INNOVATIVE AMINE CURING AGENTS FOR EPOXY RESINS FOR CONCRETE Presented by: David Fernee Sr.

Research Scientist, Coatings Formulator Authors: C. Ash, J. Elmore, D. Fernee, D. Weinmann, and D. Woodcock Hexion Specialty Chemicals 12650 Directors Drive, Suite 100 Stafford, TX 77477

Presented at a meeting of the Thermoset Resin Formulators Association at the Hilton Suites Chicago Magnificent Mile in Chicago, Illinois September 14-16, 2008

This paper is presented by invitation of the TRFA. It is publicly distributed upon request by the TRFA to assist in the communication of information and viewpoints relevant to the thermoset industry. The paper and its contents have not been reviewed or evaluated by the TRFA and should not be construed as having been adapted or endorsed by the TRFA

ABSTRACT Recent advances in new amine functional curing agents have improved the performance of waterborne two-package epoxy coating systems. These new amine adducts offer performance advancements along with the ability to meet low and ultra-low VOC levels. This paper will summarize the performance of a new Zero VOC, water-soluble, amine curing agent in WB epoxy formulations with liquid epoxy resin at less than 50g/L VOC. We will review the performance of these new starting formulations against commercially available coatings for concrete This new waterborne curing agent is designed for cementitious applications in industrial and Do-It-Yourself (DIY) markets. Formulations based on this new amine curing agent yield water reducible epoxy coatings systems with superior handling, application properties, water clean-up, and visible end of pot life; as well as, improved resistance to chemicals and staining.

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Introduction Innovative waterborne epoxy binder systems have been advancing rapidly to answer the demands of lower VOC regulations and the markets need for higher performance. Early versions of waterborne epoxy systems met the regulatory demands, but these coatings systems exhibited lower performance compared to their solvent borne counterparts. In recent years, the performance of waterborne epoxy systems has greatly improved thus meeting the higher performance requirements and allowing further reduction of VOC levels. In this work, the new product design criteria and formulated performance design requirements will be summarized. Subsequent to this, the new curing agents properties and performance in formulated systems will be reviewed against commercially available products from the market focusing on the primary modes of failure for coatings for cementitious substrates. Design For the development of this new product, a list of design criteria based on a review of curing agents currently available in the market was established. This assessment created a list of key curing agent design criteria. The design criteria included; ease of use, low viscosity, freeze/thaw stability, heat stability, dilution stability, and chemical inventory status. In addition to the curing agents design criteria, a list of formulation attributes and coating performance requirements of this new curing agent was established. This was based on paint producer input, current commercial products in the market and end-use customer interviews. The critical formulated properties included: PVC, mixed component viscosity, induction time, VOC, pot-life duration, gloss stability during pot-life, hardness development and good chemical resistance. Using the design criteria, a variety of experimental candidates were evaluated and screened. The best candidates having met the curing agents design requirements were formulated into four (4) coating systems to quantify the curing agents performance properties for cementitious applications. These formulations are (See: Appendix 1): Starting formulation A: Concrete gray primer, 4:1, low gloss Starting formulation B: Concrete topcoat clear, 3:1, high gloss Starting formulation C: Concrete topcoat clear, 3:1, high gloss Starting formulation D: Concrete gray primer, 3:1, medium gloss The candidate meeting all of these criteria is now available to formulators in the NAFTA region as a new waterborne curing agent. Experimental Sample preparation and constant calculations Samples were prepared using standard industry methods and raw materials. Reported coating constants were calculated using ASTM D-2369 Film preparation- Draw-downs were performed on Leneta Chart 5C at 5 mil w.f.t., using a standard drawdown bar. Draw downs on concrete were applied using a 60-

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Ambient conditions -All formulation components were equilibrated at 77F for at least 1 day before mixing. Draw downs and films were applied at 77F and 50% R.T and then allowed to dry at the same conditions. All physical testing was performed at 7 days, unless noted. Hardness development- Pencil hardness was determined per ASTM D3363 on the concrete blocks. Pot life, viscosity and gloss measurements- Viscosity was determined per ASTM D562. Gloss was measured at 60 geometry per ASTM D-523. Dry time- Was determined using the BYK Circular Drying timer per ASTM D-5895. Chemical Resistance- Were performed on prepared concrete blocks per ASTM D1308. MEK resistance was performed per ASTM D-5404. Adhesion testing (Pull off) was performed per ASTM D4541 using Elcometer 106 pull off tester with the 2.0 cm dollie.

