Polyurethane

The new polymers had some advantages over existing

plastics that were made by polymerizing olens, or by
polycondensation, and were not covered by patents obtained by Wallace Carothers on polyesters.[7] Early work
focused on the production of bres and exible foams
and PUs were applied on a limited scale as aircraft
coating during World War II.[7] Polyisocyanates became
commercially available in 1952 and production of exiPolyurethane synthesis, wherein the urethane groups NH- ble polyurethane foam began in 1954 using toluene di(C=O)-O- link the molecular units.
isocyanate (TDI) and polyester polyols. These materials were also used to produce rigid foams, gum rubPolyurethane (PUR and PU) is a polymer composed ber, and elastomers. Linear bers were produced from
of a chain of organic units joined by carbamate (ure- hexamethylene diisocyanate (HDI) and 1,4-butanediol
thane) links. While most polyurethanes are thermosetting (BDO).
polymers that do not melt when heated, thermoplastic In 1956 DuPont introduced polyether polyols, specipolyurethanes are also available.
cally poly(tetramethylene ether) glycol and BASF and
Dow Chemical started selling polyalkylene glycols in
1957. Polyether polyols were cheaper, easier to handle and more water resistant than polyester polyols, and
became more popular. Union Carbide and Mobay, a
U.S. Monsanto/Bayer joint venture, also began making
polyurethane chemicals.[7] In 1960 more than 45,000
metric tons of exible polyurethane foams were produced. The availability of chlorouoroalkane blowing
agents, inexpensive polyether polyols, and methylene
diphenyl diisocyanate (MDI) allowed polyurethane rigid
foams to be used as high performance insulation materials. In 1967, urethane modied polyisocyanurate
rigid foams were introduced, oering even better thermal stability and ammability resistance. During the
1960s, automotive interior safety components such as instrument and door panels were produced by back-lling
thermoplastic skins with semi-rigid foam.

Polyurethane polymers are traditionally and most commonly formed by reacting a di- or polyisocyanate with a
polyol. Both the isocyanates and polyols used to make
polyurethanes contain on average two or more functional
groups per molecule.
Some noteworthy recent eorts have been dedicated
to minimizing the use of isocyanates to synthesize
polyurethanes, because the isocyanates raise severe toxicity issues. Non-isocyanate based polyurethanes (NIPUs) have recently been developed 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 confused with ethyl carbamate,
which is also called urethane. Polyurethanes neither contain nor are produced from ethyl carbamate.
Polyurethanes are used in the manufacture of nonexible, high-resilience foam seating; rigid foam insulation panels; microcellular foam seals and gaskets;
durable elastomeric wheels and tires (such as roller
coaster, escalator and skateboard wheels); automotive
suspension bushings; electrical potting compounds; high
performance adhesives; surface coatings and surface
sealants; synthetic bers (e.g., Spandex); carpet underlay; hard-plastic parts (e.g., for electronic instruments);
condoms;[5] and hoses.

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 called
RIM, Reaction Injection Molding in which the reactants
were mixed then injected into a mold. The addition of
llers, such as milled glass, mica, and processed mineral bres gave rise to reinforced RIM (RRIM), which
provided improvements in exural modulus (stiness),
reduction in coecient of thermal expansion and thermal stability. This technology was used to make the rst
plastic-body automobile in the United States, the Pontiac
Fiero, in 1983. Further increases in stiness were obtained by incorporating pre-placed glass mats into the
RIM mold cavity, also known broadly as resin injection
molding or structural RIM.

