34

Polyurethane Adhesives
Dennis G. Lay and Paul Cranley
The Dow Chemical Company, Freeport, Texas, U.S.A.
I. INTRODUCTION
The development of polyurethane adhesives can be traced back more than 60 years to the
pioneering eorts of Otto Bayer and co-workers. Bayer extended the chemistry of poly-
urethanes initiated in 1937 [1] into the realm of adhesives about 1940 [2] by combining
polyester polyols with di- and polyisocyanates. He found that these products made excel-
lent adhesives for bonding elastomers to bers and metals. Early commercial applications
included life rafts, vests, airplanes, tires, and tanks [3]. These early developments were
soon eclipsed by a multitude of new applications, new technologies, and patents at an
exponential rate.
The uses of polyurethane adhesives have expanded to include bonding of numerous
substrates, such as glass, wood, plastics, and ceramics. Urethane prepolymers were rst
used in the early 1950s [4] to bond leather, wood, fabric, and rubber composites. A few
years [5] later one of the rst two-component urethane adhesives was disclosed for use as
a metal-to-metal adhesive. In 1957 [6] the rst thermoplastic polyurethane used as a
hot-melt adhesive (adhesive strips) was patented for the use of bonding sheet metal
containers. This technology was based on linear, hydroxy-terminated polyesters and
diisocyanates. Additional thermoplastic polyurethane adhesives began appearing in the
19581959 period [7,8]. During this period the rst metal-to-plastic urethane adhesives
were developed [9]. Waterborne polyurethanes were also being developed, with a
polyurethane latex claimed to be useful as an adhesive disclosed in 1961 by du Pont
[10]. A commercial urethane latex was available by 1963 (Wyandotte Chemicals
Corporation) [11]. The adhesive properties of urethane latexes were explored further by
W.R. Grace in 1965 [12]. In the early 1960s, B.F. Goodrich developed thermoplastic
polyester polyurethanes that could be used to bond leather and vinyl [13]. In 1968
Goodyear introduced the rst structural adhesive for berglass reinforced plastic (FRP),
used for truck hoods [14].
Polyurethane pressure-sensitive adhesives began appearing in the early 1970s [15].
By 1978 advanced two-component automotive structural adhesives (Goodyear) were com-
mercially available. Waterborne polyurethane adhesives received additional attention
during this period [16]. In 1984, Bostik developed reactive hot-melt adhesives [17].
Polyurethane adhesives are sold into an ever-widening array of markets and products,
where they are known for their excellent adhesion, exibility, low-temperature
Copyright 2003 by Taylor & Francis Group, LLC
performance, high cohesive strength, and cure speeds that can readily be tailored to the
manufacturers demands [18].
Urethanes make good adhesives for a number of reasons: (1) they eectively wet the
surface of most substrates (the energy level of very low energy surfaces such as polyethy-
lene or polypropylene must be raised before good wetting occurs) [19], (2) they readily
form hydrogen bonds to the substrate, (3) their small molecular size allows them to
permeate porous substrates, and (4) they form covalent bonds with substrates that have
active hydrogens. Figure 1 shows the typical mechanism for a urethane adhesive bonding
covalently to a polar surface.
Polyurethane adhesive consumption has been estimated at 217 million pounds (1991)
having a value of approximately $301 million (see Fig. 2). Applications contributing to this
volume are shown in Table 1. It is interesting to note that while the packaging market is
the fourth-largest market in terms of pounds of urethane adhesives sold, it is substantially
larger than the forest products market and the foundry core binder market in terms of
Figure 2 Polyurethane adhesive consumption, 1991.
Figure 1 Typical mechanism for a urethane adhesive bonding covalently to a polar surface.
Copyright 2003 by Taylor & Francis Group, LLC
dollars. Overall, the polyurethane adhesives market grew at an annual rate of approxi-
mately 3% from 1986 to 1991. Specic market segments such as automotive and recrea-
tional vehicles easily surpassed the gross national product (GNP) growth rate. In the next
few years a number of specic market segments are expected to grow at about 5% per
year. These would include vehicle assembly (automotive and recreational vehicles), elec-
tronics, furniture, and curtain wall manufacture.
II. APPLICATIONS OVERVIEW
The textile market has traditionally been the largest consumer of polyurethane adhesives.
There are a number of high-volume applications, including textile lamination, integral
carpet manufacture, and rebonded foam. Textile lamination occurs through either a solu-
tion coating process or ame bonding. Flame bonding textile lamination is accomplished
by melting a polyurethane foam by ame and then nipping the foam between two textile
rolls while it is still tacky. Integral carpet manufacture describes carpeting that is manu-
factured by attaching either nylon, wool, or polypropylene tufts that are woven through a
polypropylene scrim with a urethane adhesive to a polyurethane foam cushion in a con-
tinuous process. Rebonded foam is made using scrap polyurethane foam bonded together
with a urethane prepolymer and is used primarily as carpet underlay. Durability, exibil-
ity, and fast curing speeds are all critical parameters for these applications.
Foundry core binders are isocyanate-cured alkyd or phenolic adhesives used as
binders for sand used to produce foundry sand molds. These sand molds are used to
cast iron and steel parts. A fast, economical cure of the sand mold is required under
ambient conditions.
Packaging adhesives are adhesives used to laminate lm to lm, lm to foil, and lm
to paper in a variety of packaging constructions. A broad variety of products are sold to
