CHAPTER FIVE

PRINCIPAL REACTIONS UTILISED IN THE

POLYURETHANE TECHNOLOGY

Addition of diisocyanate to a difunctional hydroxyl compound (2)

makes the basic reaction which yields linear polyurethanes. Other
reactions, specific for isocyanates, also bring significant contributions
to the polyurethane manufacturing processes, especially to those
processes which utilise linear polyurethanes at their initial processes
and produce foamed materials, elastomers and coatings. Whether the
consequences of those reactions become apparent or not, it is decided
by both the structure of the monomers used, and by the conditions
adopted for the polyaddition process: temperature, time, type and
amount of catalyst (if any), presence of inhibitors which are employed
to stabilise isocyanate prepolymers, auxiliary agents added (if any),
initial molar ratio of monomers, and method of feeding (dosing) them.
It is important to promote the reactions desired for the given process
and to minimise at the same time the side reactions. In the foamed
polyurethane manufacturing process, for example, the urethane chain
growth reaction is important in which urea groups extend the chains
to produce the matrix for the foam. Equally important is the reaction
of free isocyanate groups which foams the polyurethane material with
in situ evolved CO2 (equations 62):
R NCO + H2O R NH2 + CO2
R NCO + R NH2 R NH CO NH R (62)

In order to avoid that reaction, the polymerisation process should be

carried out under inert gas blanketing, with the use of nitrogen or
argon in most cases.
Moreover, the isocyanate groups—with their electrophilic-nucleophilic
specifications—can enter various reactions which are more or less desir-
able, depending on specific polyurethane processes, and they can react
with all electron-donor and electron-acceptor groups [2, 54, 93].
Isocyanates can undergo dimerisation at the temperature just above
43°C and they yield yellow-coloured uretidione structures (63), while
dissociation of the dimer can be expected only above 175°C. That
46 chapter five

reaction is responsible to a high degree for unwanted yellowing of

coatings produced from TDI- and MDI-based aromatic polyurethanes
(formula 63):

OCN O
NCO
C
H3C N N CH 3 (63)
C
O

Alkaline conditions, on the other hand, promote trimerisation to iso-

cyanurates. That reaction is irreversible and the resultant isocyanurate
ring is stable up to the temperature of 200°C. Hence, that structure is
desirable in polyurethane-isocyanurate foams with improved thermal
stability (formula 64):
NCO NCO
H3C CH 3
O

C
N N

C C
O O (64)
N

OCN

CH 3

Polymerisation of diisocyanates (65) and production of polyamide-1 is

much less probable since the alkaline medium and low temperatures
(–20 to –100°C) are required, and that combination is not employed
in the production of PU goods:
principal reactions utilised in the polyurethane technology 47

n R1 N C O ~N C~ (65)
n
R1

The reaction between isocyanate groups in the presence of trialkyl-

phosphine oxides can release CO2 and form carbodiimide structures
(equation 66):
2 R1 N C O R1 N C N R 1 + C O2 (66)

The presence of urethane groups in the alkaline reaction mixture

is also favourable for the formation of allophanate compounds (equa-
tion 67):
O

~N C O~
O
120 ° C (67)
~ NH C O~ + ~ NCO ~ NH C
O

That reaction in undesirable in case when for example prepolymer

with free -NCO groups has to be stored for some time. Cross-linking
with the use of allophanate bonds is utilised on the other hand in the
production of thermoplastic polyurethane elastomers.
Inhibitors are used in order to restrict side reactions and thus improve
stability of prepolymers. These are usually Lewis acid compounds or
other base-bonding materials. The anti-catalytic performance is also
offered by metallic catalyst chelating compounds. Benzoyl chloride and
p-nitrobenzoyl chloride are the most effective inhibitors. They prevent
any polymerisation reaction of NCO-capped isocyanates and urethane
prepolymers with urethanes, amines and urea. At the same time, they
catalyse the reaction with -OH groups and water. Stability of prepoly-
mers can be also improved by the use of polyphosphoric acid [94].
New reactions of isocyanates have been revealed recently and they
have been utilised in the production of polyurethane-based powder
coatings [94–97]. The latest options utilise the reactions of “internal
masking” of diisocyanates by means of uretidione, biuret and allophan-
ate bonds for that purpose [98–109]. There are reactions of special
48 chapter five

value—these will “mask” polyisocyanates with low toxicity and high

content of reactive functional groups by means of ε-caprolactam, ben-
zyl alcohol, oximes, and some heterocyclic compounds, like pyrazole,
triazole and imidazole. Those types of polyisocyanates are synthesised
in general by obtaining the suitable tri-functional or tetra-functional
reactive isocyanate prepolymers in the reaction of diisocyanate with
tri-functional or tetra-functional compounds [110] (e.g. trimethylolpro-
pane or pentaerythritol) or in their trimerisation reaction [111]. Which
matters a lot in the production of powder coatings is the dimerisation
reaction, but that technology has some drawbacks—progress of the
competitive reaction which yields isocyanurate structures needs to be
controlled, and considerable amounts of unconverted diisocyanates
need to be removed from the reaction mixture. That, however, can be
successfully accomplished by finding high-selectivity catalysts [97]. It
should be stressed that dimerisation of aromatic diisocyanates makes a
much easier process, but application of the product in powder coatings
is limited due to its inferior weathering resistance. Aliphatic and cyclo-
aliphatic diisocyanates are of greater importance [110]. Yet, only IPDI
could so far offer satisfactory yield when subjected to dimerisation (99 %
of dimer in relation to isocyanurate structures), owing to the difference
in reactivities of isocyanate groups. When other generally employed
diisocyanates (HDI and HMDI) are subjected to dimerisation, chemical
equivalence of both their isocyanate groups results in the formation of
considerable amounts of isocyanurate structures (25–50 %). Internal
“masking” by means of biuret or allophanate bonds is easier to do and
the yield is high. Those reactions are reversible at lower temperatures
(120°C) than dimerisation is (180°C), and they can make competitive
options for relatively difficult and long dimerisation processes.