Results and Discussion A number of commercially available products were purchased for use in this study. These products properties were compared to the starting point formulations (See: Table 1). Then, the performance and chemical spot resistance of these coating systems (See: Table 2) were evaluated with a group of chemicals that are typically found in a residential garage and some common chemicals that are aggressive to coating systems. Table 1- Benchmarking review
Property Mix Ratio (vol.) Induction time, min. Pot Life @ 77F, hrs. VOC, g/L % N.V. (wt./vol.) Recommended Application, w.f.t. Pencil Hardness, Initial / 7 Days In Can Appearance @ overnight Pull-off Adhesion (average psi) Gray Enamel w/EPON 828 and New WB amine1 3:1 30 2-3 48 59% / 50% 1 coat 6-10 mils 4B / F Gelled 865 (0% failure to concrete) Commercial DIY #1 3:1 5 8. <50 43% / 33% 1 coat 6-10 mils 3B/F Liquid 475 (20% failure to concrete) Commercial DIY #2 3:1 15-30 1.5 <100 59% / 48% 1 coat 7-11 mils 5B / F Skins over liquid 450 (45% failure to concrete) Commercial DIY #3 3:1 30 2.5 <100 62% / 49% 1 coat 6-10 mils HB/F Gelled 400 (85% failure to concrete) Commercial DIY #4 2:1 15 4 0 before tinting 50% / 45% 2 coats, total film 18-20 mils 5B/B Skins over liquid 425 (2% failure to concrete)

1 Starting Formulation 1626 Hexion Specialty Chemicals

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Table 2 - Spot Resistance Results

3:1 Enamel (E828 & New WB amine) VOC 1 2 24 hrs RT. (CTCH) uncovered 3 4 5 6 7 8 9 10 MEK Gas Simple Green White Vinegar Anti Freeze (Dex cool) Transmission Fluid Yellow mustard Brake Fluid Windshield Washer fluid 30% Sulfuric Acid 10% NaOH Motor Oil (10W30) 100 double rubs 89 octane 1 hr covered Total Score 45 9 8 9 9 7 6 10 6 9 10 10 8 Commercial DIY #1 <50 7 7 7 9 6 7 6 7 7 10 4 9 Commercial DIY #2 <100 7 3 9 9 6 6 6 3 7 10 7 5 Commercial DIY #3 <100 7 7 9 9 6 7 9 4 9 10 7 8 Commercial DIY #4 0* 5 6 5 7 6 7 9 8 8 10 2 7

101 86 78 92 80 * This product, Commercial DIY #4, is supplied without tint. Addition of tint would add VOCs, but the sample was tested without tints.

Results are based on a relative scale, 10 = Best = No Effect

The adhesion properties of these epoxy coatings systems (See: Table 3) was also evaluated. It is interesting to note the mode of failure in the adhesion testing of these systems. The new amine curing system exhibited higher adhesion in contrast to the commercial DIY system, but the mode of failure was also significantly different, too. With this new waterborne amine, the mode of failure was only cohesive failure of the cement to a significant extent. Using the commercial waterbased product, the failure mode was more adhesive failure at the coating interface to the cement, as well as some cohesive failure of the concrete (See: Figure 1). Table 3 - Enamel Adhesion Pull-off Results
Property Pull off Adhesion, psi % loss of adhesion to concrete Weight of concrete removed, g Commercial Enamel 500, 400 50, 40 0.30, 0.24 Starting Formula D1 3:1 Gray (EPON 828 / New WB C.A.) 755, 975 0, 0 1.13, 1.29

1 Starting Formulation 1626 Hexion Specialty Chemicals

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Figure 1 - Enamel Adhesion

Commercial Enamel

SF 1626 3:1 Enamel (EK8547 w/E828)