this market, with solvent-based, high solids, 100% solids, and waterborne adhesives all
being used. Polyurethane adhesives are considered one of the high-performance products
oered to this industry because of their excellence in adhesive properties, heat resistance,
chemical resistance, and fast curing properties. Polyurethane adhesives can also be
designed to meet U.S. Food and Drug Administration approval, a requirement for food
packaging applications.
Table 1 Sales Distribution for Polyurethane Adhesives, 1991
Volume Sales
Market segment (lb 10
6
) (10
6
)
Textiles 82.7 $79.6
Foundry core binders 66.0 62.5
Forest products 30.7 22.6
Packaging 25.0 79.7
Automotive
a
6.2 21.4
Footwear 1.6 13.2
Furniture 3.8 15.4
Recreational vehicles 1.6 5.0
Other 0.35 1.8
a
Does not include windshield sealant volumes.
Copyright 2003 by Taylor & Francis Group, LLC
Solvent-borne adhesives represent the majority of the volume in the packaging
market, with both one- and two-component systems being used. Waterborne polyurethane
adhesives are a much smaller segment that has been driven by environmental considera-
tions. Growth has slowed in recent years because of generally inferior performance com-
pared to solvent-based adhesives and because most of the major converters have already
made capital investments in solvent recovery systems.
Isocyanates are used in the forest products industry to adhesively bond wood chips,
which are then pressed to form particleboard and oriented strandboard. Urethanes are
also used to ll knotholes and surface defects in nished plywood boards (plywood
patch). These lled systems must cure rapidly and be sanded easily.
The transportation market has used polyurethane adhesives for such diverse appli-
cations as bonding FRP and sheet molding composite (SMC) panels in truck and car
applications, polycarbonate headlamp assemblies, door panels, and weatherstrip ocking.
The construction market for polyurethane adhesives consists of a variety of applica-
tions, such as laminating thermal sandwich panels, bonding gypsum board to wood ceiling
joists is modular and mobile homes, and gluing plywood oors. Early green strength, low
shrinkage, and high bond strength are critical properties.
The furniture industry uses polyurethane adhesives to bond veneers of various com-
position to boardstock and metal substrates. Both waterborne and solvent-based adhe-
sives are used.
Footwear is a sizable niche for polyurethane adhesives that are used to attach the
soles. Polyurethane adhesives compete primarily with neoprene-based adhesives and have
replaced much of the neoprene volume due to improved performance. However, the over-
all market has declined as U.S. manufacturers have moved production overseas.
III. BASIC URETHANE CHEMISTRY
Isocyanates react with active hydrogens as depicted in Fig. 3. This addition reaction occurs
with the active hydrogen adding to the nitrogen atom and the electron-rich nucleophile
(Lewis base) reacting with the carbonyl group. Generally, the stronger the base, the more
readily it reacts with the isocyanate. Table 2 shows typical reaction rates of some active
hydrogen-containing compounds.
As expected, the aliphatic amines and aromatic amines (the strongest bases in the
table) react the fastest. The urethanes industry has taken advantage of this reactivity in
two-component commercial processes, demanding fast cure by using specially designed
metering equipment and spray heads.
Alcohols and water react readily at room temperature. Most urethane adhesives
depend on the NCO group reacting with either water or alcohols. Primary OH groups
are two to three times as fast as sterically hindered secondary OH groups under equivalent
conditions. The reaction rates shown in Table 2 reect uncatalyzed reaction rates and
should be used as an indication of relative reaction rates. Actual rates are dependent on
Figure 3 Reaction of isocyanate with active hydrogen.
Copyright 2003 by Taylor & Francis Group, LLC
solvent, temperature, and the presence of catalysts. Catalysts can signicantly accelerate
these reactions and can in some cases alter the order of reactivity [20].
A. Branching Reactions
There are a number of complex reactions that can occur besides the desired reaction of the
polyol hydroxyl group with the isocyanate group to form a urethane, as shown in Fig. 4.
Isocyanates can continue to react with undesirable consequences under conditions of high
heat or strong bases. Basic impurities and excess heat catalyze branching reactions, leading
to variations in prepolymer viscosity, gelation, and exotherms. Most basic impurities arise
from the polyol, since polyols are typically produced under basic condition. As such, the
net acidity of the overall system (contribution of acidic or basic components from the
reactants) plays a critical role in determining the nal viscosity achieved [21,22].
The presence of water will lead to the formation of ureas and evolve CO
2
as shown in
Fig. 5. This mechanism is thought to proceed through the formation of an unstable
intermediate, carbamic acid, which then decomposes to give CO
2
and an aromatic
amine. The amine will then react further with another isocyanate to give a urea linkage.
All common moisture-cured urethanes give o CO
2
upon curing, which can pose problems
Table 2 Typical Reaction Rates for Selected Hydrogen-Containing Compounds
Active hydrogen compound Typical structure
Relative
a
reaction rate
Aliphatic amine R NH
2
100,000
Secondary aliphatic amine R
2
NH 20,00050,000
Primary aromatic amine Ar NH
2
200300
Primary hydroxyl R CH
2
OH 100
Water H O H 100
Carboxylic acid R CO
2
H 40
Secondary hydroxyl R
2
CH OH 30
Urea proton R NH CO NH R 15
Tertiary hydroxyl R
3
C OH 0.5
Urethane proton R NH CO OR 0.3
Amide R CO NH
2
0.1
a
Uncatalyzed reaction rate, 80