History

Otto Bayer and his coworkers at I.G. Farben in Leverkusen, Germany, rst made polyurethanes in 1937.[6] Starting in the early 1980s, water-blown microcellular
1

2 CHEMISTRY

exible foams were used to mold gaskets for automotive panels and air lter seals, replacing PVC plastisol
from automotive applications have greatly increased market share. Polyurethane foams are now used in high temperature oil lter applications.

high. In some respects a piece of polyurethane can be regarded as one giant molecule. One consequence of this
is that typical polyurethanes do not soften or melt when
they are heated...they are thermosetting polymers. The
choices available for the isocyanates and polyols, in adPolyurethane foam (including foam rubber) is some- dition to other additives and processing conditions allow
times made using small amounts of blowing agents to polyurethanes to have the very wide range of properties
give less dense foam, better cushioning/energy absorp- that make them such widely used polymers.
tion or thermal insulation. In the early 1990s, because of Isocyanates are very reactive materials. This makes
their impact on ozone depletion, the Montreal Protocol them useful in making polymers but also requires sperestricted the use of many chlorine-containing blowing cial care in handling and use. The aromatic isocyanates,
agents, such as trichlorouoromethane (CFC-11). By the diphenylmethane diisocyanate (MDI) or toluene diisolate 1990s, the use of blowing agents such as carbon diox- cyanate (TDI) are more reactive than aliphatic isoide, pentane, 1,1,1,2-tetrauoroethane (HFC-134a) and cyanates, such as hexamethylene diisocyanate (HDI) or
1,1,1,3,3-pentauoropropane (HFC-245fa) were widely isophorone diisocyanate (IPDI). Most of the isocyanates
used in North America and the EU, although chlori- are difunctional, that is they have exactly two isocyanate
nated blowing agents remained in use in many developing groups per molecule. An important exception to this is
countries.[8]
polymeric diphenylmethane diisocyanate, which is a mixIn the 1990s new two-component polyurethane and hy- ture of molecules with two-, three-, and four- or more
brid polyurethane-polyurea elastomers were used for isocyanate groups. In cases like this the material has an
spray-in-place load bed liners and military marine ap- average functionality greater than two, commonly 2.7.
plications for the U.S. Navy. A one-part polyurethane
is specied as high durability deck coatings under MILPRF-32171[9] for the US Navy. This technique for coating creates a durable, abrasion resistant composite with
the metal substrate, and eliminates corrosion and brittleness associated with drop-in thermoplastic bed liners.
Rising costs of petrochemical feedstocks and an enhanced public desire for environmentally friendly green
products raised interest in polyols derived from vegetable
oils.[10] One of the most vocal supporters of these
polyurethanes made using natural oil polyols is the Ford
Motor Company.[11]

Chemistry

Polyurethanes are in the class of compounds called reaction polymers, which include epoxies, unsaturated
polyesters, and phenolics.[12][13][14][15][16] Polyurethanes
are produced by reacting an isocyanate containing two or
more isocyanate groups per molecule (R-(N=C=O) )
with a polyol containing on average two or more hydroxy
groups per molecule (R'-(OH) ), in the presence of a
catalyst or by activation with ultraviolet light.[17]

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
ethylene oxide and propylene oxide with a suitable
polyol precursor.[18] Polyester polyols are made similarly to polyester polymers. The polyols used to make
polyurethanes are not pure compounds since they are
often mixtures of similar molecules with dierent molecular weights and mixtures of molecules that contain different numbers of hydroxyl groups, which is why the average functionality is often mentioned. Despite them
being complex mixtures, industrial grade polyols have
their composition suciently well controlled to produce
polyurethanes having consistent properties. As mentioned earlier, it is the length of the polyol chain and the
functionality that contribute much to the properties of the
nal polymer. Polyols used to make rigid polyurethanes
have molecular weights in the hundreds, while those used
to make exible polyurethanes have molecular weights up
to ten thousand or more.

