Polyurethane Chemistry

For those from a technical and chemistry background you might find the following article an interesting insight to the
chemistry of polyurethanes. It is intended to give a brief technical introduction to the chemistry of polyurethanes and to
satisfy the frequent student requests we get to provide some details on the chemistry of polyurethane foam.
Polyurethane plastics are produced by the condensation reaction of a polyol and a di-isocyanate. Note the 'iso' within
diisocyanate which is often used as a root word in the naming of polyurethane technology companies. These chemicals
are often referred to as 'A' and 'B' when industrially mixed. The chemical reaction has the following formula:

When polyol and diisocyanate are reacted the reaction is quick and can be violent if not controlled by specific
quantities. The commercial production of spray foam polyurethane typically involves reacting the reactants, polyol and
diisocyanate, in 50:50 proportions and mixing small amounts under pressure at the focus of a spray gun to give the
resultant polyurethane foam. Heat and pressure are also used to and it is typical to produce industrial spray foams at
120 degrees temperature under 600 psi pressure to optimise the volume of foam produced and provide a quick cure
time within minutes.
No by-product is formed from the reaction of a polyol and a diisocyanate. Toluene diisocyanate is a widely used
monomer. Diols and triols produced from the reaction of glycerol and ethylene oxide or propylene oxide and are
considered very suitable for producing polyurethanes. Depending on the mix and type of the polyol, polyurethane
polymers are either rigid or flexible. For example, triols derived from glycerol and propylene oxide are used for
producing block slab foams. These polyols have moderate reactivity because the hydroxy groups are predominantly
secondary. More reactive polyols (used to produce injected moulding polyurethane foams) are formed by the reaction
of polyglycols with ethylene oxide to give the more reactive primary group:

Other polyhydric compounds with higher functionality than glycerol (three-OH) are commonly used. Examples are
sorbitol (six-OH) and sucrose (eight-OH). Triethanolamine, with three OH groups, is also used. Diisocyanates generally
employed with polyols to produce polyurethanes are 2,4-and 2,6-toluene diisocyanates prepared from dinitrotoluenes.

Synthetic Petroleum-Based Polymers

A different diisocyanate used in polyurethane synthesis is methylene diisocyanate (MDI), which is prepared from aniline
and formaldehyde. The diamine product is reacted with phosgene to get MDI. The physical properties of polyurethanes
vary with the ratio of the polyol to the diisocyanate. For example, tensile strength can be adjusted within a range of
1,200600 psi; elongation, between 150800%.
Improved polyurethane can be produced by copolymerization. Block copolymers of polyurethanes connected with
segments of isobutylenes exhibit high-temperature properties, hydrolytic stability, and barrier characteristics. The hard
segments of polyurethane block polymers consist of (RNHCOO)n, where R usually contains an aromatic moiety.
Properties and Uses of Polyurethanes
The major use of polyurethanes is to produce foam although non foam type polyurethane plastics are also made. The
density as well as the mechanical strength of the rigid and the flexible type foams can vary widely depending on the
polyol type and reaction conditions. The polyol is where the chemistry research money is spent as all the 'magic' of the
subsequently produced foam is largely in the polyol. For example, polyurethanes could have densities ranging between
10 - 100 Kg/M3 for the flexible types and 50 - 1000 Kg/M3 for the rigid and more high density foams. Densities can be
achieved such that large trucks can be driven over the foam without causing any damage. Polyurethane foams typically
have good abrasion resistance, very low thermal conductance (hence their wide use as thermal insulators) and good
load bearing characteristics. However, they have moderate resistance to organic solvents and are attacked by strong
acids. Uncured foam can be dissolved by using acetone which is quite effective at removing uncured foam but cannot
remove foam that has already cured. Foam can also be cut and shaped by carpenter tools, saws and chisels as it
behaves like very soft timber. Foams can be flammable unless specific flame retardants are added into the mix on the
polyol side. Flame retardency of polyurethanes could be improved by using special additives such has boron
compounds, spraying a coating material such as magnesium oxychloride on top of the foam, or by grafting a halogen
phosphorous moiety to the polyol. Trichlorobutylene oxide is sometimes copolymerized with ethylene and propylene
oxides to produce the polyol.
Major markets for polyurethanes are furniture, packaging, transportation, and building and construction. Other uses
include carpet underlay, textural laminates and coatings, footwear, packaging, toys, and fibres. The largest use for rigid
polyurethane is in construction and industrial insulation due to its high insulating property. The foam can be installed in
sheets or sprayed in place where it will provide the best available thermal insulation per depth of material at an
acceptable price versus performance. No other commercially available product has a better price performance point
and polyurethane foams are increasingly being specified to meet the needs of more exacting building regulations for
thermal insulation.
The diagram below compares the degree of insulation of some common insulating materials used in construction.
These figures are calculated under the assumption of 'still' air but under real world conditions polyurethane sprayed in
place foam is more than 5 times more effective per depth over products such as glass or mineral wool insulation. This
is because no air currents can pass through the polyurethane due to the tight cell structure of the foam and it acts as an
air barrier preventing air from either side from mixing.
Comparison of building materials and relative insulation values under 'still' air conditions:

Under real world conditions with thermal air currents, ventilation and wind air movements the difference between rigid,
high density polyurethane foam and mineral wool or glass fibre insulation is 5 to 6:1 depth factor in favaour of
polyurethane foam since polyurethane is an air barrier as well as an insulator and needs less depth to achieve a
specified U value. This fact is not bourne out by laboratory calulations for lamda and 'U' values which adopt still air
conditions for testing and this unduly favours mineral wool and glass fibre insulation when considering price versus
performance.
Moulded urethanes are used in the automotive industry for items such as bumpers, steering wheels, instrument panels,
and body panels. Elastomers from polyurethanes are characterized by toughness and resistance to oils, oxidation, and
abrasion. They are produced using short-chain polyols such as polytetramethylene glycol from 1, 4-butanediol.
Polyurethanes are also used to produce fibres. For example, Spandex (trade name) is a copolymer of polyurethane
(85%) and polyesters.
Polyurethane foam typically has a low melting point and so cannot be used as a fire barrier. However, polyurethane
networks based on triisocyante and diisocyanate connected by segments consisting of polyisobutylene are fairly
rubbery and exhibit high temperature properties, hydrolyic stability, and barrier characteristics. This makes these types
of polyurethanes suitable as water proof coatings.