C [1].
Figure 4 Reaction of polyol hydroxyl group with isocyanate group to form a urethane.
Copyright 2003 by Taylor & Francis Group, LLC
if not properly controlled. Urea groups are known to cause high prepolymer viscosity
because of increased hydrogen bonding and because of their ability to react further with
excess isocyanate groups to form a biuret, as shown in Fig. 6.
At room temperature the biuret reaction proceeds very slowly; however, elevated
temperatures and the presence of trace amounts of basicity will catalyze the biuret reaction
as well as other branching reactions. These would include the formation of allophanate
groups, as shown in Fig. 7 (due to the reaction of urethane groups with excess isocyanate
groups), or trimerization of the terminal NCO group (to form an isocyanurate), as shown
in Fig. 8. Biurets and allophanates are not as stable thermally or hydrolytically as branch
points achieved through multifunctional polyols and isocyanates. The allophanates shown
in Fig. 7 can continue to react with excess isocyanates to form isocyanurates (as shown in
Fig. 8), a trimerization reaction that will liberate considerable heat. In most cases the
desired reaction product is the simple unbranched urethane or a urea formed by direct
reaction of an isocyanate with an amine. Ureas are an important class because they
typically have better heat resistance, higher strength, and better adhesion. By controlling
the reaction temperature (typically less than 80