The polymerization reaction makes a polymer containing the urethane linkage, -RNHCOOR'- and is catalyzed
by tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane
(also called DABCO or TEDA), and metallic compounds, such as dibutyltin dilaurate or bismuth octanoate.
[17]
The properties of a polyurethane are greatly inuenced Alternatively, it can be promoted by ultraviolet light.
by the types of isocyanates and polyols used to make it. This is often referred to as the gellation reaction or simply
Long, exible segments, contributed by the polyol, give gelling.
soft, elastic polymer. High amounts of crosslinking give If water is present in the reaction mixture (it is often
tough or rigid polymers. Long chains and low crosslink- added intentionally to make foams), the isocyanate reing give a polymer that is very stretchy, short chains acts with water to form a urea linkage and carbon dioxide
with lots of crosslinks produce a hard polymer while gas and the resulting polymer contains both urethane and
long chains and intermediate crosslinking give a poly- urea linkages. This reaction is referred to as the blowing
mer useful for making foam. The crosslinking present reaction and is catalyzed by tertiary amines like bis-(2in polyurethanes means that the polymer consists of a dimethylaminoethyl)ether.
three-dimensional network and molecular weight is very

3
A third reaction, particularly important in making insu- able when used in seat cushions or mattresses. Closed cell
lating rigid foams is the isocyanate trimerization reaction, rigid foams are used as thermal insulation, for example in
which is catalyzed by potassium octoate, for example.
refrigerators.
One of the most desirable attributes of polyurethanes is
their ability to be turned 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 dioxide, either generated by reacting isocyanate with water. or added as a gas or produced by boiling volatile liquids. In the latter case heat generated by the
polymerization causes the liquids to vaporize. The liquids
can be HFC-245fa (1,1,1,3,3-pentauoropropane) and
HFC-134a (1,1,1,2-tetrauoroethane), and hydrocarbons
such as n-pentane.
The balance between gellation and blowing is sensitive
to operating parameters including the concentrations of
water and catalyst. The reaction to generate carbon dioxide involves water reacting with an isocyanate rst 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 molecular weight, so even though the weight percent of water may be small, the molar proportion of water
may be high and considerable amounts of urea produced.
The urea is not very soluble in the reaction mixture and
tends to form separate hard segment phases consisting
mostly of polyurea. The concentration and organization
of these polyurea phases can have a signicant impact on
the properties of the polyurethane foam.[19]
High-density microcellular foams can be formed without
the addition of blowing agents by mechanically frothing
or nucleating the polyol component prior to use.
Surfactants are used in polyurethane foams to emulsify
the liquid components, regulate cell size, and stabilize
the cell structure to prevent collapse and surface defects.
Rigid foam surfactants are designed to produce very ne
cells and a very high closed cell content. Flexible foam
surfactants are designed to stabilize the reaction mass
while at the same time maximizing open cell content to
prevent the foam from shrinking.

Microcellular foams are tough elastomeric materials used

in coverings of car steering wheels or shoe soles.

3 Raw materials
The main ingredients to make a polyurethane are
isocyanates and polyols. Other materials are added to
help processing the polymer or to change the properties
of the polymer.

3.1 Isocyanates
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 isocyanates. Industrial grade TDI and
MDI are mixtures of isomers and MDI often contains
polymeric materials. They are used to make exible foam
(for example slabstock foam for mattresses or molded
foams for car seats),[20] rigid foam (for example insulating foam in refrigerators) elastomers (shoe soles, for example), and so on. The isocyanates may be modied by
partially reacting them with polyols or introducing some
other materials to reduce volatility (and hence toxicity)
of the isocyanates, decrease their freezing points to make
handling easier or to improve the properties of the nal
polymers.

An even more rigid foam can be made with the use

of specialty trimerization catalysts which create cyclic
structures within the foam matrix, giving a harder, more
thermally stable structure, designated as polyisocyanurate
foams. Such properties are desired in rigid foam products
used in the construction sector.
MDI isomers and polymer
Careful control of viscoelastic properties by modifying the catalysts and polyols used can lead to memory Aliphatic and cycloaliphatic isocyanates are used in
foam, which is much softer at skin temperature than at smaller volumes, most often in coatings and other
room temperature.
applications where color and transparency are imFoams can be either closed cell, where most of the orig- portant since polyurethanes made with aromatic
[21]
inal bubbles or cells remain intact, or open cell, where isocyanates tend to darken on exposure to light.
the bubbles have broken but the edges of the bubbles are The most important aliphatic and cycloaliphatic isosti enough to retain their shape. Open cell foams feel cyanates are 1,6-hexamethylene diisocyanate (HDI),
soft and allow air to ow through so they are comfort- 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), and

