The polyurethane reaction

Polyurethane and its related chemistries were first discovered in

1937 by Otto Bayer however it wasn’t until the 1950’s that they
became commercially available. The basic synthesis involves the
exothermic condensation reaction of an isocyanate (R’-(N=C=O) n)
and a hydroxyl-containing compound, typically a polyol (R-(OH) n)
(Figure 3).

The reaction proceeds readily at room temperature, regardless of a

catalyst, and is typically completed in a few seconds to several
minutes depending on the formulation, in particular the choice of
isocyanate. Therefore compared to other polymers such as
polyethene or polypropene which are produced then heated and
moulded at a later stage, polyurethanes are made directly into the
final product via reaction injection moulding (RIM), or applied onto
the substrate in the case of adhesives and coatings.

Figure 3. The condensation polymerisation of an isocyanate (R’-

(N=C=O)n) and a polyol (R-(OH)n) to form polyurethane.
An important side reaction involves the isocyanate component and
water. If moisture is present in the mixture (Figure 4), then the
isocyanate will react with this water to form an unstable carbamic
acid which then decomposes to form urea and carbon dioxide gas
thus resulting in foaming. The selection of an appropriate catalyst
can either suppress this reaction or can promote this reaction if
foam formation is desired.

Figure 4. Isocyanates are highly reactive with hydroxyl (-OH)

groups. When in contact with water, isocyanates react to form
carbamic acid which then decays to form an amine and carbon
dioxide gas. This gas is responsible for foaming and is often used in
the production of PU foams for furniture or construction
applications.

Polyurethanes are typically supplied as two-component

formulations; a part A containing the polyol, catalyst, and any
additives, and a part B compromising of the isocyanate.

Raw materials used to produce polyurethane

Part A: Polyol

The majority of polyols used in polyurethane production are

hydroxyl-terminated polyethers though hydroxyl-terminated
polyesters are also used. The choice of polyol ultimately controls
the degree of cross-linking and therefore the flexibility so
formulators must consider not only the size of the molecule, the
degree of branching but also the number of reactive hydroxyl
groups present.

If a polyol containing two hydroxyl groups (a diol) is reacted with TDI

or MDI, then a linear polymer is produced. Polyols with a greater
number of reactive hydroxyls result in a higher level of crosslinking
and a more rigid final product.

Part B: Isocyanate

The most commonly used isocyanates for polyurethane production

are the aromatic diisocyanates toluene diisocyanate (TDI) and
methylene diphenyl diisocyanate (MDI) which form the basis for
>90% of all polyurethanes (Figure 5).

TDI is a mixture of two isomers and is primarily used in the

production of low-density flexible foams whereas MDI is a more
complex mixture of three isomers and is used to make rigid foams
and adhesives.
Figure 5. Chemical structures of the aromatic isocyanates toluene
diisocyanate (TDI) and methylene diphenyl isocyanate (MDI). TDI
and MDI account for 90% of all isocyanate usage globally and are
mostly used to produce flexible and rigid foams.

Less reactive are the aliphatic isocyanates (Figure 6) however

these are important for coatings applications due to their excellent
UV and colour stability. Aliphatic isocyanates account for <5% of
isocyanate usage worldwide and include hexamethylene
diisocyanate (HDI) and isophorone diisocyanate (IPDI).
Figure 6. Chemical structures of the aliphatic isocyanates
hexamethylene diisocyanate (HDI) and isophorone diisocyanate
(IPDI). HDI and IPDI mostly find use in coatings applications and
account for <5% of isocyanate usage.

Blocked isocyanates

Blocked isocyanates are a relatively new development whereby the

reactive NCO- groups are further reacted with groups such as
dimethyl malonate (DEM), dimethyl pyrazole (DMP) or methylethyl
ketoxime (MEKO) to produce inert and non-hazardous materials.
These materials can be selectively unblocked at elevated
temperatures (+100°C) thus opening up a greater variety of
applications such as usage in 1K or waterbased formulations, or for
lower free isocyanate levels.