C) and stoichiometry, and using a weakly

Figure 6 Reaction of urea with isocyanate.
Figure 5 Reaction of isocyanate with water.
Copyright 2003 by Taylor & Francis Group, LLC
basic catalyst (or none at all), the reaction will stop at the urethane or urea product.
Increasing the functionality of the polyol or the isocyanate will achieve branching or
cross-linking in a more controlled fashion.
B. Catalysts
As noted previously, strong or weak bases that are sometimes present in the polyols will
catalyze the urethane reaction. The eect of catalysts on the isocyanate reaction is well
documented. Indeed, the rst reported examples occur in the literature well before
urethanes became a commercially signicant class of compounds. The rst use of a
catalyst with an isocyanate was reported by Leuckart in 1885 [23]. Other early reports
Figure 8 Reaction of allophanate with isocyanate.
Figure 7 Reaction of urethane with isocyanate.
Copyright 2003 by Taylor & Francis Group, LLC
were from French and Wirtel (1926), who used triethylamine to catalyze the reaction of
phenols with 1-naphthylisocyanate [24]. Baker and Holdsworth (1947) detailed the
mechanism of the urethane reaction [25].
Commercial catalysts consists of two main classes: organometallics and tertiary
amines. Both classes have features in common in that the catalytic activity can be
described as a combination of electronic and steric eects. Electronic eects arise as the
result of the molecules ability to donate or accept electrons. For example, in the tertiary
amines, the stronger the Lewis base, generally the stronger the polyurethane catalyst.
Empty electronic orbitals in transition metals allow reactants to coordinate to the metal
center, activating bonds and placing the reactants in close proximity to one another.
Steric eects arise from structural interactions between substituents on the catalyst
and the reactants that will inuence their interaction. The importance of steric eects can
be seen by comparing the activity for triethylenediamine to that of triethylamine. The
structure of triethylenediamine (see Fig. 9) forces the nitrogens to direct their lone electron
pairs outward in a less shielded position than is true of triethylamine. This results in a rate
constant for triethylenediamine that is four times that of triethylamine at 23

C [1].
Organometallic complexes of Sn, Bi, Hg, Zn, Fe, and Co are all potent urethane
catalysts, with Sn carboxylates being the most common. Hg catalysts have long induction
periods that allow long open times. Hg catalysts also promote the isocyanatehydroxyl
reaction much more strongly than the isocyanatewater reaction. This allows their use in
casting applications where pot life and bubble-free parts are critical. Bismuth catalysts are
replacing mercury salts in numerous applications as the mercury complexes have come
under environmental pressure.
Catalysts will not only accelerate reaction rates but may also change the order of
reactivity. Table 3 illustrates this behavior. These data indicate that amines do not aect
the relative reactivities of dierent isocyanates and show that Zn, Fe, and Co complexes
actually raise the reactivity of aliphatic isocyanates above aromatic isocyanates.
IV. URETHANE POLYMER MORPHOLOGY
One of the advantages that a formulator has using a polyurethane adhesive is the ability to
tailor the adhesive properties to match the substrate. Flexible substrates such as rubber or
plastic are obvious matches for polyurethane adhesives because a tough elastomeric pro-
duct can easily be produced. Polyurethanes derive much of their toughness from their
morphology.
Polyurethanes are made up of long polyol chains that are tied together by shorter
hard segments formed by the diisocyanate and chain extenders if present. This is depicted
schematically in Fig. 10. The polyol chains (typically referred to as soft segments) impart
Figure 9 Structure of (a) triethylenediamine and (b) triethylamine.
Copyright 2003 by Taylor & Francis Group, LLC
low-temperature exibility and room-temperature elastomeric properties. Typically, the
lower-molecular-weight polyols give the best adhesive properties, with most adhesives
being based on products of molecular weight less than 2000. Generally, the higher the
soft segment concentration, the lower will be modulus, tensile strength, hardness, and tear
strength, while elongation will increase. Varying degrees of chemical resistance and heat
resistance can be designed by proper choice of the polyol.
Short-chain diols or diamines are typically used as chain extenders. These molecules
allow several diisocyanate molecules to link forming longer-segment hard chains with
higher glass transition temperatures. The longer-segment hard chains will aggregate
together because of similarities in polarity and hydrogen bonding to form a pseudo-
cross-linked network structure. These hard domains aect modulus, hardness, and tear
Figure 10 Polyol-chain structure of polyurethane.
Table 3 Gelation Times (min) at 70

C
Catalyst TDI
Isocyanate
m-xylene
diisocyanate
Hexamethylene
diisocyanate
None >240 >240 >240
Triethylamine 120 >240 >240
Triethylenediamine 4 80 >240
Stannous octoate 4 3 4
Dibutyltin di(ethylhexoate) 6 3 3
Bismuth nitrate 1 0.5 0.5
Zinc naphthenate 60 6 10
Ferric chloride 6 0.5 0.5
Ferric 2-ethylhexoate 16 5 4
Cobalt 2-ethylhexoate 12 4 4
TDI, toluene diisocyanate.
Source: Ref. 20.
Copyright 2003 by Taylor & Francis Group, LLC
strength and also serve to increase resistance to compression and extension. The hard
segments will yield under high shear forces or temperature and in fact determine the
upper use temperature of the product. Once the temperature or shear stress is reduced,
the domains will re-form.
The presence of both hard segment and soft segment domains for polyurethanes
gives rise to several glass transition temperatures, one below 30

