Crosslinking Technology for Latex or

Acrylic Emulsions
Katie L. Skok and Roeland J. Tuinman, PhD
Auburn Hills, Michigan
 Emulsion Polymer Isocyanate Adhesives

 An EPI consists of two components:

1. A water based emulsion polymer

 Poly Vinyl Acetate (PVAc)
 Ethylene Vinyl Acetates (EVA)
 Styrene- Butadiene (SB)
 Acrylics

2. An isocyanate crosslinker
 Polymeric MDI (PMDI)
 Emulsifiable Polymeric MDI (EPMDI)

Polyurethanes
 Emulsion Polymer Background

 PVA and EVA Dispersion Adhesives

 Nontoxic
 Low VOC
 Dispersed in water

 Common white glue Carpenters glue

Limitations
 Thermoplastic (not cured)
 Low strength at high moisture levels
 Good flow, but little penetration into
surfaces

Polyvinyl acetate homopolymer

Polyurethanes
 Emulsion Polymer Background

 SB latex
 Better resistance to water
and solvents
 Good low temp properties
 More expensive than PVA
type

 Acrylic emulsions Adhesive for carpet backing

 Bonds a variety of
substrates
 More expensive than PVA
type

Pressure Sensitive Adhesives

Polyurethanes
MDI Background

MDI
Methylene Di-Phenyl Di-
Isocyanate

Polymeric MDI
Fn=2.7

Pure MDI’s
Fn=2.0

Polyurethanes
 Emulsifiable MDI

 What is an Emulsifiable MDI?

 An isocyanate which has been
50/50 blend of water and MDI
modified by adding hydrophilic
solubolising groups to become
easily emulsified in water

 Emulsifiable Polymeric MDI

Advantages
 Does not easily separate after
mixing
 Faster reactivities achieved
 Quicker strength build up achieved
 Stronger overall physical
properties
RUBINATE® M RUBINATE 9259
Polymeric MDI Emulsifiable MDI

Polyurethanes
 Product Data

 Huntsman Product Offering

%NCO Viscosity Specific Functionalit Equivalent

(cps) Gravity @25C y Weight

RUBINATE 9236 31.0 220 1.23 2.69 135

Isocyanate
SUPRASEC 9600 31.2 400 1.23 2.70 135
Isocyanate
RUBINATE 9259 30.2 210 1.23 2.67 139
Isocyanate
RUBINATE M 31.2 190 1.23 2.70 135
Isocyanate

Recommended as Crosslinker for Emulsion Polymer Adhesives

Polyurethanes
 Emulsifiable MDI for Emulsion Polymer
Adhesives

RUBINATE 9236 Isocyanate

 Standard product for use as a crosslinker for Latex
emulsions
– Improves adhesion
– Chemical resistance
– Physical properties

 SUPRASEC 9600 Isocyanate

 Similar in performance to RUBINATE 9236
– Provides an extended open time
– Strength build maximized

Polyurethanes
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

Polyurethanes
Typical Emulsion Formulation

SB Latex 50% Solids; 6.0 pH; Anionic Surfactant 30.0%

Calcium Carbonate OmyaCarb 5 Omya 25.0%

Polyvinyl Alcohol 10% Cevol 523 Celanese 35.0%

Defoamer Surfonyl DF-210 Air Products 0.2%

Biocide Rocima BTNV2 Rohm & Haas 0.2%

Dispersant Dynol 604 Air Products 0.2%

Water 9.4%

MDI Isocyanate SUPRASEC 9600 or RUBINATE 9236 15.0%

Emulsion Polymer 85.0%

Polyurethanes
Lap Shear Adhesion

Strength Build

300

200

PSI

100 RUBINATE M
SUPRASEC 9600
RUBINATE 9236
No MDI
0
0 100 200 300 400 500
Time (min)

* Fastest adhesive strength build up *

Polyurethanes
Viscosity Profiles

Viscosity Build

1,000,000

RUBINATE M
100,000
SUPRASEC 9600
RUBINATE 9236
cps 10,000

1,000

100
0 10 20 30 40
Time (min)

* Suprasec 9600 builds viscosity at a slower rate *

Polyurethanes
 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

Polyurethanes
 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

Polyurethanes
 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

Polyurethanes
Photos of ASTM-D5751

Glue
line

Wood
Failure

Polyurethanes
ASTM D-5751

Strength Properties of Adhesive Bonds in Shear by Compression

Loading

1400

1200

1000

800
Standard
PSI

Vac/Pres
600
Boil

400

200

0
Rubinate M Rubinate 9236 Suprasec 9600 Emulsion Polymer Alone

Polyurethanes
 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 MDI’s:
 Provide better mixing
 Flexibility in reactivity rate
 Higher physical properties than
traditional MDI

Polyurethanes
 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 New Product

 Fast strength build up
 Slower viscosity build Longer open
times achieved!

Polyurethanes
Thank You!