Polyurethane Adhesive

One-part solvent-borne polyurethane adhesive

The one part adhesive is essentially a thermoplastic PU (TPU) dissolved in a
solvent. The solvated TPU is applied to the prepared surface as a contact
cement, or is applied, allowed to dry, and then adhesion generated by
contacting the adherends with heat.
polyether soft segments dominate the adhesive application, many
onecomponent solventborne PU adhesives will employ a polyester soft
segment such as polybutylene adipate for the simple reason that its ability to
crystallize can increase the initial adhesion between adherends.

In one part solvent borne PU adhesives, pretreatment of the surface ie.

extensive roughening of the surface and the use of a primer coating that has
preferential adhesion to the substrate and the TPU.

Typical primer polymers are substances such as chlorinated polyethylene at

high dilution in an aromatic solvent such as toluene.
For these systems, the solvent can also be a major participant in the growth
of adhesion by swelling both the substrate and the adhesive polymers to
promote polymer chain entanglement or physical interlocking of larger
polymer segments that form as the adhesive laminate swells and then
contracts.

Two part solvent borne polyurethane adhesive

A two part solvent borne version of PU adhesives is typically an isocyanate
tipped prepolymer with relatively low isocyanate content (512%) on the one
side, and chain extender (diol or diamine), catalyst, and often a crosslinker
for the second component.
A two part solvent borne system has the benefit of allowing the opportunity
to tune adhesive modulus and improve solvent resistance via the crosslinking capability.
Blocked isocyanates are standard polyisocyanates prereacted with weakly
bonded active hydrogen groups.
When heated, the weakly reacted components decouple releasing the
original polyisocyanate and the blocking agent.
In addition, PU side reactions, particularly with ambient water, are capable of
producing CO2 gas. In the limit of high humidity, this can have the very
undesirable effect of foaming the adhesive layer.
Hotmelt Adhesives
Hot melt adhesive (HMA) is a form of thermoplastic adhesive that is
commonly supplied in solid cylindrical sticks of various diameters, designed
to be melted in an electric hot glue gun.
The gun uses a continuous-duty heating element to melt the plastic glue,
which the user pushes through the gun either with a mechanical trigger
mechanism on the gun, or with direct finger pressure.
hotmelt adhesives are thermoplastic materials that
(i) are heated and applied to a substrate in the molten state,
(ii) the bonding substrates are assembled, and

(iii) the thermoplastic resolidifies back to its thermoplastic state.

non-reactive hot melt adhesive
This is ascribed to the higher viscosity of TPU at standard application gun
temperatures that limit substrate wetting. It is possible to reduce viscosity
and thereby improve hotmelt adhesive properties by addition of a monol
(e.g., replacing some amount of butanediol with 1butanol), substitution of
even 5% of the butanediol chain extender with 1butanol can reduce
molecular weight of the chain limited polymer by a factor of 23 and reduce
the viscosity of the polymer melt by over an order of magnitude based on
the Mn rule
formulation of a nonreactive polyurethane hotmelt adhesive

Reactive Hotmelt Adhesive

Reactive PU hotmelt adhesives are essentially a low percentage isocyanate
prepolymer that is applied to a substrate and allowed to cure by reaction via
adventitious moisture, or by direct reaction with substrates possessing active
hydrogen on their surface.
Reactive hotmelts possess a highly desirable grouping of properties including
low viscosity at application temperatures, rapid generation of green strength
when using crystalizable soft segments, gradual development of very strong
adhesive bonding, no VOCs, and the excellent material properties of PU
elastomers.
Formulation of a reactive polyurethane hotmelt adhesive

Polycaprolactone based MDI prepolymer with 2.3% isocyanate useable as a

reactive PU hotmelt adhesive.
Polyether polyols can also be used to make very good reactive hotmelt
adhesives, especially when the prepolymers are made of blended molecular
weights to provide the mix of low viscosity and rapid green strength build.

Waterborne PU Adhesives (PUd)

PUds enable delivery of a low viscosity urethane polymer to a substrate, while reducing or
eliminating the use of fugitive organic solvents
The polyol and isocyanate structures in PUd prepolymers can vary widely depending on final
application and requirements.
While PUd prepolymers are typically isocyanate terminated, they can also employ hydroxylterminated prepolymers for two component waterborne urethanes.

Prior to dispersing in water, the carboxylic acid groups in the prepolymer are neutralized
with a strong base such as triethylamine to convert the acid to the carboxylate.
It is this hydrophilic neutralized carboxylate that serves to disperse and stabilize the
particles in the aqueous phase. Immediately following this aqueous dispersion step, a chain
extender is added to the dispersion to complete conversion of the remaining isocyanate
groups to the final polymer within the particles.
Due to the competing reactivity of water, the selection of chain extender is limited to chain
extenders with higher reactivity toward isocyanates than water. Most commonly, these chain
extenders are primary or secondary polyamines that chain extend the polymer via formation
of urea bonds

Batch Process for PUd

The PUd ionomer process is often done with low levels of a solvent, such as acetone or nmethyl pyrrolidinone (nMP) to lower prepolymer viscosity in the process.
In the case of acetone, the solvent is removed in a final step, while low levels of high boiling
solvents such as nMP may be left in the final product.

PUd ionomer process