Polyurethane (PUR and PU) is a polymer composed of a chain of organic units join

ed by carbamate (urethane) links. While most polyurethanes are thermosetting pol

ymers that do not melt when heated, thermoplastic polyurethanes are also availab
le.
Polyurethane polymers are traditionally and most commonly formed by reacting a d
i- or polyisocyanate with a polyol. Both the isocyanates and polyols used to mak
e polyurethanes contain on average two or more functional groups per molecule.
Some noteworthy recent efforts have been dedicated to minimizing the use of isoc
yanates to synthesize polyurethanes, because the isocyanates raise severe toxici
ty issues. Non-isocyanate based polyurethanes (NIPUs) have recently been develop
ed as a new class of polyurethane polymers to mitigate health and environmental
concerns.[1][2][3][4]
Polyurethane products often are simply called urethanes , but should not be confuse
d with eth
yl carbamate, which is also called urethane. Polyurethanes neither contain nor a
re produced from ethyl carbamate.
Otto Bayer and his coworkers at I.G. Farben in Leverkusen, Germany, first made p
olyurethanes in 1937.[6] The new polymers had some advantages over existing plas
tics that were made by polymerizing olefins, or by polycondensation, and were no
t covered by patents obtained by Wallace Carothers on polyesters.[7] Early work
focused on the production of fibres and flexible foams and PUs were applied on a
limited scale as aircraft coating during World War II.[7] Polyisocyanates becam
e commercially available in 1952 and production of flexible polyurethane foam be
gan in 1954 using toluene diisocyanate (TDI) and polyester polyols. These materi
als were also used to produce rigid foams, gum rubber, and elastomers. Linear fi
bers were produced from hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO
).
In 1956 DuPont introduced polyether polyols, specifically poly(tetramethylene et
her) glycol and BASF and Dow Chemical started selling polyalkylene glycols in 19
57. Polyether polyols were cheaper, easier to handle and more water resistant th
an polyester polyols, and became more popular. Union Carbide and Mobay, a U.S. M
onsanto/Bayer joint venture, also began making polyurethane chemicals.[7] In 196
0 more than 45,000 metric tons of flexible polyurethane foams were produced. The
availability of chlorofluoroalkane blowing agents, inexpensive polyether polyol
s, and methylene diphenyl diisocyanate (MDI) allowed polyurethane rigid foams to
be used as high performance insulation materials. In 1967, urethane modified po
lyisocyanurate rigid foams were introduced, offering even better thermal stabili
ty and flammability resistance. During the 1960s, automotive interior safety com
ponents such as instrument and door panels were produced by back-filling thermop
lastic skins with semi-rigid foam.
In 1969, Bayer exhibited an all plastic car in Dsseldorf, Germany. Parts of this
car, such as the fascia and body panels were manufactured using a new process ca
lled RIM, Reaction Injection Molding in which the reactants were mixed then inje
cted into a mold. The addition of fillers, such as milled glass, mica, and proce
ssed mineral fibres gave rise to reinforced RIM (RRIM), which provided improveme
nts in flexural modulus (stiffness), reduction in coefficient of thermal expansi
on and thermal stability. This technology was used to make the first plastic-bod
y automobile in the United States, the Pontiac Fiero, in 1983. Further increases
in stiffness were obtained by incorporating pre-placed glass mats into the RIM
mold cavity, also known broadly as resin injection molding or structural RIM.
Starting in the early 1980s, water-blown microcellular flexible foams were used
to mold gaskets for automotive panels and air filter seals, replacing PVC plasti