C which is usually
associated with the soft segment, transitions in the range 80 to 150

C, and transitions
above 150

C. Transitions in the range 80 to 150

C are associated with the breakup of

urethane hydrogen bonds in either the soft segment or the hard segment. Transitions
higher than 150

C are associated with the breakdown of hard segment crystallites or

aggregates. Linear polyurethane segmented prepolymers can act as thermoplastic adhe-
sives which are heat activated. A typical use for this type of product is in the footwear
industry.
By proper choice of either the isocyanate or the polyol, actual chemical cross-links
can be introduced in either the hard or soft segments that may be benecial to some
properties. The eectiveness of these cross-links is oset by a disruption of the hydrogen
bonding between polymer chains. Highly cross-linked polyurethanes are essentially amor-
phous in character exhibiting high modulus, hardness, and few elastomeric properties.
Many adhesives fall into this category.
V. PREPOLYMER FORMATION
Most urethane adhesives are based on urethane prepolymers. A prepolymer is made
by reacting an excess of diisocyanate with a polyol to yield an isocyanate-terminated
urethane as shown in Fig. 11. Prepolymers may have excess isocyanate present (quasi-
prepolymers) or they may be made in a 2:1 stoichiometric ratio to minimize the amount of
free isocyanate monomer present. Most moisture-cured prepolymers are based on 2:1 stoi-
chiometric ratios. Two-component adhesives generally are based on quasi-prepolymers,
which use the excess isocyanate to react with either chain extenders present in the other
component or with the substrate surface.
Prepolymers are isocyanates and react like isocyanates, with several important dif-
ferences. Prepolymers typically are much higher in molecular weight, are higher in visc-
osity, are lower in isocyanate content by weight percent, and have lower vapor pressures.
Prepolymers are important to adhesives for a number of reasons. The desired polymeric
structure of the adhesive can be built into the prepolymer, giving a more consistent
Figure 11 Reaction of isocyanate with polyol.
Copyright 2003 by Taylor & Francis Group, LLC
structure with more reproducible physicals. In addition, since part of the reaction has been
completed, reduced exotherms and reduced shrinkage are normally present. For two-
component systems, better mixing of components usually occurs, since the viscosity of
the two components more closely match. In addition, the ratios of the two components
match more closely. Side reactions such as allophanate, biuret, and trimer are lessened.
Finally, prepolymers typically react more slowly than does the original diisocyanate,
allowing longer pot lives.
VI. ADHESIVE RAW MATERIALS
Polyols for adhesive applications can be generally broken down into three main categories:
(1) polyether polyols, (2) polyester polyols, and (3) and polyols based on polybutadiene.
Polyether polyols are the most widely used polyols in urethane adhesives because of their
combination of performance and economics. They are typically made from the ring-
opening polymerization of ethylene, propylene, and butylene oxides, with active proton
initiators in the presence of a strong base as shown in Fig. 12.
Polyether polyols are available in a variety of functionalities, molecular weights,
and hydrophobicity, depending on the initiator, the amount of oxide fed, and the type
of oxide. Capped products are commercially available as well as mixed-oxide
feed polyols, as shown in Fig. 13. Polyether polyols typically have glass transitions
in the 60

C range, reecting the ease of rotation about the backbone and little chain
interaction. As one would expect from such low glass transition temperatures, they
impart very good low-temperature performance. The polyether backbone is resistant to
alkaline hydrolysis, which makes them useful for adhesives used on alkaline substrates
such as concrete. They are typically very low in viscosity and exhibit excellent substrate
wetting. In addition, their low cost and ready availability from a number of suppliers
add to their attractiveness.
The more commonly used polyether polyols range in molecular weight from 500 to
2000 for diols and 250 to 3000 for triols. Lower-molecular-weight, higher-functionality
polyols are traditionally used in rigid-foam applications but have also been used as
cross-linkers for two-component, fast-curing urethane adhesives. Polytetramethylene gly-
cols (PTMOs; see Fig. 14) can be considered a subset of polyether polyols. They oer
Figure 12 Ring-opening polymerization to form polyether polyols.
Copyright 2003 by Taylor & Francis Group, LLC
improved physical properties compared to polyethers based on ethylene oxide, propylene
oxide, or butylene oxide, combining high tensile strength (due to stress crystallization)
with excellent tear resistance. They are also noted for their excellent resistance to hydro-
lysis. They are typically priced at a premium to other polyols.
Polyester polyols are used widely in urethane adhesives because of their excellent
adhesive and cohesive properties. Compared to polyether-based polyols, polyester-based
polyol adhesives have higher tensile strengths and improved heat resistance. These benets
come at the sacrice of hydrolytic resistance, low-temperature performance, and chemical
resistance. One of the more important application areas for these products is in the
solvent-borne thermoplastic adhesives used in shoe sole binding. These products are typi-
cally made from adipic acid and various glycols (see Fig. 15).
Some glycerine or trimethylolpropane may be used to introduce branching structures
within the polyester backbone. Phthalic anhydride may also be used to increase hardness
and water resistance. Inexpensive terephthalic acid-based polyesters from recycled poly-
ethyleneterephthalate (PET) resins have more recently become popular.
Figure 13 Various commercially available capped products and mixed-oxide feed polyols.
BO, butylene oxide; EO, ethylene oxide; PO, propylene oxide.
Figure 15 Reaction of diol with diacid to form polyester polyol.
Figure 14 Structure of polytetramethylene oxide.
Copyright 2003 by Taylor & Francis Group, LLC
Polycaprolactones (see Fig. 16), another type of polyester polyol, oer improve-
ments in hydrolysis resistance and in tensile strength (can stress crystallize) over adipic
acid-based polyester polyols. They are typically higher in viscosity and higher in cost than
polyether polyols of comparable molecular weight. When moisture resistance is critical,
urethane adhesives incorporating polybutadiene polyols are used. These products are
hydroxy-terminated, liquid polybutadiene resins. The hydrocarbon backbone greatly
decreases water absorption, imparting excellent hydrolytic stability. Polybutadiene
compounds also have exceptional low-temperature properties, with glass transition tem-
peratures being reported below 70

