POLYURETHANE CHEMISTRY & CALCULATIONS

Commercial polyurethane polymers are typically made by the reaction of a diisocyanate with a molecule
containing at least two active hydrogens. (Active hydrogen is defined as hydrogen that can be replaced by sodium.)
The reaction is self-sustaining, without byproduct formation, and is relatively easily controlled. This mechanism of
polymerization is often named polyaddition.

Polyaddition polymerization
OCN-R-NCO + HO-R-OH - (O-OC-HN-R-NH-CO-O-R) nDiisocianate
Polyol
Polyurethane
Reactions of Isocyanates with Active Hydrogen Compounds
When an isocyanate reacts with an alcohol, a urethane is formed:
R-NCO
+
Isocyanate

R-OH R-NH-CO-O-R
Alcohol
Urethane

If the active hydrogen compound is a primary amine, a substituted urea results:

R-NCO
+
Isocyanate

R-NH2
Amine

R-NH-CO-NH-R
Substituted Urea

When the active hydrogen compound is water, the first stage of the reaction is the production
of an unstable carbamic acid derivative, RHNCOOH, which quickly decomposes to the
amine, liberating carbon dioxide. If this CO2 is contained within the forming polyurethane, it
results in the production of polyurethane foam. The amine can then go on to react with further
isocyanate to give form a substituted urea:
R-NCO
+
Isocyanate
R-NH2
Amine

H 2O
Water

R-NH2 + CO2
Amine Carbon Dioxide (Released)

R-NCO
R-NH-CO-NH-R
Further Isocyanate
Substituted Urea

The substituted ureas are themselves active hydrogen compounds and further reaction can
take place with any remaining isocyanate to give the biuret:
R-NH-CO-NH-R
Substituted Urea

R- NCO R-N-CO-NH-R
Isocyanate

CO-NH-R

Biuret

Similarly, the urethanes formed from the reaction of Isocyanates with alcohols can go on
to react with any remaining isocyanate to give allophanates:
R- NCO
Isocyanate

R-NH-CO-O-R R-N-CO-O-R
Urethane

CO-NH-R

Allophanate

Biuret and allophanate formation can be encouraged by using a stoichiometric excess of

isocyanate. This will result in an increase in the level of hard segments in the polymer
structure and extensive crosslinking of the polymer network. The hard: soft segment ratio and
the degree of crosslinking is a critical parameter in determining the final properties of the
polyurethane polymer.
Other Reactions of Isocyanates
The most common reaction of an isocyanate with anything other than an active hydrogen
compound is the reaction with another isocyanate. Two moles of isocyanate can react to form
the carbodiimide releasing carbon dioxide, although this is not very common. More usually,
two moles of isocyanate react to form the four membered uretidine Dione (uretidone) ring
structure. This reaction is important commercially for the production of isocyanate variants
with improved storage and handling characteristics:
OCN-R
+ R-NCO (R-NCO)2
Isocyanate
Isocyanate
Uretidone
Three moles of isocyanate can react to form the 6 membered isocyanurate ring structure, this
is the most common reaction where there is a significant excess of free isocyanate.
Trimerisation, as this is sometimes called, is most important in the production of highly
crosslinked polyurethane based polymers - for example, fire resistant rigid foams and certain
varnishes.
3 x R-NCO (R-NCO)3
3x Isocyanate
Isocyanurate
Polyurethane Formation
Literally thousands of different polyurethanes can be made from the array of commercially
available isocyanate and active hydrogen compounds. In the production of CASE materials,
(coatings, adhesives, sealants and elastomers), the main active hydrogen containing
compounds are hydroxy functional, with a functionality of two, or sometimes three. In
flexible foams, hydroxy functional compounds with a functionality of three are used. For rigid
foams hydroxy compounds with functionality as high as eight have been used. In all cases,
these hydroxy compounds are often polymers themselves and are known as polyols.
Polyurethanes can be divided into two component and one component systems:Two component systems
Two component systems can take two forms;In the first type, known as "one shot" systems, the polyol is first blended with catalysts and
flame retardants, plasticizers, fillers etc as required to form what is known as the "resin"
component, this is then mixed/reacted with the "iso" component, made up of only the
diisocyanate. Multi-component one shot systems are also possible, with these, the iso
component is again only the diisocyanate, but the resin side of the system is split into it's

