1

Training Courses on Polyurethane

Adhesives
Part I: Formulation
How to Formulate Polyurethane Based Adhesives:
A Complete Overview of Key Ingredients and Latest
Formulation Techniques
Edward M. Petrie
(SpecialChem Expert Team)
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Seminar Objectives
Learn capability of
polyurethane adhesives
Learn about their
versatility and breadth
Learn the formulation
possibilities
Chapter 1 - Introduction
3
Seminar Contents - Part I
1) Slide Show Presentation
Chapter
1. Introduction
2. Types of PU adhesives
3. PU chemistry
Morphology and physical properties
4. PU adhesive composition
5. Isocyanates and Polyols
6. Additives and other raw materials
7. Common formulations
8. Current and future development
Chapter 1 - Introduction
60 minutes
30 minutes
2) Questions and Answers
On-line interaction
4
Chapter 1
Introduction
5
Definition
PU adhesives contain a number of urethane
groups in the molecular backbone or are formed
during use
Urethane group
Many complex reactions can occur
simultaneously or sequentially
O
N C O
H
Diversity
Versatility
Diversity
Versatility
Chapter 1 - Introduction
6
Why the Attraction to PU Adhesives?
Good adhesion achieved through:
Chemical bonding with water, hydroxyls on substrate surface
Physical bonding through van der Waals forces and low surface energy
Mechanical through low viscosity and diffusion into porous substrates
Specific mechanical properties achieved through molecular
composition
Toughness and other viscoelastic properties
Elasticity and modulus
Crosslinking density
Many types, methods of application, and cure speeds are
possible
Chapter 1 - Introduction
7
Advantages and Disadvantages of PU Adhesives
Advantages
Highly versatile chemistry
Flexible, tough, or rigid
Bonds a variety of plastics
Can be formulated as 1 or 2
component system
Slow to fast curing time
Good low temperature
properties
Good environmental
resistance
Good chemical, oil
resistance below 50C
Disadvantages
Moisture sensitivity during
storage and application
Only average bond strength
to metal without a primer
Precise mix ratio required
for certain products
Requires good mixing
Maximum temperature of
100-150C for specially
formulated PUs
Hydrolytic stability is a
problem for certain types
Chapter 1 - Introduction
8
Chapter 2
Types of Polyurethane
Adhesives
9
Classification of PU Adhesives and Sealants
Polyurethane adhesives vary widely in composition
and are used in many different applications and in
various market segments
Chapter 2 Types of PU Adhesives
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Chapter 3
Polyurethane Chemistry
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Polyurethane Chemistry
Urethanes are generally produced from isocyanates,
represented as:
R N = C = O
Properties revolve around the universal and rapid reaction
between the NCO group and any organic compound
containing an extractable hydrogen atom
Reaction with a hydroxyl terminated polymer (e.g., alcohol,
polyester or polyether polyol, derivatives of castor oil or
hydrocarbons)
H O
| ||
R N = C = O + HO - R R N C O R
(Isocyanate) (Alcohol) (Urethane)
Chapter 3 PU Chemistry
12
Isocyanate Polyol Reaction
Polyether or Polyester Diisocyanate
Polyol
HO~~~~~~~ OH + OCN R NCO
O O

~~~~O C NH R NH C O~~~~~
Urethane Group
Polyurethane
Chapter 3 PU Chemistry
13
Chapter 4
Polyurethane Adhesive
Composition
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Polyurethane Adhesive Composition
Isocyanate
Active Hydrogen Compound
Catalyst
Chain Extender
Additives
Drying agents
Antioxidant
UV Inhibitor
Antimicrobial
Leveling agent
Colorant
Adhesion Promoters
Fillers and Extenders
Other Polymers
Chapter 4 PU Adhesive Composition
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Manufacture of Polyurethane Adhesives
Urethane adhesive and sealants are generally made in a batch
process
Prepolymer is made in a standard mix tank
Adhesive or sealant is made in a high torque mixer
Mixer control is important for consistent viscosity
It is necessary to avoid moisture contamination
Reactions run under a nitrogen blanket or in a vacuum
Reactors are always jacketed for temperature control
Chapter 4 PU Adhesive Composition
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Chapter 5
Isocyanates and Polyols
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Isocyanates
MDI (methylene diphenyl diisocyanate)
TDI (toluene diisocyanate)
Polymeric isocyanates used for crosslinking (e.g.,
polymethylene polyphenylene isocyanate)
Prepolymers Isocyanate prereacted with some or all of the
polyol (not all of the polyol is used) very low viscosity
Chapter 5 Isocyanates and Polyols
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Isocyanates
Triphenylmethane triisocyanate (Desmodur R)
Polymethylene polyphenyl isocyanate (PAPI)
Aliphatic isocyanates - Less reactive, non-yellowing, more
resistant to UV, slightly higher thermal resistance, lower
resistance to oxidation, more expensive
HDI (hexamethylene diisocyanate)
IPDI (isophorone diisocyanate)
O = C = N - - CH2 - - N = C = O
MDI (methylene diphenyl diisocyanate)
Chapter 5 Isocyanates and Polyols
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Polyols
Polyether Polyol
Low temperature properties
Hydrolysis resistance
Lower cost
Easier processing
Low viscosity
Not as reactive as polyester
Polyester Polyol
Good adhesion
High strength, modulus, and
hardness
Better resistance to
oxidation, elev. temp.
