UTECH Conference Charlotte, NC, 2014

Development of Organometallic and Metal-Organic Catalysts for

Polyurethane Applications

Brandon Parks, Reaxis Inc.

June 4th, 2014

UTECH Conference Charlotte, NC, 2014

Overview

Catalyst reactivity and physical property development in several MDI/HDI elastomers and 2K waterborne/solventborne coatings

Impact of catalyst loading on reactivity in a MDI elastomer formulation

Effect of relative humidity and NCO/OH selectivity

using C333 W50 in a 2K WB coating

Influences on catalyst stability and shelf life in a MDI elastomer system

UTECH Conference Charlotte, NC, 2014

Effect of Catalyst Selection in a MDI Elastomer Formulation

0.00

5.00

10.00

15.00

20.00

25.00

C726

C226

C320

C325

C717

C218(DBTL)

C321

C333E50

C716

C739E50

C114

C125

C129

C723

C109

C620

GelTim

e(min)

Catalyst

= Organotin = Inorganic Tin = Bismuth

= Zinc

UTECH Conference Charlotte, NC, 2014

Effect of Catalyst Selection in a HDI Elastomer Formulation

0.00

20.00

40.00

60.00

80.00

100.00

120.00

C726

C716

C717

C311X

C233

C325

C218(DBTL)

C129

C228

C216

C739E50

C333E50

C620

GelTim

e(min)

Catalyst

= Organotin = Inorganic Tin = Bismuth

= Zinc

UTECH Conference Charlotte, NC, 2014

Shore A Hardness Development in a MDI Formulation

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

1.0x10-4 1.0x10-4 1.0x10-4 1.0x10-4 1.0x10-4 1.0x10-4 1.0x10-4 1.0x10-4 2.0x10-4 1.0x10-4 2.0x10-4

C129 C214 C216 C218(DBTL) C228 C325 C333E50 C716 C726

ShoreAHardness

CatalystLoading(mol)Catalyst

UTECH Conference Charlotte, NC, 2014

Impact of Catalyst Loading in a MDI Elastomer Formulation

0.00

5.00

10.00

15.00

20.00

25.00

1.0x10-4 1.0x10-4 2.0x10-4 1.0x10-4 2.0x10-4 1.0x10-4 2.0x10-4 1.0x10-4 1.5x10-4 2.0x10-4

C218(DBTL) C109 C620 C723 C739E50

GelTim

e(min)

CatalystLoading(mol)Catalyst

= Organotin = Inorganic Tin = Bismuth

= Zinc

UTECH Conference Charlotte, NC, 2014

Curing Profile in a 2K WB PU Formulation

0

30

60

90

120

150

180

210

240

270

300

C739W50 C739E50 C333W50 C333E50 C622W78C218(DBTL)NoCatalyst

Time(min) Set-to-Touch

Tack-Free

Dry-Hard

Dry-Through

Pot-life

UTECH Conference Charlotte, NC, 2014

Color, Gloss, and Physical Property Development in a 2K WB Formulation

L* a* b* 20° 60°

C739W50 90.85 -1.23 1.17 46.1 79.7

C739E50 91.05 -1.10 1.41 59.1 82.4

C333W50 90.54 -1.36 0.84 59.7 84.2

C333E50 90.77 -1.23 1.19 60.3 84.4

C622W78 90.94 -1.17 1.30 41.3 78.2

C218 (DBTL) 91.22 -1.12 1.35 64.1 80.3

No Catalyst 90.68 -1.16 1.35 50.9 81.6

GlossColorCatalyst

C739W50 F 5B 68

C739E50 3H 4B 68

C333W50 B 3B 54

C333E50 HB 3B 52

C622W78 HB 4B 52

C218 (DBTL) HB 5B 48

No Catalyst HB 5B 38

CatalystPencil

Hardness

Cross-Cut

Tape

Adhesion

MEK

Double

Rubs

UTECH Conference Charlotte, NC, 2014

Effect of Catalyst Loading on Dry Times in a 2K WB PU Formulation

0

30

60

90

120

150

180

0.20% 0.40% 0.20% 0.40% 0.20% 0.40% 0.20% 0.40% 0.20% 0.40% 0.20% 0.40%

C218(DBTL) C333E50 C333W50 C739E50 C739W50 C622W78

DryTim

e(min)

Set-to-Touch

TackFree

DryHard

DryThrough

UTECH Conference Charlotte, NC, 2014

Effect of Relative Humidity on Dry Times Using C333 W50 in a 2K WB Formulation

0

50

100

150

200

250

50 75 90 50 75 90

C333W50 C218(DBTL)

Time(min)

Rela veHumidity(%)

Set-to-Touch

DustFree

DryHard

UTECH Conference Charlotte, NC, 2014

Selectivity of C333 W50 Towards the NCO/OH Reaction in a 2K WB Formulation

2.5

2.7

2.9

3.1

3.3

3.5

3.7

3.9

4.1

0 50 100 150 200 250 300

-Ln

(Ab

s)