constituent parts - commercial production of flexible slabstock foam is done in this way.
Commercial one-shot systems are typically dispensed using accurate metering machines.
In the second type, known as the "prepolymer" route, the first step is to produce a precursor to
the final polyurethane polymer by reacting one equivalent of polyol with up to two
equivalents of isocyanate. This results in an isocyanate terminated intermediate product,
called a prepolymer, which has little or no free diisocyanate monomer and more controllable
reactivity. When only a portion of the diisocyanate molecules are pre-reacted in this way, the
diisocyanate rich product is known as a "quasi-prepolymer". Prepolymers normally have
molecular weights in the range 1000-8000 and have viscosities in the range 2000-20000
centistokes.
Polyurethanes are then produced by the reaction of prepolymers with "chain extenders", (also
known as a curative), such as a short chain polyols or diamines. The chain extender "zips-up"
the prepolymer molecules, increasing molecular weight and creating the final PU polymer.
Prepolymer systems can be hand or machine mixed and additives such as catalysts, flameretardants, plasticizers, fillers etc are typically blended into the prepolymer prior to chain
extension.
One component systems
The most common type of one component system is where a specially formulated prepolymer
is allowed to chain extend/cure with water vapour in the atmosphere, these are known as
"moisture curing" systems. In a similar way, cure can also be effected by exposing the
prepolymer to an atmosphere of diamine or triamine, this is known as "vapour cure".
One component systems can also be produced by the "blocking" of isocyanate groups so that
they are temporarily unable to react. This is usually achieved by reaction of the isocyanate
with specific hydroxy containing molecules, such as phenols or tertiary alcohols that are
characterized by their comparatively unstable urethane links. The blocked isocyanate, which
can be a diisocyanate, a quasi-prepolymer or a prepolymer, can then be handled and processed
without concern for further reaction/gelation, since non-unreacted isocyanate remains. When
processing is complete, heat is applied to break the bonds of the blocking groups, regenerating
the isocyanate compound, and allowing the polyurethane to fully cure. Many attempts have
been made to lower unblocking temperatures, but commercial systems still often have to be
raised to at least 100oC in order to effect the unblocking reaction.
Polyurethane Raw Materials
Isocyanates: Both aromatic and aliphatic Isocyanates are commercially available, aromatic
Isocyanates are faster reacting by a factor of between 2 -10 depending on their chemical
structure.
Aromatic Isocyanates (TDI, MDI): Toluene diisocyanate, (TDI), CH3(C6H3)(NCO)2, has
two common isomers, the 2,4 & the 2,6 diisocyanate. The pure (100%) 2,4 isomer is available
and is used commercially, but most TDI is sold as 80/20 or 65/35 2,4/2,6 blends.

The other major group of aromatic isocyanate products is based diphenylmethane 4,4'
diisocyanate, (MDI), NCO(C6H4)CH2(C6H4)NCO. The pure product has a functionality of
two, but it is common to blend pure material with mixtures of higher functionality MDI
oligomers (often known as crude MDI) to create a range of functionalities/crosslinking
potential.
Aliphatic isocyanates: The most common ones are based on isophorone diisocyanate and
hexamethylene diisocyanate. These monomers can be modified to produce a range of dimers,
trimers and biurets. The key property of aliphatic Isocyanates is their excellent UV stability.
Polyols
Polyether polyols: In the presence of a hydroxy terminated alkoxide initiator, propylene
oxide will ring open and polymerize. This produces a polyether polyol where secondary
(rather than primary) hydroxyl groups are preferentially formed. Secondary hydroxyl groups
are less reactive than primary hydroxyl groups and, if higher reactivity polyols are required,
copolymerization with ethylene oxide (which produces exclusively primary hydroxyl groups)
is carried out.
The functionality of the final polyol is controlled by the functionality of the initiator.
Commonly, dipropylene glycol is used for diols, glycerine for triols, ethylene diamine for
tetrols and sorbitol for hexols.
Polyester polyols: In CASE applications, these are typically adipate esters, formed by
reacting difunctional adipic acid with a short chain diol/triol and removing the water
byproduct. Polycaprolactone polyols are a special type of polyester made by a different, noncondensation route. As a result, polycaprolactones typically offer performance benefits over
adipates, particularly with regard to hydrolysis resistance & cold flex. Additionally, orthophthalate polyesters offer excellent hydrolysis resistance and enhanced adhesion to many
substrates.
Chain Extenders: These are low molecular weight difunctional compounds containing
active hydrogen. They are often used to cure prepolymers, and their role is to increase the
molecular weight of urethane polymers without affecting elongation at break. The choice of
chain extender can have a considerable influence on final physical properties; those in
common use include the following:
HO(CH2)4OH
H2N-(C6H3Cl)-CH2-(C6H3Cl) - NH2
H-(O-CH(CH3)-CH2)nOH)

1,4 Butane Diol

MOCA (other less toxic diamine alternatives are available)
Low molecular weight polyether diols (MW 400-760)

Crosslinkers: These are low molecular weight compounds, containing active hydrogen, and
with a minimum functionality of 3 - such as triols & tetrols. Their purpose is to crosslink the
polymer network and so increase the hardness & modulus of the polyurethane.