Linear to highly branched
R R
HO (CH2-CH-O)
n
R (O-CH-CH2)
m
OH
Polyether polyol
R R
HO (CH2-CH-O)
n
R (O-CH-CH2)
m
OH
Polyether polyol
OH R O (CO-R-CO-O-R-O)
n
H
Polyester polyol
OH R O (CO-R-CO-O-R-O)
n
H
Polyester polyol
Chapter 5 Isocyanates and Polyols
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Polyols
Polytetramethylene ether glycol (PTMG)
Polycaprolactone glycol
Polybutadiene (PolyBD) glycol
Improved hydrolytic stability
Lower moisture vapor transmission
Lower tensile strength and modulus
Others
Polycarbonates
Fatty alcohols
Castor oil
Polyester amide
Chapter 5 Isocyanates and Polyols
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Polyols
Important factors in selection of a polyol:
Flexible Rigid
Molecular Weight 1000-6500 150-1600
Functionality 2 to 3 3 to 8
Hydroxyl value (mg KOH/g) 28-160 250-1000
Glass Transition Temperature -40 to 60C +60 to 40C
NCO / OH Ratio Lower Higher
Chapter 5 Isocyanates and Polyols
Chemical type
MW
Functionality
Chain structure
Chemical type
MW
Functionality
Chain structure
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Comparison of PU Polyols
Chapter 5 Isocyanates and Polyols
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Prepolymers
A prepolymer is a low molecular weight urethane
polymer that retains the ability to react further
Prepolymers are formed by partially reacting the
available isocyanate groups with a curative
Partial reaction is possible by controlling the ratios of the reactants
Called xmers
Important parameters in prepolymer design:
Mc: average MW between crosslinks
% NCO: if value is too high in one-part systems gassing can occur
NCO/OH ratio control mole % of xmer formed
Chapter 5 Isocyanates and Polyols
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Chapter 6
Additives and Other Raw
Materials
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Catalysts, Chain Extenders, Crosslinkers
Catalysts
Tertiary amines (e.g., triethanol amine)
Transition metals (e.g., dibutyl tin dilaurate, DBTDL)
Chain Extenders (diamines or diols)
Reacts with isocyanate then phase separates into domains (hard
segments)
Each extender molecule more than doubles the length of the rigid
segment
Used to produce stiffer hard segments
Used to crosslink
Crosslinkers
Low molecular weight compounds containing active hydrogen
with a minimum functionality of 3
Chapter 6 Additives and Other Raw Materials
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Other Curatives
Polythioethers
React with isocyanate
Provides some of the properties of polysulfide sealants
Amines
Aromatic amines provide rigid, hard adhesives
Aliphatic amines (e.g., polyetheramine) are extremely reactive with
isocyanates
Necessary to slow down the rate of reaction for practical use; therefore,
blocking agents are used
Blocking Agents
Reversibly react with isocyanates (phenols, methylethylketoxime,
caprolactam, malonates, etc.)
