUIDE LINES

CATALYST INHIBITION - DEACTIVATIONPIGMENT ABSORPTIONWATERACID NUMBERAMINE

HIGH SOLIDSPOTLIFE - REACTIVITYSOLUBILITY

WATERBORNEGASING CATALYSTHYDROLYSIS

0.0001

0.001

0.01

0.1

1

10

K-KA

T %

ON

BIN

DER

0.0001 0.001 0.01 0.1 1 DBTDL % ON BINDER

K-348 XC-9213 XC-8203 XC-6212 K-4205, K-5218

K-KAT CATALYST CONCENTRATIONDBTDL REPLACEMENT LEVEL

ALL CATALYST LEVELSAS SUPPLIED

CATALYSTS FORMULATION GUIDELINE Zr Chelate XC-6212, XC-9213

Add to isocyanateZr Chelate 4205

Water free formulation low in acid number

Bismuth carboxylate K-348, XC-8203COOH beneficialLow water contentDehydrating agents

Al Chelate K-5218Low acid number, neutralizationLow water content2,4-pentanedione addition

12

13

14

15

16

17 IC

I VIS

CO

SITY

, 25°

C, P

oise

initialy 2 weeks

CONTROL XC-6212

STABILITY OF HDI-TRIMER 50°CK-KAT XC-6212 (4%)

SL2079

0 60

120 180 240 300 360 420 480 540 600

VISC

OSI

TY, 2

X (m

in @

25°

C)

1.8 1.23 0.58 02,4-PENTANEDIONE on SOLIDS, %

K-KAT 5218 DBTDL

POLYESTER/HDI-TRIMERTACK FREE TIME 3.0-4.0 HOURS

SL2021

K-KAT 5218 1.3 %DBTDL 0.023%

0

10

20

30

40

50

60

VISC

OSI

TY, m

inut

es

0

2

4

6

8

10

12

TAC

K F

REE

, hou

rs

4 376 748 13472,4 PENTANEDION/Zr mole ratio

2X visc (min) Tack Free (hrs)

POLYESTER/HDI-TRIMER CATALYSTCATALYST Me 0.0065% ON SOLIDS

SL2015F

HIGH REACTION SPEEDPLURAL COMPONENT GUN…………….POT LIFEHEAT CURE……………………...EXTERIOR DURABILITYHIGH HUMIDITY…………………..WATERBORNENCO BLOCKEDPU-PREPOLYMER………………..RIM

K-348 Bi K-4205 Zr K-6212 ZrK-5218 AlDBTDL

CATALYST SELECTION

SL2210

0 2 4 6 8

10 12 14

AC

ID N

UM

BER

0 2 4 8 13 18TIME (weeks)

DBTDAc CONTROL K-KAT XC-6212

K-Kat 4205 K-Kat 348 K-Kat 5218

Hydrolysis of polyesterin presence of catalyst (0.01%on TRS)

SL2072

SUMMARYORGANO 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 RNCO + BL

RNCO + R’OH RNHCO-OR’

RNHCO-BL + R’OH RNHCO-OR’+BL

k1

k2

k1

k2

k3

BLOCKED ISOCYANATES

ROH

NN

H

RO-C

RO-CHCH

O

O

>C=N-OHRR

OH

O

NH

0 50 100 150 200

DBTDL

K-KAT 348

Phenol Pyrazol Oxime

Carbitol Caprolactam Uretdione

BLOCKED ISOCYANATE++++++++

++++++++++++++++

++++++++++++

++++++++++++

MEK + °C

0 50 100 150 200

MEK / °C

uretdione

caprolactam

carbitol

pyrazol

phenol

oxime

K-KAT 348 No Cat Temp, °C

BLOCKED ISOCYANATE

ACKNOWLEDGEMENT

TECHNICAL SERVICE DEPARTMENT

wblank@kingindustries.comwww.kingindustries.comwww.wernerblank.com

SL2211