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)

Seminar Objectives
Learn capability of
polyurethane adhesives
Learn about their
versatility and breadth
Learn the formulation
possibilities

Chapter 1 - Introduction

Seminar Contents - Part I

1) Slide Show Presentation
Chapter
1. Introduction
2. Types of PU adhesives
3. PU chemistry

4.
5.
6.
7.
8.

Morphology and physical properties

PU adhesive composition
Isocyanates and Polyols
Additives and other raw materials
Common formulations
Current and future development

60 minutes

2) Questions and Answers

On-line interaction

30 minutes
Chapter 1 - Introduction

Chapter 1
Introduction

Definition
PU adhesives contain a number of urethane
groups in the molecular backbone or are formed
during use
Urethane group

O
NCO
H

Many complex reactions can occur

simultaneously or sequentially

Diversity
Diversity
Versatility
Versatility
Chapter 1 - Introduction

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

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

Chapter 1 - Introduction

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 2
Types of Polyurethane
Adhesives

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

Chapter 3
Polyurethane Chemistry

10

Polyurethane Chemistry
Urethanes are generally produced from isocyanates,
represented as:
RN=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)
R N = C = O + HO - R
(Isocyanate)
(Alcohol)

Chapter 3 PU Chemistry

H O
| ||
R N C O R
(Urethane)

11

Isocyanate Polyol Reaction

Polyether or Polyester

Diisocyanate

Polyol

HO~~~~~~~ OH

OCN R NCO

O
O


~~~~O C NH R NH C O~~~~~

Polyurethane

Urethane Group
Chapter 3 PU Chemistry

12

Chapter 4
Polyurethane Adhesive
Composition

13

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

14

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

15

Chapter 5
Isocyanates and Polyols

16

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

17

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

18

Polyols
Polyether Polyol

Low temperature properties

Hydrolysis resistance
Lower cost
Easier processing
Low viscosity
Not as reactive as polyester

RR
RR
HO
R(O-CH-CH2)
(O-CH-CH2)m OH
OH
HO(CH2-CH-O)
(CH2-CH-O)n R
n

Polyether
Polyetherpolyol
polyol

Polyester Polyol
Good adhesion
High strength, modulus, and
hardness
Better resistance to
oxidation, elev. temp.
Linear to highly branched
Chapter 5 Isocyanates and Polyols

OH
OHRROO(CO-R-CO-O-R-O)
(CO-R-CO-O-R-O)nnHH
Polyester
Polyesterpolyol
polyol

19

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

20

Polyols
Important factors in selection of a polyol:
Chemical
Chemicaltype
type
MW
MW
Functionality
Functionality
Chain
Chainstructure
structure
Flexible
Molecular Weight
1000-6500
Functionality
2 to 3
Hydroxyl value (mg KOH/g)
28-160
Glass Transition Temperature -40 to 60C
NCO / OH Ratio
Lower
Chapter 5 Isocyanates and Polyols

Rigid
150-1600
3 to 8
250-1000
+60 to 40C
Higher
21

Comparison of PU Polyols

Chapter 5 Isocyanates and Polyols

22

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

23

Chapter 6
Additives and Other Raw
Materials

24

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

25

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

26

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 H20 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

27

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

28

Chapter 7
Common Formulations

29

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

30

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

31

Typical Two Component PU Formulation

Chapter 7 Common Formulations

32

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

33

Blocked One Component Adhesives

Reaction is reversible, and generally temperatures of 120-160C
are required for deblocking
OCN R NCO + 2BH

O
O
||
||
B C HN R NH C B

Blocking agents include phenols, branched alcohols,

methylethyl ketoxime and e-caprolactam

Chapter 7 Common Formulations

34

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

35

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

36

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

37

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

38

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

39

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

40

Chapter 8
Current and Future
Development

41

Recent Development Activities

) Examples of development:
9 Hybrid PU adhesives
Ethylene / vinyl acetate copolymers
Epoxy
Acrylics
9 Blocked isocyanates
9 Pressure sensitive acrylic prepolymers
9 Urethane toughened acrylate adhesives
9 Reactive hot melts
9 Pressure sensitive
9 Anaerobic and radiation curing mechanisms
9 Non-sagging without fillers
Chapter 8 Current and Future Development

42

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

43

End of Presentation for

Session I

44

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
45

Backup Slides and

Additional Material

47

Common PU Adhesive Reactions

Chapter 3 PU Chemistry

48

Common PU Adhesive Reactions

Chapter 3 PU Chemistry

49

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

Polycaprolactones

Polyether Polyols

Polyglycols

Amines

Natural and Hydroxyl Containing Oils

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

Chapter 3 PU Chemistry

50

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

51

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

52

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

53

Polyurethane Morphology

1 Flexible PUR
2- 40% rigid segments
3- 60% rigid segments
4- Rigid PUR

Chapter 3 PU Chemistry

54

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

55

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

56

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

57

Fillers
Fillers that reduce shrinkage, improve strength, reduce costs,
adjust viscosity
Barytes
Hydrated Alumina
Clays

Quartz Flour
Slate Flour
Fumed Silica

Particulate fillers increase density and hardness

CaCO3 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

Chapter 6 Additives and Other Raw Materials

58

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 Bstage development

Chapter 6 Additives and Other Raw Materials

59

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

60

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)

Zinc oxide
Certain molybdates

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

Chapter 6 Additives and Other Raw Materials

61

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

62

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

63

Polymers Sometimes Used with PU Adhesives

64

Polyurethane Metal Adhesive

65

Solvent-Free
General Purpose Reactive Adhesive

66

Solvent Based Reactive Adhesive

67

Thermoplastic PU Contact Adhesive

68