RAW MATERIALS

4,4'-diisocyanato dicyclohexylmethane, (H12 MDI or polyurethane spray foam insulation.

hydrogenated MDI).
Specialty polyols include polycarbonate polyols,
polycaprolactone polyols, polybutadiene polyols, and
polysulde polyols. The materials are used in elastomer,
3.2 Polyols
sealant, and adhesive applications that require superior
Polyols can be polyether polyols, which are made by the weatherability, and resistance to chemical and environreaction of epoxides with an active hydrogen containing mental attack. Natural oil polyols derived from castor
starter compounds, or polyester polyols, which are made oil and other vegetable oils are used to make elastomers,
by the polycondensation of multifunctional carboxylic exible bunstock, and exible molded foam. Copolyacids and hydroxyl compounds. They can be further merizing chlorotriuoroethylene or tetrauoroethylene
classied according to their end use. Higher molecular with vinyl ethers containing hydroxyalkyl vinyl ether
weight polyols (molecular weights from 2,000 to 10,000) produces uorinated (FEVE) polyols. Two component
are used to make more exible polyurethanes while lower uorinated polyurethane prepared by reacting FEVE
uorinated polyols with polyisocyanate have been
molecular weight polyols make more rigid products.
applied for make ambient cure paint/coating. Since
Polyols for exible applications use low functionality ini- uorinated polyurethanes contain high percentage of
tiators such as dipropylene glycol (f=2), glycerine (f=3) or uorine-carbon bond which is the strongest bond among
a sorbitol/water solution (f=2.75).[22] Polyols for rigid ap- all chemical bonds. Fluorinated polyurethanes have
plications use high functionality initiators such as sucrose excellent resistance to UV, acids, alkali, salts, chemicals,
(f=8), sorbitol (f=6), toluenediamine (f=4), and Mannich solvents, weathering, corrosion, fungi and microbial
bases (f=4). Propylene oxide and/or ethylene oxide is attack. These have become the rst choice for high
added to the initiators until the desired molecular weight performance coating/paints.
is achieved. The order of addition and the amounts
of each oxide aect many polyol properties, such as
compatibility, water-solubility, and reactivity. Polyols 3.3 Chain extenders and cross linkers
made with only propylene oxide are terminated with secondary hydroxyl groups and are less reactive than poly- Chain extenders (f=2) and cross linkers (f=3 or greater)
ols capped with ethylene oxide, which contain primary are low molecular weight hydroxyl and amine terminated
hydroxyl groups. Graft polyols (also called lled poly- compounds that play an important role in the polymer
ols or polymer polyols) contain nely dispersed styrenemorphology of polyurethane bers, elastomers, adheacrylonitrile, acrylonitrile, or polyurea (PHD) polymer sives, and certain integral skin and microcellular foams.
solids chemically grafted to a high molecular weight
The elastomeric properties of these materials are depolyether backbone. They are used to increase the load- rived from the phase separation of the hard and soft
bearing properties of low-density high-resiliency (HR)
copolymer segments of the polymer, such that the urefoam, as well as add toughness to microcellular foams and thane hard segment domains serve as cross-links between
cast elastomers. Initiators such as ethylenediamine and
the amorphous polyether (or polyester) soft segment dotriethanolamine are used to make low molecular weight mains. This phase separation occurs because the mainly
rigid foam polyols that have built-in catalytic activity due non-polar, low melting soft segments are incompatible
to the presence of nitrogen atoms in the backbone. A spe- with the polar, high melting hard segments. The soft
cial class of polyether polyols, poly(tetramethylene ether) segments, which are formed from high molecular weight
glycols, which are made by polymerizing tetrahydrofuran, polyols, are mobile and are normally present in coiled
are used in high performance coating, wetting and elas- formation, while the hard segments, which are formed
tomer applications.
from the isocyanate and chain extenders, are sti and imConventional polyester polyols are based on virgin raw
materials and are manufactured by the direct polyesterication of high-purity diacids and glycols, such as
adipic acid and 1,4-butanediol.
Polyester polyols
are usually more expensive and more viscous than
polyether polyols, but they make polyurethanes with
better solvent, abrasion, and cut resistance. Other
polyester polyols are based on reclaimed raw materials.
They are manufactured by transesterication (glycolysis) of recycled poly(ethyleneterephthalate)
(PET) or dimethylterephthalate (DMT) distillation bottoms with glycols such as diethylene glycol. These low
molecular weight, aromatic polyester polyols are used in
rigid foam, and bring low cost and excellent ammability
characteristics to polyisocyanurate (PIR) boardstock and