Chapter 6 Additives and Other Raw Materials
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Additives
Usually added to the polyol component
Generally does not take part in the reaction
All additives must be free of water (or foaming and poor
adhesion); solvents must have a H
2
0 and alcohol content of less
than 0.02%
Stabilizers
Antioxidant (e.g., phenolic) at a 2% level
UV stabilizer
Antimicrobial at a 0.3% level
Hydrolysis stabilizer
Adhesion promoters (e.g., organosilane)
Fillers
Drying agents at a 2-5% level
Triethyl ortho formate
Calcium sulfate
Molecular sieves Zeolite
Others
Chapter 6 Additives and Other Raw Materials
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Plasticizers, Extenders, and Solvents
Not usually required urethane is typically flexible enough
Plasticizers are used to improve elongation, reduce prepolymer
viscosity, and lower hardness
Phthalate type plasticizer commonly used
Extenders are used to primarily lower cost
Aromatic oils
Asphalts
Coal tars
Solvent containing adhesives are formulated with dry organic
solvents
Ketones, lower alkyl esters (e.g., acetates), methylene chloride and
trichloroethylene
Certain flow agents (cellulose acetate butyrate, vinyl acetate copolymers,
etc.) can be added
Chapter 6 Additives and Other Raw Materials
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Chapter 7
Common Formulations
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PU Adhesive Formulation
Reactive Polyurethane Adhesives
One-component adhesives (solvent, water, and 100% solids)
Two-component adhesives (solvent, water, and 100% solids)
Reactive hot melts
Wood binders
Non-Reactive Polyurethane Adhesives
Solvent borne adhesives
Hot melt adhesives
Water based adhesives
Chapter 7 Common Formulations
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Two Component Reactive Adhesives
Generally composed of a diisocyanate terminated prepolymer as
one component, and a polyol and polyamine crosslinking agent
and catalyst as a second component
Solventless and low solvent content adhesives
Function as an adhesive or sealant
Chapter 7 Common Formulations
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Typical Two Component PU Formulation
Chapter 7 Common Formulations
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Moisture Cured One Component Adhesives
Moisture cure
Ambient conditions, shelf life, and
foaming can be a problem
Can be applied either with or
without solvent
Chapter 7 Common Formulations
34
Blocked One Component Adhesives
Reaction is reversible, and generally temperatures of 120-160C
are required for deblocking
O O
|| ||
OCN R NCO + 2BH B C HN R NH C B
Blocking agents include phenols, branched alcohols,
methylethyl ketoxime and e-caprolactam
Chapter 7 Common Formulations
35
Other One Component PU Adhesive Types
Anaerobic
Prepared by reacting hydroxyethyl methacrylate with TDI or an NCO
terminated prepolymer; a hydroperoxide is added, and the mixture
stored in an oxygen permeable container with air
Polymerization takes place when access to oxygen is eliminated in
the joint
Solid Polyol
A solid polyol, such as pentaerythritol, is simply mixed into the
adhesive/sealant. When heated, the polyol melts and reacts with the
isocyanate
Chapter 7 Common Formulations
36
Reactive Hot Melt (HMPUR) Adhesives
Solid polyether or polyester polyol mixtures are reacted with an
excess of diisocyanate to produce a prepolymer
The prepolymer is cooled into a hot melt product that can flow at
relatively low temperatures 85-140C
Molten prepolymer has a high degree of green strength
Once applied the residual non-reacted isocyanate groups react
with moisture to form a thermosetting structure
Prepolymer contributions:
Higher NCO/OH ratio: lower melt viscosity, lower elongation, higher
tensile modulus and extended open times
Lower NCO/OH ratio: thermoplastic characteristics with improved
flexibility and toughness
Chapter 7 Common Formulations
37
Isocyanate Wood Binders, Primers, Solutions
Aromatic isocyanates (predominantly MDI) used for manufacture
of:
Oriented strand board (OSB),
Medium density fiberboard (MDF), and
Particleboard
Isocyanates solutions can be used as primers for coatings and
adhesives
Isocyanates solutions can be blended with various types of
elastomers (solvent blends) as rubber cements
SBR
Natural Rubber
Neoprene
Nitrile
Chapter 7 Common Formulations
38
Solvent Based and
Hot Melt Non-Reactive Adhesives
Thermoplastic polyurethanes such as Estane (Goodrich) and
Desmocoll (Bayer)
Solvent systems can either be applied directly (permeable
substrate), as a contact adhesive, or as a coating and then hot
pressed
Hot melt adhesives are most commonly applied as an extruded
film for laminating applications
Properties depend on formulation and selection of
diisocyanates, polyols, chain extenders, and plasticizers
Chapter 7 Common Formulations
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Water Based Adhesives
PU lattices can be prepared in various ways:
Special monomers are polymerized in an aqueous medium to produce a
thermoplastic PU
Thermoplastic PU is dissolved in solvent and emulsified in water, then the
solvent is removed
Isocyanate terminated PU prepolymer is blocked and emulsified in water
together with a crosslinking agent.