sol from automotive applications have greatly increased market share. Polyuretha
ne foams are now used in high temperature oil filter applications.
Polyurethane foam (including foam rubber) is sometimes made using small amounts
of blowing agents to give less dense foam, better cushioning/energy absorption o
r thermal insulation. In the early 1990s, because of their impact on ozone deple
tion, the Montreal Protocol restricted the use of many chlorine-containing blowi
ng agents, such as trichlorofluoromethane (CFC-11). By the late 1990s, the use o
f blowing agents such as carbon dioxide, pentane, 1,1,1,2-tetrafluoroethane (HFC
-134a) and 1,1,1,3,3-pentafluoropropane (HFC-245fa) were widely used in North Am
erica and the EU, although chlorinated blowing agents remained in use in many de
veloping countries.[8]
In the 1990s new two-component polyurethane and hybrid polyurethane-polyurea ela
stomers were used for spray-in-place load bed liners and military marine applica
tions for the U.S. Navy. A one-part polyurethane is specified as high durability
deck coatings under MIL-PRF-32171[9] for the US Navy. This technique for coatin
g creates a durable, abrasion resistant composite with the metal substrate, and
eliminates corrosion and brittleness associated with drop-in thermoplastic bed l
iners.
Rising costs of petrochemical feedstocks and an enhanced public desire for envir
onmentally friendly green products raised interest in polyols derived from veget
able oils.[10] One of the most vocal supporters of these polyurethanes made usin
g natural oil polyols is the Ford Motor Company.[11]
Chemistry[edit]
Polyurethanes are in the class of compounds called reaction polymers, which incl
ude epoxies, unsaturated polyesters, and phenolics.[12][13][14][15][16] Polyuret
hanes are produced by reacting an isocyanate containing two or more isocyanate g
roups per molecule (R-(N=C=O)n = 2) with a polyol containing on average two or m
ore hydroxy groups per molecule (R'-(OH)n = 2), in the presence of a catalyst or
by activation with ultraviolet light.[17]
The properties of a polyurethane are greatly influenced by the types of isocyana
tes and polyols used to make it. Long, flexible segments, contributed by the pol
yol, give soft, elastic polymer. High amounts of crosslinking give tough or rigi
d polymers. Long chains and low crosslinking give a polymer that is very stretch
y, short chains with lots of crosslinks produce a hard polymer while long chains
and intermediate crosslinking give a polymer useful for making foam. The crossl
inking present in polyurethanes means that the polymer consists of a three-dimen
sional network and molecular weight is very high. In some respects a piece of po
lyurethane can be regarded as one giant molecule. One consequence of this is tha
t typical polyurethanes do not soften or melt when they are heated...they are th
ermosetting polymers. The choices available for the isocyanates and polyols, in
addition to other additives and processing conditions allow polyurethanes to hav
e the very wide range of properties that make them such widely used polymers.
Isocyanates are very reactive materials. This makes them useful in making polyme
rs but also requires special care in handling and use. The aromatic isocyanates,
diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) are more react
ive than aliphatic isocyanates, such as hexamethylene diisocyanate (HDI) or isop
horone diisocyanate (IPDI). Most of the isocyanates are difunctional, that is th
ey have exactly two isocyanate groups per molecule. An important exception to th
is is polymeric diphenylmethane diisocyanate, which is a mixture of molecules wi
th two-, three-, and four- or more isocyanate groups. In cases like this the mat
erial has an average functionality greater than two, commonly 2.7.
Polyols are polymers in their own right and have on average two or more hydroxyl
groups per molecule. Polyether polyols are mostly made by co-polymerizing ethyl

ene oxide and propylene oxide with a suitable polyol precursor.[18] Polyester po
lyols are made similarly to polyester polymers. The polyols used to make polyure
thanes are not "pure" compounds since they are often mixtures of similar molecul
es with different molecular weights and mixtures of molecules that contain diffe
rent numbers of hydroxyl groups, which is why the "average functionality" is oft
en mentioned. Despite them being complex mixtures, industrial grade polyols have
their composition sufficiently well controlled to produce polyurethanes having
consistent properties. As mentioned earlier, it is the length of the polyol chai
n and the functionality that contribute much to the properties of the final poly
mer. Polyols used to make rigid polyurethanes have molecular weights in the hund
reds, while those used to make flexible polyurethanes have molecular weights up
to ten thousand or more.
PU reaction mechanism catalyzed by a tertiary amine
reaction meachanism
generalized urethane reaction
generalized polyurethane reaction
The polymerization reaction makes a polymer containing the urethane linkage, -RN
HCOOR'- and is catalyzed by tertiary amines, such as 1,4-diazabicyclo[2.2.2]octa
ne (also called DABCO or TEDA), and metallic compounds, such as dibutyltin dilau
rate or bismuth octanoate. Alternatively, it can be promoted by ultraviolet ligh
t.[17] This is often referred to as the gellation reaction or simply gelling.
If water is present in the reaction mixture (it is often added intentionally to
make foams), the isocyanate reacts with water to form a urea linkage and carbon
dioxide gas and the resulting polymer contains both urethane and urea linkages.
This reaction is referred to as the blowing reaction and is catalyzed by tertiar
y amines like bis-(2-dimethylaminoethyl)ether.
A third reaction, particularly important in making insulating rigid foams is the
isocyanate trimerization reaction, which is catalyzed by potassium octoate, for
example.
One of the most desirable attributes of polyurethanes is their ability to be tur
ned into foam. Making a foam requires the formation of a gas at the same time as
the urethane polymerization (gellation) is occurring. The gas can be carbon dio
xide, either generated by reacting isocyanate with water. or added as a gas or p
roduced by boiling volatile liquids. In the latter case heat generated by the po
lymerization causes the liquids to vaporize. The liquids can be HFC-245fa (1,1,1
,3,3-pentafluoropropane) and HFC-134a (1,1,1,2-tetrafluoroethane), and hydrocarb
ons such as n-pentane.
carbon dioxide gas formed by reacting water and isocyanate
water isocyanate reaction
The balance between gellation and blowing is sensitive to operating parameters i
ncluding the concentrations of water and catalyst. The reaction to generate carb
on dioxide involves water reacting with an isocyanate first forming an unstable
carbamic acid, which then decomposes into carbon dioxide and an amine. The amine
reacts with more isocyanate to give a substituted urea. Water has a very low mo
lecular weight, so even though the weight percent of water may be small, the mol
ar proportion of water may be high and considerable amounts of urea produced. Th
e urea is not very soluble in the reaction mixture and tends to form separate "h
ard segment" phases consisting mostly of polyurea. The concentration and organiz
ation of these polyurea phases can have a significant impact on the properties o
f the polyurethane foam.[19]
High-density microcellular foams can be formed without the addition of blowing a
gents by mechanically frothing or nucleating the polyol component prior to use.
Surfactants are used in polyurethane foams to emulsify the liquid components, re