mobile. Because the hard segments are covalently coupled to the soft segments, they inhibit plastic ow of
the polymer chains, thus creating elastomeric resiliency.
Upon mechanical deformation, a portion of the soft segments are stressed by uncoiling, and the hard segments
become aligned in the stress direction. This reorientation of the hard segments and consequent powerful hydrogen bonding contributes to high tensile strength, elongation, and tear resistance values.[14][23][24][25][26] The
choice of chain extender also determines exural, heat,
and chemical resistance properties. The most important
chain extenders are ethylene glycol, 1,4-butanediol (1,4BDO or BDO), 1,6-hexanediol, cyclohexane dimethanol
and hydroquinone bis(2-hydroxyethyl) ether (HQEE). All
of these glycols form polyurethanes that phase sepa-

5
rate well and form well dened hard segment domains,
and are melt processable. They are all suitable for
thermoplastic polyurethanes with the exception of ethylene glycol, since its derived bis-phenyl urethane undergoes unfavorable degradation at high hard segment
levels.[12] Diethanolamine and triethanolamine are used
in ex molded foams to build rmness and add catalytic
activity. Diethyltoluenediamine is used extensively in
RIM, and in polyurethane and polyurea elastomer formulations.

4 Production

Polyurethanes are produced by mixing two or more liquid streams. The polyol stream contains catalysts, surfactants, blowing agents and so on. The two components are
referred to as a polyurethane system, or simply a system.
The isocyanate is commonly referred to in North America
as the 'B-side' or just the 'iso'. The blend of polyols and
other additives is commonly referred to as the 'A-side' or
as the 'poly'. This mixture might also be called a 'resin'
or 'resin blend'. In Europe the meanings for 'A-side' and
'B-side' are reversed. Resin blend additives may include
chain extenders, cross linkers, surfactants, ame retar3.4 Catalysts
dants, blowing agents, pigments, and llers. Polyurethane
Polyurethane catalysts can be classied into two can be made in a variety of densities and hardnesses by
broad categories, amine compounds and metal varying the isocyanate, polyol or additives.
complexes.
Traditional amine catalysts have
been tertiary amines such as triethylenediamine
(TEDA, 1,4-diazabicyclo[2.2.2]octane or DABCO),
dimethylcyclohexylamine
(DMCHA),
and
dimethylethanolamine (DMEA). Tertiary amine 5 Health and safety
catalysts are selected based on whether they drive the
urethane (polyol+isocyanate, or gel) reaction, the urea
(water+isocyanate, or blow) reaction, or the isocyanate Fully reacted polyurethane polymer is chemically
[32]
No exposure limits have been established in
trimerization reaction (e.g., using potassium acetate, to inert.
the
U.S.
by OSHA (Occupational Safety and Health
form isocyanurate ring structure). Catalysts that contain
Administration)
or ACGIH (American Conference of
a hydroxyl group or secondary amine, which react into
Governmental
Industrial
Hygienists). It is not regulated
the polymer matrix, can replace traditional catalysts
by
OSHA
for
carcinogenicity.
thereby reducing the amount of amine that can come out
of the polymer.[28][29]
Polyurethane polymer is a combustible solid and can be
[33]
Decomposition
Metallic compounds based on mercury, lead, tin, ignited if exposed to an open ame.
bismuth, and zinc are used as polyurethane catalysts. from re can produce mainly carbon monoxide, and trace
Mercury carboxylates, are particularly eective catalysts nitrogen oxides and hydrogen cyanide. Because of the
for polyurethane elastomer, coating and sealant applica- ammability of the material, it has to be treated with
tions, since they are very highly selective towards the ame retardands (at least in case of furniture), almost all
[34][35]
polyol+isocyanate reaction, but they are toxic. Bismuth of which are considered harmful.
and zinc carboxylates have been used as alternatives. Liquid resin blends and isocyanates may contain hazAlkyl tin carboxylates, oxides and mercaptides oxides are ardous or regulated components. Isocyanates are known
used in all types of polyurethane applications. Tin mer- skin and respiratory sensitizers. Additionally, amines,
captides are used in formulations that contain water, as glycols, and phosphate present in spray polyurethane
tin carboxylates are susceptible to hydrolysis.[30][31]
foams present risks.[36]