C [26]. These products are priced at a 40 to 50%

premium over comparable polyether polyols. The structure of polybutadiene polyols is
shown in Fig. 17.
A. Isocyanates for Adhesive Applications
Toluene diisocyanate (TDI) is a colorless, volatile, low-viscosity liquid commonly used in
the adhesives area to manufacture low-viscosity prepolymers for exible substrates. The
structure of TDI is shown in Fig. 18. TDI is typically supplied as an 80:20 mixture of the
2,4 and 2,6 isomers, respectively, with two grades of acidity available. Type I TDI is low in
acidity (10 to 40 ppm); type II TDI is higher (80 to 120 ppm). Type II TDI is generally used
for prepolymer applications because the additional acidity is available to neutralize trace
bases found in polyether polyols. These trace bases can cause branching reactions during
prepolymer cooks, causing high viscosities and even gelations if not properly controlled
(see Section V). The extra acidity present also serves to stabilize the prepolymer, extending
the shelf stability. In addition, since TDI is predominately the 2,4 isomer, a reactivity
dierence is noted for the isocyanate groups. Since the less hindered site reacts rst, the
sterically hindered site is left when prepolymers are formed, leading to prepolymers that
are more shelf stable. TDI prepolymers are used in adhesives for the textile and food
packaging laminates industry, where a t is found for their low viscosity and low cost.
The volatility of TDI and additional handling precautions that must be taken when using
TDI has limited its growth in adhesive applications.
Methylene diphenyl disiocyanate (MDI) is used where high tensile strength,
toughness, and heat resistance are required. MDI is less volatile than TDI, making it
Figure 17 Structure of polybutadiene polyol.
Figure 16 Structure of polycaprolactone diol.
Copyright 2003 by Taylor & Francis Group, LLC
less of an inhalation hazard. The acidity levels in MDI are very low, typically on the order
of 0 to 10 ppm, so the trace base levels in the polyols are much more critical in prepolymer
production than with TDI. The structure of MDI is shown in Fig. 19. There are several
commercial suppliers of MDI that typically supply grades with 98% or better 4,4
0
isomer.
MDI is a solid at room temperature (melting point 38