(22

70

cm

-1)

Time (min)

C333W50 - Water

C333W50 - Butanol

Krel = 6.7

UTECH Conference Charlotte, NC, 2014

Dry Times in 2K Solventborne Formulation

0

60

120

180

240

300

360

420

480

540

600

660

720

C739E50 C333E50 C218(DBTL) NoCatalyst

DryTim

es(m

in)

Set-to-Touch

Tack-Free

Dry-Hard

Dry-Through

>720.0

UTECH Conference Charlotte, NC, 2014

Catalyst Shelf Life in a MDI Elastomer Formulation

0.00

1.00

2.00

3.00

4.00

5.00

6.00

0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2 0 1 2

C216 C218(DBTL) C227 C320 C321 C333E50 C726 C739E50

GelTim

e(min)

Time(weeks)Catalyst

UTECH Conference Charlotte, NC, 2014

Change in Reactivity Over Time in a MDI Elastomer Formulation

-2.0

18.0

38.0

58.0

78.0

98.0

118.0

138.0

158.0

178.0

1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2

C216 C218(DBTL) C227 C320 C321 C333E50 C726 C739E50

Chan

geinGelTim

e(%)

Time(weeks)Catalyst

UTECH Conference Charlotte, NC, 2014

Conclusions

Evaluated a library of viable catalysts in several MDI/HDI elastomer and 2K WB/SB coating formulations

Demonstrated the development of several novel, water-soluble, hydrolytically stable, organotin-, Bi-, and Zn-based catalysts (C333, C739, C622) that exhibit excellent curing and physical property development in 2K WB/SB formulations

Exhibited enhanced reactivity of C333 W50 under elevated levels

of relative humidity and high levels of selectivity towards the NCO/OH reaction in a 2K WB formulation

Demonstrated feasibility for a series of inorganic Sn-, Bi-, and Zn-based materials as potential alternatives to organotin systems

UTECH Conference Charlotte, NC, 2014

Future Studies

Further develop understanding of catalyst stability and factors influencing shelf life

Expand NCO/OH selectivity study to include C739 W50 and C622 W78

Heat activation of catalysts (“activated cure”)

UTECH Conference Charlotte, NC, 2014

Acknowledgments

Dr. Lanny Venham

Carl Holsinger

Michael Curcione

Dr. Leon Perez

Reaxis Inc.

UTECH Conference Charlotte, NC, 2014

Thanks For Your Attention!

Visit us at booth #124!

Check us out on www.reaxis.com for a full product list and more information!

Questions?

UTECH Conference Charlotte, NC, 2014

General MDI/HDI Elastomer Formulation

Material Weight (g)

NCO:OH

1,4-Butanediol 1.2 1.05

Polymeric MDI-Based

Isocyanate8.0

Total 68

Polypropylene Oxide-

Based Triol58.8

Material Weight (g)

NCO:OH

1,4-Butanediol 1.2 1.05

Aliphatic HDI-Based

Isocyanate Trimer11.0

Total 71

Polypropylene Oxide-

Based Triol58.8

UTECH Conference Charlotte, NC, 2014

Catalyst Comparison 2K WB Formulation

Material Weight (g) Weight Solids (g)

Rutile TiO2 Pigment 65.31 65.31

Rheological Modifier 0.86 2.15

Dispersant 2.3 1.04

Flow Modifier 3.4 0.10

Water 71.22 0

Catalyst 0.018-0.020 0.018-0.020

Total 361.36 154.39

82.2

Defoamer 3.8 3.59

Polyester Polyol

Dispersion205.5

3:1 Water-Dispersable,

Aliphatic

Polyisocyanate (HDI) in

EEP

8.97 -

Weight % Solids NCO:OH

42.72 1.10

UTECH Conference Charlotte, NC, 2014

Catalyst Loading and Relative Humidity 2K WB Formulation

Material Weight (g) Weight Solids (g)

Wetting Agent 4.4 3.16

Water Letdown 641.3 0

Catalyst 0.08 or 0.16 0.08 or 0.16

Total 1426.7 615.71

10% Aqueous

Ammonia Solution23.4 0

Water-Dispersable,

Aliphatic

Polyisocyanate (HDI)

462.0 346.53

Water-Reducible

Polyester Polyol295.6 266.02

Weight % Solids NCO:OH

43.16 1.4-1.15

UTECH Conference Charlotte, NC, 2014

Solventborne Formulation

Material Weight (g)

Rutile TiO2 38.0

Flow Modifier 2.36 NCO:OH

Dispersant 2.3 1.1-1.2

EEP 71.2

1-Methoxy-2-Propanol

Acetate18.22

Catalyst 0.01% wt.

Total 654.1

Aliphatic

Polyisocyanate HDI-

Based Resin

462.0

Polyester Polyol 58.6

Dispersant 1.42