gulate cell size, and stabilize the cell structure to prevent collapse and surfa
ce defects. Rigid foam surfactants are designed to produce very fine cells and a
very high closed cell content. Flexible foam surfactants are designed to stabil
ize the reaction mass while at the same time maximizing open cell content to pre
vent the foam from shrinking.
An even more rigid foam can be made with the use of specialty trimerization cata
lysts which create cyclic structures within the foam matrix, giving a harder, mo
re thermally stable structure, designated as polyisocyanurate foams. Such proper
ties are desired in rigid foam products used in the construction sector.
Careful control of viscoelastic properties
by modifying the catalysts and polyol
s used can lead to memory foam, which is much softer at skin temperature than at
room temperature.
Foams can be either "closed cell", where most of the original bubbles or cells r
emain intact, or "open cell", where the bubbles have broken but the edges of the
bubbles are stiff enough to retain their shape. Open cell foams feel soft and a
llow air to flow through so they are comfortable when used in seat cushions or m
attresses. Closed cell rigid foams are used as thermal insulation, for example i
n refrigerators.
Microcellular foams are tough elastomeric materials used in coverings of car ste
ering wheels or shoe soles.
Raw materials[edit]
The main ingredients to make a polyurethane are isocyanates and polyols. Other m
aterials are added to help processing the polymer or to change the properties of
the polymer.
Isocyanates[edit]
Isocyanates used to make polyurethane must have two or more isocyanate groups on
each molecule. The most commonly used isocyanates are the aromatic diisocyantes
, toluene diisocyanate (TDI) and methylene diphenyl diisocyanate, MDI.
TDI and MDI are generally less expensive and more reactive than other isocyanate
s. Industrial grade TDI and MDI are mixtures of isomers and MDI often contains p
olymeric materials. They are used to make flexible foam (for example slabstock f
oam for mattresses or molded foams for car seats),[20] rigid foam (for example i
nsulating foam in refrigerators) elastomers (shoe soles, for example), and so on
. The isocyanates may be modified by partially reacting them with polyols or int
roducing some other materials to reduce volatility (and hence toxicity) of the i
socyanates, decrease their freezing points to make handling easier or to improve
the properties of the final polymers.
MDI isomers and polymer
Aliphatic and cycloaliphatic isocyanates are used in smaller volumes, most often
in coatings and other applications where color and transparency are important s
ince polyurethanes made with aromatic isocyanates tend to darken on exposure to
light.[21] The most important aliphatic and cycloaliphatic isocyanates are 1,6-h
examethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl
-cyclohexane (isophorone diisocyanate, IPDI), and 4,4'-diisocyanato dicyclohexyl
methane, (H12MDI or hydrogenated MDI).
Polyols[edit]
Polyols can be polyether polyols, which are made by the reaction of epoxides wit
h an active hydrogen containing starter compounds, or polyester polyols, which a
re made by the polycondensation of multifunctional carboxylic acids and hydroxyl
compounds. They can be further classified according to their end use. Higher mo
lecular weight polyols (molecular weights from 2,000 to 10,000) are used to make

more flexible polyurethanes while lower molecular weight polyols make more rigi
d products.
Polyols for flexible applications use low functionality initiators such as dipro
pylene glycol (f=2), glycerine (f=3) or a sorbitol/water solution (f=2.75).[22]
Polyols for rigid applications use high functionality initiators such as sucrose
(f=8), sorbitol (f=6), toluenediamine (f=4), and Mannich bases (f=4). Propylene
oxide and/or ethylene oxide is added to the initiators until the desired molecu
lar weight is achieved. The order of addition and the amounts of each oxide affe
ct many polyol properties, such as compatibility, water-solubility, and reactivi
ty. Polyols made with only propylene oxide are terminated with secondary hydroxy
l groups and are less reactive than polyols capped with ethylene oxide, which co
ntain primary hydroxyl groups. Graft polyols (also called filled polyols or poly
mer polyols) contain finely dispersed styrene-acrylonitrile, acrylonitrile, or p
olyurea (PHD) polymer solids chemically grafted to a high molecular weight polye
ther backbone. They are used to increase the load-bearing properties of low-dens
ity high-resiliency (HR) foam, as well as add toughness to microcellular foams a
nd cast elastomers. Initiators such as ethylenediamine and triethanolamine are u
sed to make low molecular weight rigid foam polyols that have built-in catalytic
activity due to the presence of nitrogen atoms in the backbone. A special class
of polyether polyols, poly(tetramethylene ether) glycols, which are made by pol
ymerizing tetrahydrofuran, are used in high performance coating, wetting and ela
stomer applications.
Conventional polyester polyols are based on virgin raw materials and are manufac
tured by the direct polyesterification of high-purity diacids and glycols, such
as adipic a