C, 100

F), requiring handling

procedures dierent from those for TDI. MDI should be stored as a liquid at 115

F or
frozen as a solid at (20

F) to minimize dimer growth rate. MDI reacts faster than TDI,

and because the NCO groups in MDI are equivalent, they have the same reactivity, a
contrast to TDI. MDI is used in packaging adhesives, structural adhesives, shoe sole
adhesives, and construction adhesives.
Several MDI products have been introduced that address the inconvenience
of handling a solid. They are seeing increased usage in the adhesives industry and are
expected to experience a higher growth rate. Most MDI producers oer a uretonimine-
modied form of MDI that is a liquid at room temperature. The uretonimine structure
is shown in Fig. 20. In addition, several producers have introduced MDIs containing
elevated levels of the 2,4
0
isomer, as shown in Fig. 21. At approximately the 35%, 2,4
0
isomer level, the product becomes a liquid at room temperature, greatly increasing the
handling ease. A number of advantages are seen: slower reactivity, longer pot life, lower-
viscosity prepolymers, prepolymers with lower residual monomeric MDI, and improved
shelf stability.
Polymeric MDIs are made during the manufacturing of monomeric MDI. These
products result as higher-molecular-weight oligomers of aniline and formaldehyde
get phosgenated. A typical structure for these products is shown in Fig. 22. These oligo-
mers average 2.3 to 3.1 in functionality and contain 30 to 32% NCO. Much of the
hydrolyzable chlorides and color bodies produced in the manufacturing process of MDI
is left behind in these products. The acidity levels can be 10 to 50 times the level found in
pure MDI, and the products are dark brown in color. The higher acidity level decreases
reactivity; however, this decrease is oset somewhat by the higher functionality.
Polymeric MDIs are typically lower in cost than pure MDI and because of the
increased asymmetry have a lower freeze point (liquids at room temperature). They are
less prone to dimerization, and as a consequence are more storage stable than are pure
MDI and derivatives. Polymeric MDIs are used whenever the color of the nished
Figure 18 Structure of the 2,4 and 2,6 isomers of toluene diisocyanate.
Figure 19 Structure of methylene diphenyl diisocyanate.
Copyright 2003 by Taylor & Francis Group, LLC
adhesive is not a concern. They are generally not used for prepolymers because high-
viscosity branched structures typically result. They are widely used as adhesives in the
foundry core binder area, in oriented strandboard or particleboard, and between rubber
products and fabric or cord. It is interesting to note that the polymeric isocyanates used
commercially today are structurally very similar to the Desmodur R (trademark, Bayer)
products used over 50 years ago [2].
Aliphatic isocyanates are used whenever resistance to ultraviolet light is a critical
concern. Examples of aliphatic isocyanates are hexamethylene diisocyanate, hydrogenated
MDI, isophorone diisocyanate, and tetramethylxylene diisocyanate. Structures for these
molecules are shown in Fig. 23. The aliphatic isocyanates are usually more expensive
than aromatic isocyanates and nd limited use in adhesive applications. Resistance
to ultraviolet light is usually not a critical concern in adhesives because the substrate
shields the adhesive from sunlight.
Blocked isocyanates are also used in urethane adhesives. Blocking or masking
of the isocyanates refers to reacting the isocyanate groups with a material that will prevent
the isocyanate from reacting with active hydrogen-containing species at room temperature
but will allow that reaction to occur at elevated temperatures. Blocked isocyanates are
easily prepared and their chemistry has been developed extensively since their inception
by Bayer and co-workers during the early 1940s [2729]. As an example, the preparation of
a methylethylketoxime blocked isocyanate is shown in Fig. 24.
Blocked isocyanates oer a number of advantages to unblocked isocyanates.
The traditional concern for moisture sensitivity can be addressed by blocking the
isocyanate. Heat activation is then required, but most commercial adhesive applications
can meet this requirement. Water-based dispersions and dispersions of the isocyanate
in the polyol or other reactive media become possible using blocked isocyanates. There
are a number of blocked isocyanates commercially available that could be used in adhesive
Figure 22 Structure of polymeric MDI.
Figure 20 Structure of uretonimine.
Figure 21 Structure of the 2,4
0
isomer of MDI.
Copyright 2003 by Taylor & Francis Group, LLC
applications. Miles (Bayer) produces a series of aromatic and aliphatic blocked
isocyanates marketed for primers, epoxy exibilizers, wire coatings, and automotive top-
coat applications. Blocked isocyanates are widely patented for fabric laminating adhesives
[30], fabric coating adhesives [3134], and tire cord adhesives [3540].
B. Toxicology
Polyether polyols are generally considered to be low in toxicity with respect to eye and skin
irritation; however, amine-initiated polyether polyols have been found to be more irritat-
ing to the skin and eyes. The manufacturers material safety data sheet (MSDS) should
always be consulted before use. Oral toxicity is generally a secondary concern in an
industrial environment. The vapor pressure of polyols is generally negligible; thus vapor
inhalation is not usually a concern [41]. Low-molecular-weight glycols (chain extenders)
are considered more problematical than polyether polyols. While generally the vapor
pressure of these products is low, there are processes that could potentially result in
vapor concentrations close to the exposure limits [41]. The exposure guidelines for chain
extenders may be written to dierentiate between aerosols and vapors. For more specic
handling information the manufacturer should be consulted.
Figure 24 Preparation of a methylethylketoxime blocked isocyanate.
Figure 23 Structure of various aliphatic isocyanates.
Copyright 2003 by Taylor & Francis Group, LLC
The toxicology of isocyanates is a primary concern when developing or using poly-
urethane adhesives. Respiratory eects are the primary toxicological manifestation of
repeated overexposure to diisocyanates [4246]. In addition, most of the monomeric iso-
cyanates are eye and skin irritants. Precautions should be taken in the workplace to
prevent exposure. The risk of overexposure is primarily (but not limited to) allergic sensi-
tization with asthma-type symptoms. Manufacturers guidelines (MSDS) should be con-
sulted for the most current information and legal requirements.
C. Fillers and Additives
Fillers are used in adhesives to improve physical properties, to control rheology, and to
lower cost. The most common polyurethane llers are calcium carbonate, talc, silica, clay,
and carbon black. A more rigorous treatment of this subject can be found in Katz and
Milewski [47]. Fumed silicas and carbon blacks are used primarily as thixotropes in
application areas that require a nonsagging bead. Calcium carbonates, clays, and talcs
are used to improve the economics of an adhesive formulation. A major concern using
llers with urethane prepolymers is the moisture content associated with the llers. Fillers
typically must be dried prior to use with urethane prepolymers or isocyanates.
Hygroscopic llers should be avoided, as moisture introduced by the ller can lead to
poor shelf stability of the nished product.
Pigments are sometimes used in polyurethane adhesive systems, but since most
adhesives are generally hidden from view, pigments do not play major roles. Pigments
may be used to color the adhesive to match the substrate. Pigments are more typically used
to color one side of a two-component system to help the user distinguish between the
isocyanate and the polyol. They are also sometimes used as an aid to judge mix ratios.
Carbon black and titanium dioxide are two commonly used pigments.
Plasticizers can also be used in polyurethane adhesives to lower viscosity, improve
ller loadings, improve low-temperature performance, and plasticize the polyurethane
adhesive. Phthalate esters, benzoate esters, phosphates, and aromatic oils are common
examples [48]. Plasticizers should be used sparingly, as adhesion will generally decrease as
levels increase.
VII. SURFACE PREPARATION AND PRIMERS
Proper surface preparation is the key to obtaining good adhesive bonds having a predict-
able service life. Substrate surfaces may have dirt, grease, mold-release agents, processing
additives, plasticizers, protective oils, oxide scales, and other contaminants that will form
a weak boundary layer. When the adhesive fails it is usually through this region, giving a
low-strength bond. Some form of surface treatment is necessary to obtain optimum bond
strength. The primary goal of surface treatment is to remove any weak surface boundary
layer on the substrate [49]. A large number of surface treatments have been developed,
with many targeted toward specic substrates. These would include mechanical abrasion,
etching, solvent cleaning, detergent washing, ame treatments, chemical treatments,
and corona discharges [19,5055].
Primers are also used in conjunction with a surface treatment either to improve
adhesive performance or to increase production exibility in a bonding operation.
Isocyanates have been used for over 50 years as primers on substrates such as rubber,
Copyright 2003 by Taylor & Francis Group, LLC
plastic, bers, and wood [56]. Isocyanates will react with polar groups on the surface and
promote bonding.
Silane coupling agents are commonly used as primers for glass, ber composites,
mineral-lled plastics, and cementacious surfaces. The silane coupling agents have
been found to be especially eective with glass substrates. One end of the coupling
agent is an alkoxysilane that condenses with the silanol groups on the glass
surface. The other end of the coupling agent is an amino, mercapto, or epoxy
functionality that will react with the isocyanate group in the adhesive. Epoxy silanes
have also been used as additives to adhesives to improve water resistance [57]. Other
organometallic primers are based on organotitanates, organozirconates, and some
chromium complexes [49].
VIII. COMMON ADHESIVE TYPES
A. One-Component Adhesives
The oldest types of one-component polyurethane adhesives were based on di- or triiso-
cyanates that cured by reacting with active hydrogens on the surface of the substrate or
moisture present in the air or substrate. The moisture reacts with the isocyanate groups to
form urea and biuret linkages, building molecular weight, strength, and adhesive proper-
ties. Prepolymers are also used either as 100% solids or solvent-borne one-component
adhesives. Moisture-cured adhesives are used today in rebonded foam, tire cord,
furniture, and recreational vehicle applications.
A second type of one-component urethane adhesive comprises hydroxypolyurethane
polymers based on the reaction products of MDI with linear polyester polyols and
chain extenders. There are several commercial suppliers of these types of thermoplastic
polyurethanes. The polymers are produced by maintaining the NCO/OH ratio at slightly
less than 1:1 to limit molecular weight build to the range 50,000 to 200,000 with a slight
hydroxy content (approximately 0.05 to 0.1%). These are typically formulated in solvents
for applications to shoe soles or other substrates. After solvent evaporation heat is used
to melt the polymer (typically 50 to 70