Additives: Polyurethane systems contain any compatible additives, but all materials should
be free of water to avoid invalidating stoichiometric calculations and/or inadvertent CO2
formation.
Catalysts: amines, metal salts & organometallic compounds used to promote the various
urethane reactions.
Surfactants: typically silicones, used to facilitate mixing and control cell structure in foams.
Fire Retardants: phosphorus and/or halogen containing molecules that are added to foam
formulations to meet certain flammability specifications - also used as mild plasticizers.
Fillers: Inorganic fillers, like calcium carbonate and barium sulphate, can be used to extend
certain formulations, but they reduce most of the physical properties. Organic polymer
dispersions in polyols can be used as reinforcing fillers, (these polyols are called "polymer
polyols").
Plasticisers: phthalates, benzoates and aromatic oils can be used, here again, physical
properties are often reduced.
Other widely used additives are dyes, pigments, solvents and blowing agents.
POLYURETHANE CALCULATIONS
Stoichiometry
Stoichiometry in a polyurethane reaction is the ratio of the number of isocyanate groups (NCO) to active hydrogen groups (-OH/-NH2) available for reaction. It is frequently expressed
as the index defined as follows:
No. of Equivalents NCO x 100
No. of Equivalents OH/-NH2
Most polyurethane reactions are run at an index of 105. However, for flexible systems, there
can be good reasons to operate in the range 85-130 and in the case of isocyanurate foams, 400
is not uncommon.
Calculation of Reaction Index
The principle is to determine the number of reactive active hydrogen groups in a given
formulation and then calculate the number of isocyanate groups required for the desired
index.
The basic data for all products are given in the manufacturer's specification. It is important to
transpose this data into functions/kg according to the following definitions:
For polyols, No of OH groups/kg (FOH/kg)

For water, which is HOH, the equivalent weight is 9, so FOH/kg = 1000 = 111.1
9
For Isocyanates, manufacturers' specifications normally list % NCO or equivalent weight. The
following definitions apply:

Example 1
An NCO terminated TDI prepolymer is required at 100% index using a 2000 MW diol such as
ARCOL PPG2000.
OH Index (IOH) for ARCOL PPG2000 from manufacturer's specification is 56.
Therefore the number of OH groups/kg (FOH/kg) = OH Index = 56 = 1 (approx)
56.1
56.1
%NCO of TDI from manufacturer's specification is 48.2
Therefore F.NCO/kg of TDI is %NCO = 48.2 = 11.48
4.2
4.2
If batch size is such that 1000 kg of ARCOL PPG2000 is used, total OH will be 1000kg x
FOH/kg = 1000 x 1 = 1000.
For an NCO terminated prepolymer, each OH group will react with one NCO group. TDI has
2 NCO groups and ARCOL PPG2000, being a diol, has 2 OH groups. Therefore to make an
NCO terminated prepolymer, 4 NCO groups will be required for 2 OH groups.
Amount of TDI required will be: Total OH x 2 = 1000 x 2 = 174.2 kg
F.NCO/kg of TDI 11.48
This calculation assumes the polyol is dried before the reaction. If this is not the case, it is
common to increase the TDI accordingly.
For example, consider that the polyol contains 0.02% water.
The total water present in 1000kg polyol = 1000 x 0.02 = 0.20kg
100
FOH/kg water = 111.1

Therefore total OH from the water = 111.1 x 0.2 = 22.22

and the additional TDI required = Total OH due to water = 22.22 = 1.94kg
F.NCO of TDI
11.48
In practice, the total TDI requirement might be rounded down to 175 kg, (if the prepolymer
was to be made at 100% index).
Example 2
A one-shot elastomer system is required based on crude MDI. A typical formulation would be:
Parts by
weight
ARCOL 1025 100
MP Diol Glycol 10
Catalyst
1
Total

OH Index

FOH/kg

Total OH

28.5
1200
nil

0.51
21.39
-

51
213.9
264.9

Crude MDI (Suprasec 5025) has a published % NCO of 30.7%.

F.NCO/kg = %NCO = 30.7 = 7.31
4.2
4.2
If the system is run at 105% index, then the amount of Suprasec 5025 required will be:
Total OH x Index = 264.9 x 1.05 = 38.05kg
F.NCO/kg of MDI
7.31
In practice, 38 kg of Suprasec 5025 would probably be used.