Chapter 7 Common Formulations
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Water Based Adhesives
Aqueous polyurethane dispersion usually contain:
40% thermoplastic resin (for aqueous inertness)
Aliphatic diisocyanate polymer (for light stability), and
An anionic surfactant
Can be cured at room temperature; however strength, adhesion,
and water resistance are greater when dried for several minutes
at 120-175C
Chapter 7 Common Formulations
41
Chapter 8
Current and Future
Development
42
Recent Development Activities
Examples of development:
Hybrid PU adhesives
Ethylene / vinyl acetate copolymers
Epoxy
Acrylics
Blocked isocyanates
Pressure sensitive acrylic prepolymers
Urethane toughened acrylate adhesives
Reactive hot melts
Pressure sensitive
Anaerobic and radiation curing mechanisms
Non-sagging without fillers
Chapter 8 Current and Future Development
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Reactive Epoxy Urethanes
Mixture of epoxy and
polyurethane oligomers with
pendant epoxy groups
Curing of epoxy groups unites
the urethane and non-urethane
components
Tough, durable adhesive films
Good adhesion to oily surfaces
and plastics
Chapter 8 Current and Future Development
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End of Presentation for
Session I
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Seminar Contents - Part II
Selecting and Applying Polyurethane Adhesives:
Overview of major applications and key performances to match your
end-use requirements
1. Introduction
Markets and applications
Comparison to other adhesive systems
Range of types and properties
2. Application variables
Health and Safety
3. Reaction rates
4. Types of polyurethane adhesives and their use
5. Stability in various environments
Part II: Wed May 26, 2004
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Backup Slides and
Additional Material
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Common PU Adhesive Reactions
Chapter 3 PU Chemistry
49
Common PU Adhesive Reactions
Chapter 3 PU Chemistry
50
Reaction Versatility
Isocyanates react with active hydrogen compounds in the order:
R2NH > R-NH2 > Ar-NH2 > R-OH > R2OH ~ H20 > Ar-OH > R-SH
Isocyanate coreactants of commercial significance are:
Polyester Polyols
Polyether Polyols
Amines
Polymerization and/or crosslinking will occur depending on the
amount and nature of the diisocyanates, stoichiometric amount
and type of comonomer, and conditions of curing
As with other polymers, additives are used to further modify the
systems for specific end-use properties
Polycaprolactones
Polyglycols
Natural and Hydroxyl Containing Oils
Chapter 3 PU Chemistry
51
Crosslinking Capability
Linear, thermoplastic PUs are obtained by using compounds
with two reactive groups such as diisocyanates and diols
Crosslinking occurs when:
Polyols with three or more hydroxyl groups (i.e., a functionality of 3 or
more) are reacted with an isocyanate, or when
Isocyanates with three or more Isocyanate groups are reacted with a
polyol.
There is an excess of isocyanates (linkages of allophanate and biuret).
The amount of crosslinking determines the stiffness of the
polymer, strength, and resistance to environmental factors
Chapter 3 PU Chemistry
52
Crosslinking
Polyurethanes exhibit both chemical crosslinking and physical
crosslinking
Physical and chemical crosslinking sometimes overlap
Crosslinking does not always produce the expected effect
because of disruption of the domain structure (especially at low
levels of crosslinking)
Chapter 3 PU Chemistry
53
Polyurethane Morphology
PU molecule consists of two
separate phases or
microdomains
(pseudocrosslinking)
Hard segment
polyisocyanate and low molecular
weight hydroxy compound (a short
chain polyol or a diamine chain
extender)
Crosslinks the soft segment
Soft segments
Hydroxy terminated diols
Greater flexibility and elongation,
resistance to low temperature
Lower hardness, modulus,
abrasion resistance
At elevated temperatures two
phases become one amorphous,
soft phase
Chapter 3 PU Chemistry
54
Polyurethane Morphology
1 Flexible PUR
2- 40% rigid segments
3- 60% rigid segments
4- Rigid PUR
Chapter 3 PU Chemistry
55
Polyisocyanates Provide
Varied Adhesion Properties
Isocyanates react readily with a variety of other functional
groups
Di- and polyisocyanates can undergo self-polymerization to form
three dimension resins in situ
Isocyanates are quite soluble in many organic substances, and
due to their small molecular size readily permeate insoluble
porous structures
The reaction of di- and polyisocyanates with hydroxyl bearing
polyesters and polyethers produce the strong, polar, hydrogen
bonded flexible PUs which wet substrates very well
Isocyanates provide elastomer- metal bonds with flexible to rigid
gradation in physical properties between the elastomer and
metal which provides superior fatigue life
56
Polyols and Hydrolytic Stability
Hydrolysis Resistance as a Function of Change in Stress at Break
All polyurethane elastomers: 80 shore A, immersed in water at 80C
Chapter 5 Isocyanates and Polyols
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Polyols
Properties of Adhesive Films
Based on Mixtures of Polyols
Polyol PO1 = 5% hydroxyl content
Polyol PO2 = 1.3% hydroxyl
content
A = modulus at 100% elongation
B = tensile strength
C = elongation at break
Chapter 5 Isocyanates and Polyols
58
Fillers
Fillers that reduce shrinkage, improve strength, reduce costs,
adjust viscosity
Barytes
Hydrated Alumina
Clays
Particulate fillers increase density and hardness
CaCO
3
has a catalytic effect on isocyanate reaction
Aluminum hydroxide reduces flammability
Carbon black reinforces and provides UV protection
Colloidal and microexpanded silica are thixotropic agents
Flaky fillers are used for surface properties, appearance, etc.