The key observation is that the starting formulation adhesion is much greater and the amount of concrete removed was significantly more, than that exhibited by the commercial waterbased product. During this side-by-side testing, it was noticed that Hexions starting formulations based on the new WB curing agent and DIY #2 exhibited easy water clean up. An evaluation of clear coat systems was also performed. The properties were compared to the properties of a commercially available clear versus our new formulated system was followed (See: Table 4). The clear coat system based on the new amine-curing agent exhibits excellent adhesion (See: Table 5). The mode of adhesion failures as exhibited in the previous study was similarly exhibited in this study, too (See: Figure 2). Table 4 Clear Coat Formulation Comparison
Property Mix Ratio (vol.) Induction time, min. Pot Life @ 77F, hrs. VOC, g/L % N.V. (wt./vol.) Pencil Hardness, Initial / 7 Days In use appearance Commercial DIY Clear coat 2:1 1 1.5 250 max 66% / 61% 1 3B / HB Clear 3:1 10 min 6 hrs 250max 42%/ 45% 5B / B 2:1 15 min. 4 hrs 100max 52% / 42% 3B / B Starting Formula B 2 (EPON 863 / New WB C.A.) 3:1 30 3 0 54% / 43% 5B / HB White emulsion Gelled 450 (93% failure of concrete)

White emulsion White emulsion Soft Gel Liquid

In Can Appearance @ Gelled overnight Pull-off Adhesion, 400 average psi (32% failure of concrete)

300 238 (<5% failure to (50% failure to cement) cement)

1 As calculated from MSDS 2 Starting Formulation 1622 Hexion Specialty Chemicals

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Figure 2 - Clear coat Adhesion

Starting Formulation B Commercial Clear coat Table 5 Clear Coat Adhesion Pull-off Results
Property Pull off Adhesion, psi % loss of adhesion to concrete Weight of concrete removed, g Commercial DIY Clear coat 350, 450 75, 60 0.24, 0.44 Starting Formula B 3:1 Clear (EPON 863 / New WB C.A.) 400, 500 >5, 10 0.52, 0.49 (EK 8547 w/E863)

An unexpected result was found when we evaluated the gray enamel + clear systems. When the clear enamel (Starting Formula B) was used over the commercial DIY enamel, the resulting coating system showed superior adhesion and pull-off values, when compared to the commercial clear coat companion system from the same supplier (See Table 6). Table 6 Enamel + Clear Coat Adhesion Pull-off Results
Enamel Clear Coat Adhesion Failure mode cohesive Force (psi) loss of adhesion to failure of concrete concrete 0% 100% 200 0% 0% 0% 99% 98% 80% 100% 100% 100% 1% 2% 20% 700 300 600 500 400 400 Net weight of coating + concrete removed, g 0.83 1.04 0.82 1.06 0.15 0.19 0.14

Starting Formula D 3:1 Gray (EPON 828 / New WB C.A.)

Commercial DIY Clear Coat Starting Formula B 3:1 Clear (EPON 863 / New WB C.A.)

Commercial DIY Commercial DIY Clear Coat 3:1 enamel Starting Formula B 3:1 Clear

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(EPON 863 / New WB C.A.)

5%

95%

400

0.52

Conclusion This study demonstrates that high performance and ultra-low VOC coatings for concrete can be achieved by using this newly introduced waterborne curing agent. This new technology gives paint formulators an excellent new tool to meet existing and new regulatory hurdles without any sacrifice of performance. In addition to this, this newly developed curing agent offers advantages over competitive product in terms of chemical resistance, adhesion to concrete and overall ease of use. As identified from interviews with end users, specifiers and owners, these are among the critical design criteria incorporated in this new WB curing agent for advanced coating systems. Base on this resent side-by-side comparison of this new WB curing agent for epoxy concrete coatings, we believe that this new WB curing agent established a new standard of performance for this application. The results of this comparison are summarized below. Table 7 Performance Comparison of WB Curing agents for concrete Property New WB Curing agent Competitor A Competitor B Easy Handling ++ Easy Application ++ + 0 Performance ++ Appearance + Economics == == == ACKNOWLEDGEMENTS I have been working with a good and dynamic team and I would be remise if I did not acknowledge their contributions, efforts and support C. Ash, A. Bernard, J. Elmore, P. Deudon, J. Hite, C. Medlock, V. Maksymowsk, D. Weinmann and D. Woodcock.