Catalysts

Catalysts play an important role in the production of polyurethane

as not only do they increase the reaction rate and control gelling
time, they also assist with balancing the side reactions including the
water reaction and therefore control gas-formation and foaming.
Broadly speaking, the catalysts used for polyurethane manufacture
fall into two categories: amines or organometallic catalysts including
organotin, bismuth and zinc.

Amine catalysts

Amine catalysts are derived from ammonia (NH3) by substituting one

(primary) or two (secondary) or three (tertiary) of the hydrogen
atoms with an alkyl group. Their catalytic activity is determined by
both the structure and the bascity with increased steric hinderance
of the nitrogen atom resulting in decreased activity and increased
bascity increasing activity. Tertiary amines are predominantly used
in the manufacture of foam as whilst they drive urethane formation,
they also promote the water reaction leading to CO 2 gas generation.

Mercury catalysts

Mercury catalysts such as phenylmercuric acetate, propionate, and

neodecanoate are highly efficient at driving urethane formation and
characteristically result in a long pot life in combination with rapid
back-end cure. However despite their excellent performance,
mercury catalysts are less common due to their poor toxicological
status.

Tin catalysts

Outside of amine catalysts, organotin catalysts are the most widely

used in polyurethane production with grades such as TIB KAT® 218
(dibutyltin dilaurate DBTL), TIB KAT® 216 (dioctyltin dilaurate
DOTL), and TIB KAT® 318 (dioctyltin carboxylate) widely used in
CASE applications (coatings, adhesives, sealants, and elastomers).

TIB KAT® 218 (DBTL) is the workhorse grade (Figure 7) and

strongly drives the urethane reaction however in some instances
longer ligand dioctyltins such as TIB KAT® 216 (DOTL) or TIB
KAT® 318 are preferred due to more favourable labelling.
Other grades such as TIB KAT® 223 or TIB KAT® 214 can provide
varying curing profiles such as a rapid cure in the case of TIB KAT®
223 or a “mercury-like” curing profile with TIB KAT® 214.

Figure 7. Mechanism of polyurethane catalysis using TIB KAT®

218 (dibutyltin dilaurate DBTL). DBTL acts as a Lewis acid and
accepts the non-bonding electrons from the oxygen on
the isocyanate molecule to initiate the reaction.

Bismuth and zinc catalysts

Bismuth and zinc catalysts are growing in popularity due to their low
toxicity and both TIB KAT® 716 (bismuth) and TIB KAT® 616
(zinc) are used in CASE applications as they are strongly selective
towards the urethane reaction.

Bismuth, in particular, can mimic DBTL performance and in some

instances offers a shorter pot life than organotins. However, bismuth
typically requires higher dosage levels than organotins and is
sensitive to hydrolysis; even low moisture levels can have a
detrimental effect on activity.
Zinc on the other hand results in increased pot life with a good
through cure and is especially useful when curing at elevated
temperatures (>60 °C).

Other metallic catalysts

Other catalysts such as aluminium, titanium and zirconium

complexes are being used in some instances though are not
widespread as have lower activity and can require much higher
dosages. They can also be more selective towards primary alcohols
in a polyol mixture leading to poorer and breakable polyurethane
material.

Table 1: Advantages and disadvantages of amine and metallic

catalysts for polyurethane production.

Other components

Depending on the final application, polyurethane formulators will

also include other additives in the formulation including, but not
limited to:

 Pigments to create coloured polyurethanes

  Fillers for mechanical reinforcement and to reduce overall costs such
as those from Quarzwerke, from KaMin or from 3M
 Plasticisers to increase flexibility
 Cross-linkers and chain-extenders to improve physical properties
 Blowing agents and foam stabilisers to control bubble formation and
cell structure in foams
 Moisture scavengers and zeolites to remove moisture and suppress
foam formation such as those from Zeochem
 Flame retardants and smoke suppressants to reduce flammability and
reduce smoke generation if burnt
 UV absorbers and antioxidants to minimize degradation such as
those from Chitec

Summary

Polyurethanes can be used in a wide variety of applications and

their properties can tailored through the correct selection of
isocyanate and polyol components, catalysts and other additives in
the formulation. Lawrence Industries are supplying a number of
materials into PU applications including organometallic catalysts,
functional fillers and additives.