3.5

Surfactants

Surfactants are used to modify the characteristics of both

foam and non-foam polyurethane polymers. They take
the form of polydimethylsiloxane-polyoxyalkylene block
copolymers, silicone oils, nonylphenol ethoxylates, and
other organic compounds. In foams, they are used to
emulsify the liquid components, regulate cell size, and
stabilize the cell structure to prevent collapse and subsurface voids. In non-foam applications they are used as
air release and anti-foaming agents, as wetting agents, and
are used to eliminate surface defects such as pin holes, orange peel, and sink marks.

Substrates used during application of Polyurethane Spray

Foam (such as isocyanates) are harmful to human health
and therefore special precautions are required during and
after this process.[37]
In the United States, additional health and safety information can be found through organizations such as the
Polyurethane Manufacturers Association (PMA) and the
Center for the Polyurethanes Industry (CPI), as well as
from polyurethane system and raw material manufacturers. Regulatory information can be found in the Code of
Federal Regulations Title 21 (Food and Drugs) and Title
40 (Protection of the Environment). In Europe, health
and safety information is available from ISOPA,[38] the
European Diisocyanate and Polyol Producers Association.

6 MANUFACTURING

Manufacturing

The methods of manufacturing polyurethane nished

goods range from small, hand pour piece-part operations
to large, high-volume bunstock and boardstock production lines. Regardless of the end-product, the manufacturing principle is the same: to meter the liquid isocyanate
and resin blend at a specied stoichiometric ratio, mix
them together until a homogeneous blend is obtained, dispense the reacting liquid into a mold or on to a surface,
wait until it cures, then demold the nished part.

6.1

Dispensing equipment

Although the capital outlay can be high, it is desirable

to use a meter-mix or dispense unit for even low-volume
production operations that require a steady output of nished parts. Dispense equipment consists of material
holding (day) tanks, metering pumps, a mix head, and a
control unit. Often, a conditioning or heater-chiller unit is
added to control material temperature in order to improve
mix eciency, cure rate, and to reduce process variability. Choice of dispense equipment components depends
on shot size, throughput, material characteristics such as
viscosity and ller content, and process control. Material
day tanks may be single to hundreds of gallons in size, and
may be supplied directly from drums, IBCs (intermediate bulk containers, such as totes), or bulk storage tanks.
They may incorporate level sensors, conditioning jackets,
and mixers. Pumps can be sized to meter in single grams
per second up to hundreds of pounds per minute. They
can be rotary, gear, or piston pumps, or can be specially
hardened lance pumps to meter liquids containing highly
abrasive llers such as wollastonite, chopped or hammer
milled glass bres.

or fourth stream capability for adding pigments or metering in supplemental additive packages.
A low pressure mix head with calibration chamber
installed, showing material supply and air actuator
lines.
Low pressure mix head components, including mix
chambers, conical mixers, and mounting plates.
5-gallon (20-liter) material day tanks for supplying
a low pressure dispense unit.