Fibrous fillers (organic and inorganic) reinforce PU; generally
increase rigidity and elastic modulus
Quartz Flour
Slate Flour
Fumed Silica
Chapter 6 Additives and Other Raw Materials
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Thixotropy
Thixotropic agents are used to provide non-sag properties or to
reduce penetration in absorbent substrates
Usually fumed silica or bentonite is used as an additive to
provide thixotropy
However, carbon black, fibers, and treated clays can also
increase thixotropy
Bayer has developed amine terminated prepolymers (ATEP) that
provide fast B-stage reaction for thixotropy
Generally need automated meter, mix, and dispense equipment for fast B-
stage development
Chapter 6 Additives and Other Raw Materials
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Silane Primer / Additive
Improves Moisture Resistance
Adhesion promoters can be
applied as a primer or as a
component in the adhesive
formulation
Generally silanes are used to
provide:
A chemical bridge between the
surface and organic polymer or
between organic polymers
A barrier to prevent moisture
penetration into the interface
Effective dispersion of fillers and
reduction in the apparent viscosity
of the system
Isocyanate Terminated PU, Adhesion to Al
(1. Urethane is Adiprene L-100, 2. Substrates
degreased and etched, 3. Most commonly
recommended for pot life)
Chapter 6 Additives and Other Raw Materials
61
UV Stabilizers and Antioxidants
Required with aromatic isocyanates and polyether polyols
UV absorbers and stabilizers are commonly employed when PU
is exposed to light
Carbon black
Titanium dioxide
Tinuvin P (Ciba-Giegy)
Antioxidants neutralize free radicals that are formed by the
reaction of various chemical bonds with oxygen
Iganox 1010 (Ciba-Giegy)
Hindered phenols and amines
UV stabilizers and antioxidants work synergistically, so they are
often used together
Zinc oxide
Certain molybdates
Chapter 6 Additives and Other Raw Materials
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Stabilizers Hydrolytic Stability
Improved hydrolytic stability
(most often required for
polyester urethanes)
Carbodiimide (e.g., Staboxal P
from Bayer)
Satrastab developed by SATRA
(Shoe and Allied Trades Assoc.,
Kettering, England)
Elimination or reduction of ester
groups in the polyol
Hydrolysis resistance increases in
the order of ether >
polycaprolactone > polyester
Chapter 6 Additives and Other Raw Materials
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Other Stabilizers
Fungicides (most often required for polyester urethane)
Copper-8-quinolinolate
N-(trichloromethylthio) phthalimide (e.g., Fungitrol 11 from Nuodex)
Improved heat resistance
Non-stabilized PU are not recommended for service temperatures greater
than 100C
Heat resistance can be improved through exclusion of catalyst residues
from the polymer and by tailoring the polyurethane structure
Antioxidants and hybrid with epoxy and other resins
Chapter 6 Additives and Other Raw Materials
64
Polymers Sometimes Used with PU Adhesives
65
Polyurethane Metal Adhesive
66
Solvent-Free
General Purpose Reactive Adhesive
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Solvent Based Reactive Adhesive
68
Thermoplastic PU Contact Adhesive