C; at these temperatures the polymers reach

the soft, rubbery, amorphous state), so the shoe upper can be press t to the sole. Upon
cooling, the adhesive recrystallizes to give a strong, exible bond [58]. More recently,
polyisocyanates have been added to these to increase adhesion and other physical
properties upon moisture curing. In Section IX.B we discuss this in more detail.
The use of waterborne polyurethane adhesives has grown in recent years as they have
replaced solvent-based adhesives in a number of application areas. There are a number
of papers and patents covering the use of waterborne polyurethanes in shoe soles, packa-
ging laminates, textile laminates, and as an adhesive binder for the particleboard industry
[5962]. Because waterborne polyurethane adhesives have no VOC (volatile organic
content) emissions and are nonammable, they are more environmentally friendly.
Typically they can be blended with other dispersions without problems and exhibit
good mechanical strength. Water-based systems are fully reacted, linear polymers that
are emulsied or dispersed in water. This is accomplished by building hydrophilicity
into the polymer backbone with either cationic or anionic groups or long hydrophilic
polyol segments or, less frequently, through the use of external emulsiers. Figure 25
illustrates the more common functional groups that can be built into the urethane mole-
cule that will confer hydrophilicity.
Copyright 2003 by Taylor & Francis Group, LLC
A typical example of how these groups are built into the polymer backbone is shown
in Fig. 26. A urethane prepolymer is reacted with chain extenders containing either car-
boxylates or sulfonates in a water-miscible solvent (e.g., acetone). The reaction product is
an isocyanate-terminated polyurethane or polyurea with pendant carboxylate or sulfonate
groups. These groups can easily be converted to salts, which as water is added to the
prepolymersolvent solution, allows the prepolymer to be dispersed in water. The solvent
is then stripped, leaving the dispersed product. There are variations on this theme that
allow lower solvent volumes to be used [63]. Long hydrophilic polyol segments can also be
introduced. Chain extenders with hydrophilic ethylene oxide groups pendant to the back-
bone are reacted with the prepolymer to form a nonionic self-emulsifying polyurethane.
This reaction is also carried out in a water-miscible solvent that can later be stripped from
the solventwater solution.
Blocked isocyanates can also be considered a one-component adhesive. The use of a
blocking agent allows the isocyanate to be used in a reative medium that can be heat
activated. One-component adhesives based on blocked isocyanates are thus not amenable
to room-temperature curing applications. The chemistry of these products is covered in
more detail in Section VI.A.
B. Two-Component Adhesives
The second major classication of common polyurethane adhesives is the two-component
system. Two-component polyurethane adhesives are widely used where fast cure speeds
are critical, as on OEM (original equipment manufacturers) assembly lines that require
quick xture of parts, especially at ambient or low bake temperatures. Two-component
urethanes are required in laminating applications where no substrate moisture is available
or where moisture cannot penetrate through to the adhesive bond. Two-component
urethanes are also useful where CO
2
(generated by a one-component moisture cure) or
a volatile blocking agent would interfere with the adhesive properties.
Two-component adhesives typically consist of low-equivalent-weight isocyanate or
prepolymer that is cured with a low-equivalent-weight polyol or polyamine. They may be
100% solids or solvent borne. Since the two components will cure rapidly when mixed,
they must be kept separate until just before application. Application is followed quickly by
mating of the two substrates to be bonded.
Figure 25 Common functional groups that confer hydrophilicity in the urethane molecule.
Copyright 2003 by Taylor & Francis Group, LLC
Ecient mixing of the two components is essential for complete reaction and full
development of designed adhesive properties. In-line mixing tubes are adequate for low-
volume adhesive systems. For larger-volume demands, sophisticated meter mix machines
are required that will mix both components just prior to application. Commercial systems
for delivering two-component adhesives are segmented based on the viscosity ranges of the
components. The ranges can be broken down into low, middle, and high viscosity, with,
for example, Liquid Control Corp., Sealant Equipment and Engineering Inc., and Graco
Inc., respectively, supplying equipment for the three ranges [64].
In present-day high-speed assembly line operations, adhesives are applied roboti-
cally. The adhesive bead is applied quickly and evenly to parts on a conveyor line just prior
to being tted. These operations, especially the need to handle the adhered substrates soon
after assembly, demand fast-curing adhesive systems [65]. Two-component adhesives are
used to bond metals to plastics in automobiles, to laminate panels in the construction
industry, to laminate foams to textiles, to laminate plastic lms together, and to bond
poly(vinylidene chloride) lms to wood for furniture. A commercial waterborne two-
component adhesive is sold by Ashland under the trademark ISOSET. This system is
used for exterior sandwich panels by recreational vehicle manufacturers and is composed
of a water-emulsiable isocyanate and a hydroxy-functionalized emulsion latex.
Figure 26 How functional groups are built into the polymer backbone of urethane.
Copyright 2003 by Taylor & Francis Group, LLC
IX. RECENT DEVELOPMENTS
A. Hybrid Adhesives
Over the last four decades there have been a number of attempts to wed the unique
benets of polyurethane adhesives with the benets of other adhesive systems. These
attempts have led to the reporting of a variety of urethane hybrids. Early work focused
on simple blends; for example, in 1964 Union Carbide blended organic isocyanates with
ethylenevinyl acetate copolymers [66]. These blends were used as an adhesive interlayer in
glass laminations, particularly safety glass laminates. Similarly, polylurethaneepoxy
blends for safety glass laminates were reported in 1970 [67].
More recent eorts have focused on developments that create true hybrids. For
example, blocked isocyanate prepolymers have been mixed with epoxy resins and cured
with amines [6870]. These blocked prepolymers will react initially with the amines to form
amine-terminated prepolymers that cross-link the epoxy resin. Several blocked isocyanates
are commercially available. The DESMOCAP (Bayer) 11A and 12A products are isocya-
nates (believed to be blocked with nonylphenol) used as exibilizing agents for epoxy
resins. ANCAREZ (trademark, Pacic Anchor, Inc.) 2150 is a blocked isocyanate
epoxy blend used as an adhesion promoter for vinyl plastisols. A one-package, heat-
cured hybrid adhesive was reported consisting of isophorone diisocyanate, epoxy resin,
and a dispersed solid curative based on the salt of ethylenediamine and bisphenol A [71].
Urethane amines are oered commercially that can be used with epoxy resins to develop
hybrid adhesive systems [72].
Urethane acrylic hybrids have been reported based on several approaches. Pacic
Anchor has developed a urethane acrylate that is commercially available (ANCAREZ
300A). Acrylic polyols have been synthesized in the presence of polyether polyols by
Saunders for use in two-component structural adhesives with improved tensile and
impact strength [73,74]. Pressure-sensitive acrylic prepolymers with hydroxyl groups
have been formulated with isocyanate prepolymers to give adhesives with improved
peel strength [75,76]. Aqueous-based vinyl-to-berboard adhesives were reported by
Chao using water-dispersible MDI with a functionalized acrylic latex and an aqueous
dispersion polyurethane to given improved shear and hot peel strength [77]. Acrylo-
nitrile dispersion graft polyether polyols have also been used in two-component SMC
adhesives [78].
Urethanes have also been used to toughen vinyl-terminated acrylic adhesives for
improved impact resistance. Thus rubber-toughened urethane acrylates [79,80], water-
dispersible urethane acrylates [81], and high-temperature-performance urethaneacrylate
structural adhesives have been reported [82]. Polyurethanes terminated with acrylic
functionality are also used for anaerobic or radiation-cured adhesives with improved
toughness [83].
B. Reactive Hot Melts
Polyurethane reactive hot melts are 100% solid, hot-melt thermoplastic prepolymers that
moisture cure slowly after application. Conventional hot melts are known for their quick
setting, excellent green strength, ease of application, and low toxicity. Their primary
limitation is low heat resistance (at elevated temperatures, the adhesive will soften and
ow) and poor adhesion to some substrates, due to insucient wetting. The use of a
polyurethane prepolymer with low levels of free isocyanates as a hot melt oers distinct
Copyright 2003 by Taylor & Francis Group, LLC
advantages: initial green strength is still achieved, and in addition, the isocyanate will
moisture cure slowly, converting the thermoplastic adhesive to a thermoset. There are a
number of recent patents on reactive hot melts [8487]. The tensile strength of the adhesive
increases, heat resistance is improved, and the nal cured adhesive will not ow at elevated
temperatures [88]. A limitation of this technology is the need for porous substrates or bond
designs that will allow the diusion of moisture into the adhesive so that moisture curing
will occur. The adhesive itself must be protected from moisture prior to use. This technol-
ogy should be applicable to assembly line operations which require an adhesive that gets
high initial green strength.
C. Pressure-Sensitive Adhesives
The use of polyurethanes in the pressure-sensitive adhesives market has been relatively
small. Polyurethanes have been somewhat limited to being used as additives to pressure-
sensitive adhesives to improve their cohesive strength. Recent developments in the institu-
tional carpet backing or automotive carpet oor mat markets suggest that pressure-
sensitive urethanes can succeed commercially [89].
X. SUMMARY
Polyurethane adhesives as a class can no longer be perceived as new raw materials. From
a base of 217 million pounds, double-digit growth can no longer be expected. Even
so, signicant growth will continue. Formulators are taking advantage of the tremendous
exibility of urethane chemistry in designing new adhesive products. Specialty niches such
as waterbornes and reactive hot melts, for example, will continue to emerge and fuel
growth. Exciting times lie ahead for innovative formulators of polyurethane adhesives!
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