6.2 Tooling
Distinct from pour-in-place, bun and boardstock, and
coating applications, the production of piece parts requires tooling to contain and form the reacting liquid.
The choice of mold-making material is dependent on the
expected number of uses to end-of-life (EOL), molding
pressure, exibility, and heat transfer characteristics.
RTV silicone is used for tooling that has an EOL in the
thousands of parts. It is typically used for molding rigid
foam parts, where the ability to stretch and peel the mold
around undercuts is needed. The heat transfer characteristic of RTV silicone tooling is poor. High-performance,
exible polyurethane elastomers are also used in this way.

Epoxy, metal-lled epoxy, and metal-coated epoxy is

used for tooling that has an EOL in the tens-of-thousands
of parts. It is typically used for molding exible foam
cushions and seating, integral skin and microcellular
foam padding, and shallow-draft RIM bezels and fascia.
A high pressure polyurethane dispense unit, show- The heat transfer characteristic of epoxy tooling is fair;
ing control panel, high pressure pump, integral day the heat transfer characteristic of metal-lled and metaltanks, and hydraulic drive unit.
coated epoxy is good. Copper tubing can be incorporated
into the body of the tool, allowing hot water to circulate
A high pressure mix head, showing simple controls.
and heat the mold surface.
Front view.
Aluminum is used for tooling that has an EOL in the
A high pressure mix head, showing material supply hundreds-of-thousands of parts. It is typically used for
and hydraulic actuator lines. Rear view.
molding microcellular foam gasketing and cast elastomer
parts, and is milled or extruded into shape.
The pumps can drive low-pressure (10 to 30 bar, ~1 to
3 MPa) or high-pressure (125 to 250 bar, ~12.5 to 25.0 Mirror-nish stainless steel is used for tooling that imMPa) dispense systems. Mix heads can be simple static parts a glossy appearance to the nished part. The heat
mix tubes, rotary element mixers, low-pressure dynamic transfer characteristic of metal tooling is excellent.
mixers, or high-pressure hydraulically actuated direct im- Finally, molded or milled polypropylene is used to crepingement mixers. Control units may have basic on/o ate low-volume tooling for molded gasket applications.
dispense/stop switches, and analogue pressure and tem- Instead of many expensive metal molds, low-cost plastic
perature gauges, or may be computer controlled with ow tooling can be formed from a single metal master, which
meters to electronically calibrate mix ratio, digital tem- also allows greater design exibility. The heat transfer
perature and level sensors, and a full suite of statistical characteristic of polypropylene tooling is poor, which
process control software. Add-ons to dispense equip- must be taken into consideration during the formulation
ment include nucleation or gas injection units, and third process.

Applications

Main articles: List of polyurethane applications and

Polyurethane varnish
In 2007, the global consumption of polyurethane raw materials was above 12 million metric tons, the average annual growth rate is about 5%.[39] Revenues generated with
PUR on the global market are expected to rise to approximately US$80 billion by 2020.[40]

Eects of visible light

Polyurethanes, especially those made using aromatic isocyanates, contain chromophores which interact with light.
This is of particular interest in the area of polyurethane
coatings, where light stability is a critical factor and is
the main reason that aliphatic isocyanates are used in
making polyurethane coatings. When PU foam, which
is made using aromatic isocyanates, is exposed to visible light it discolors, turning from o-white to yellow
to reddish brown. It has been generally accepted that
apart from yellowing, visible light has little eect on foam
properties.[41][42] This is especially the case if the yellowing happens on the outer portions of a large foam, as the
deterioration of properties in the outer portion has little
eect on the overall bulk properties of the foam itself.
It has been reported that exposure to visible light can
aect the variability of some physical property test
results.[43]
Higher-energy UV radiation promotes chemical reactions
in foam, some of which are detrimental to the foam
structure.[44]