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Appendix I Starting formulation A1: Concrete gray primer, 4:1, low gloss
Curing Agent Component New WB curing agent2 Citric Acid Solution, 50% DI Water DrewPlus L-475 Alcolec S Disparlon L-1982 DI Water Aerosil R812 Kronos 2310 (TiO2) Optiflo H600 VF Elementis Black tint NV 7317 (20% pigment content) Zeeosphere W 410 Zeeosphere W 600 DrewPlus L-475 DI Water Epoxy Component EPON Resin 863 PnP (Propylene Glycol n-Propyl Ether) DPnB (Dipropylene Glycol n-Butyl Ether)

Formulations
Weight (lbs) 231.9 6.8 13.6 2.9 18.5 Gallons (US) 26.06 0.49 1.63 0.41 2.15

Supplier Hexion Specialty Chem. Aldrich/ Fisher Scientific Drew Chemical American Lecithin Corp. King Industries

6.5 0.77 24.3 2.92 Degussa Corp 21.4 1.17 Grind to minimum of 6 - 7 Hegman Kronos Inc. 131.6 3.99 Southern Clay Products 6.8 0.78 Elementis Specialties 2.1 0.21 3M Corp. 3M Corp Drew Chemical Final grind of 6 - 7 Hegman 24.3 1.21 92.6 4.63 3.9 0.55 32.97 275.2 862.8 80.00 Total Part A 177.4 7.7 7.7 Total Part B Grand Total 192.9 1055.7 17.92 1.05 1.02 20.00 100.00

Hexion Specialty Chem.

1
2

Starting Formulation 1620 Hexion Specialty Chemicals EPIKURE 8547-W-60

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Starting formulation B1: Concrete topcoat clear, 3:1, high gloss

Supplier Curing Agent Component New WB curing agent2 Lutensol OP-10 DI Water Epoxy Component EPON Resin 863 Hexion Specialty Chem. BASF Total Part A Hexion Specialty Chem. Total Part B Grand Total
Starting Formulation 1622 Hexion Specialty Chemicals EPIKURE 8547-W-60

Weight (lbs) 317.0 47.6 287.3 651.9 242.5 242.5 894.4

Gallons (US) 35.22 5.35 34.43 75.00 25.00 25.00 100.00

1
2

Starting formulation C1: Concrete topcoat clear, 3:1, high gloss

Supplier Curing Agent Component New WB curing agent2 Lutensol OP-10 DI Water Epoxy Component EPON Resin 828 Hexion Specialty Chem. BASF Total Part A Hexion Specialty Chem. Total Part B Grand Total
Starting Formulation 1623 Hexion Specialty Chemicals EPIKURE 8547-W-60

Weight (lbs) 287.2 72.7 2914 651.4 242.5 242.5 897.4

Gallons (US) 31.91 8.17 34.91 75.00 25.00 25.00 100.00

1
2

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Starting formulation D1: Concrete gray primer, 3:1, medium gloss

Supplier Curing Agent Component New WB curing agent2 DrewPlus L-475 Alcolec S Disparlon L-1982 DI Water Aerosil R812 Hexion Specialty Chem. Drew Chemical American Lecithin Corp. King Industries Degussa Corp 250.3 3.0 28.06 0.42 Weight (lbs) Gallons (US)

13.6 1.59 6.3 0.75 105.2 12.60 12.6 0.68 Grind to minimum of 6 - 7 Hegman 126.2 7.3 3.83 0.84

Kronos 2310 (TiO2) Optiflo H600 VF Elementis Black tint NV 7317 (20% pigment content)

Kronos Inc. Southern Clay Products Elementis Specialties

2.3 0.23 Final grind of 6 - 7 Hegman 73.6 2.3 183.2 786.2 206.6 6.3 2.5 9.9 9.9 235.2 1021.4 3.68 0.32 21.95 75.00 21.30 0.74 0.30 1.34 1.31 25.00 100.00

Zeeosphere W 410 DrewPlus L-475 DI Water Epoxy Component EPON Resin 828 Heloxy Modifier 65 Byk 346 PnP (Propylene Glycol n-Propyl Ether) DPnB (Dipropylene Glycol n-Butyl Ether)

3M Corp. Drew Chemical Total Part A Hexion Specialty Chem. Hexion Specialty Chem. BYK Chemie

Total Part B Grand Total

1 Starting Formulation 1626 Hexion Specialty Chemicals 2 EPIKURE 8547-W-60

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