1. Crosslinking Technology for Latex or Acrylic Emulsions Katie L. Skok and Roeland J. Tuinman, PhD Auburn Hills, Michigan

2. Emulsion Polymer Isocyanate Adhesives

An EPI consists of two components:

• A water based emulsion polymer

• • Poly Vinyl Acetate (PVAc)

• • Ethylene Vinyl Acetates (EVA)

• • Styrene- Butadiene (SB)

• • Acrylics

• An isocyanate crosslinker

• • Polymeric MDI (PMDI)

• • Emulsifiable Polymeric MDI (EPMDI)

3. Emulsion Polymer Background

PVA and EVA Dispersion Adhesives

• Nontoxic

• Low VOC

• Dispersed in water

Limitations

• Thermoplastic (not cured)

• Low strength at high moisture levels

• Good flow, but little penetration into surfaces

Polyvinyl acetate homopolymer Common white glue Carpenters glue 4. Emulsion Polymer Background

SB latex

• Better resistance to water and solvents

• Good low temp properties

• More expensive than PVA type

Acrylic emulsions

• Bonds a variety of substrates

• More expensive than PVA type

Pressure Sensitive Adhesives Adhesive for carpet backing 5. MDI Background

MDI

M ethyleneD i-Phenyl Di- I socyanate

Polymeric MDI Fn=2.7 Pure MDIs Fn=2.0 6. Emulsifiable MDI 50/50 blend of water and MDI RUBINATE M Polymeric MDI RUBINATE 9259 Emulsifiable MDI

Emulsifiable Polymeric MDI Advantages

• Does not easily separate after mixing

• Faster reactivities achieved

• Quicker strength build up achieved

• Stronger overall physical properties

What is an Emulsifiable MDI?

• An isocyanate which has been modified by adding hydrophilic solubolising groups to become easily emulsified in water

7. Product Data

Huntsman Product Offering

Recommended as Crosslinker for Emulsion Polymer Adhesives 139 2.67 1.23 210 30.2 RUBINATE 9259 Isocyanate 2.70 2.70 2.69 Functionality 135 1.23 190 31.2 RUBINATE M Isocyanate 135 1.23 400 31.2 SUPRASEC 9600 Isocyanate 135 1.23 220 31.0 RUBINATE 9236 Isocyanate Equivalent Weight Specific Gravity @25C Viscosity (cps) %NCO 8. Emulsifiable MDI for Emulsion Polymer Adhesives

RUBINATE 9236Isocyanate

• Standard product for use as a crosslinker for Latex emulsions

• • • Improves adhesion

• • • Chemical resistance

• • • Physical properties

SUPRASEC 9600Isocyanate

• Similar in performance to RUBINATE 9236

• • • Provides an extended open time

• • • Strength build maximized

9. Formulating Approaches

• Hydroxy functionalized emulsion latex

• • Number of hydroxy groups can control crosslinking

• • Latex copolymers can be varied to allow a wide range of stress-strain behaviors

• • pH of the latex will affect reactivity

• Isocyanate

• • Amount added, affects degree of crosslinking

• • • Generally between 1% and 20%

• • Type can affect reactivity and build of green strength

10. Typical Emulsion Formulation 9.4% Water 0.2% Air Products Dynol 604 Dispersant 0.2% Rohm & Haas Rocima BTNV2 Biocide 0.2% Air Products Surfonyl DF-210 Defoamer 35.0% Celanese 10% Cevol 523 Polyvinyl Alcohol 25.0% Omya OmyaCarb 5 Calcium Carbonate 30.0% 50% Solids; 6.0 pH; Anionic Surfactant SB Latex 85.0% Emulsion Polymer 15.0% SUPRASEC 9600 or RUBINATE 9236 MDI Isocyanate 11. Lap Shear Adhesion * Fastest adhesive strength build up * 12. Viscosity Profiles * Suprasec 9600 builds viscosity at a slower rate * 13. EPI Adhesive Applications

Adhesives for bonding wood to:

• Phenolic papers

• Plastics

• Metals

• Wood

• Concrete

High performance wet-use adhesives for wood bonding

• Edge to edge

• Finger joints

• Laminating

Adhesive for Doors and Windows 14. Door and Window Adhesive

Benefits of an EPI

• Improved adhesion at low and elevated temps

• Good water resistance and durability

• Faster development of adhesive strength

• Improved physical properties

Test Requirements

• ASTM D 5751

• • Adhesives used for Laminate Joints in Nonstructural Lumber Products

15. ASTM D-5751

Dry

• Specimens tested as is

Vacuum/Pressure test

• Specimens submerged under water and sealed in a vacuum at 25 inch of Hg for 30 minutes

• Followed by pressurizing the tank to 75 PSI for 30 minutes

• Samples tested wet

Boiling

• Samples are boiled for 4 hrs and then placed in an oven at 160F for 20 hours

• The 4 hour boil is repeated

• Samples tested wet

16. Photos of ASTM-D5751 Glue line Wood Failure 17. ASTM D-5751 18. Conclusions

The addition of a MDI crosslinker to an emulsion polymer:

• Increases green strength development

• Increases overall physical properties

• Is necessary for wet use applications

Emulsifiable MDIs:

• Provide better mixing

• Flexibility in reactivity rate

• Higher physical properties than traditional MDI

19. Conclusions (cont.)

Huntsman is a leader in Emulsifiable MDI technology

For EPI adhesive applications use:

• Rubinate 9236

• • Fast strength build up

• • Fast viscosity build up

• Suprasec 9600

• • Fast strength build up

• • Slower viscosity build

New Product Longer open times achieved! 20. Thank You!