11 References
[1] Delebecq, E.; Pascault, J.-P.; Boutevin, B.; Ganachaud,
F. (2013).
On the Versatility of Urethane/Urea
Bonds: Reversibility, Blocked Isocyanate, and NonIsocyanate Urethane. Chemical Reviews 113: 80118.
doi:10.1021/cr300195n.
[2] Helou, M.; Carpentier, J.-F.; Guillaume, S. M.
(2011).
Poly(carbonate-urethane): an isocyanatefree procedure from a,w-di(cyclic carbonate) telechelic
poly(trimethylene carbonate)s. Green Chem. 13: 266.
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[3] Javni, I.; Hong, D. P.; Petrovic, Z. S. Polyurethanes from
Soybean Oil, Aromatic, and Cycloaliphatic Diamines by
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Derived
upon
the Reaction of Amines with Cyclocarbonate
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[5] About Health: Polyurethane Condoms
[6] Bayer,
Otto (1947).
Das Di-IsocyanatPolyadditionsverfahren (Polyurethane)".
Angewandte
Chemie 59: 257272. doi:10.1002/ange.19470590901.;
See also German Patent 728.981 (1937) I.G. Farben
[7] Seymour, Raymond B.; Kauman, George B. (1992).
Polyurethanes: A Class of Modern Versatile Materials.
J. Chem. Ed. 69: 909. doi:10.1021/ed069p909.
[8] Feske, Bert (October 2004). The Use of Saytex RB9130/9170 Low Viscosity Brominated Flame Retardant
Polyols in HFC-245fa and High Water Formulations
(PDF). Polyurethanes Expo 2004. Las Vegas, NV: Alliance for the Polyurethane Industry Technical Conference. p. 309. Retrieved 2007-08-01.
[9] NST Center. (2010). Mil Specs for High Durability
Deck Coatings (Mil-prf-32171) Durabak-M26

Biodegradation

[10] Niemeyer, Timothy; Patel, Munjal and Geiger, Eric

(September 2006). A Further Examination of Soy-Based
Polyols in Polyurethane Systems. Salt Lake City, UT: Alliance for the Polyurethane Industry Technical Conference.

Two species of the Ecuadorian fungus Pestalotiopsis are

capable of biodegrading Polyurethane in aerobic and
anaerobic conditions such as found at the bottom of
landlls.[45] Degradation of polyurethane items at muse- [11] New Twist on Green: 2008 Ford Mustang Seats Will
ums has been reported.[46] Polyester type polyurethanes
Be Soy-Based Foam. Edmunds inside line. July 12,
are more easily biodegraded by fungus than polyether
2007. Archived from the original on 2008-05-31. Retrieved 2010-06-15.
type.[47]

10

See also

Thermoplastic polyurethanes
Passive re protection
Penetrant (mechanical, electrical, or structural)

[12] Gum, Wilson; Riese, Wolfram; Ulrich, Henri (1992). Reaction Polymers. New York: Oxford University Press.
ISBN 0-19-520933-8.
[13] Harrington, Ron; Hock, Kathy (1991).
Flexible
Polyurethane Foams. Midland: The Dow Chemical Company.
[14] Oertel, Gunter (1985). Polyurethane Handbook. New
York: Macmillen Publishing Co., Inc. ISBN 0-02948920-2.

[15] Ulrich, Henri (1996). Chemistry and Technology of Isocyanates. New York: John Wiley & Sons, Inc. ISBN 0471-96371-2.
[16] Woods, George (1990). The ICI Polyurethanes Book. New
York: John Wiley & Sons, Inc. ISBN 0-471-92658-2.
[17] Soto, Marc; Sebastin, Rosa Mara; Marquet, Jordi
(2014).
Photochemical Activation of Extremely
Weak Nucleophiles: Highly Fluorinated Urethanes and
Polyurethanes from Polyuoro Alcohols. J. Org. Chem.
79: 50195027. doi:10.1021/jo5005789.
[18] Polyurethanes from Vegetable Oils; Zoran S. Petrovi;
Polymer Reviews, Volume 48, Issue 1, 2008
[19] Kaushiva, Byran D. (August 15, 1999). StructureProperty Relationships of Flexible Polyurethane Foams.
PhD Thesis. Virginia Polytechnic Institute.

11

REFERENCES

[33] Health Alert: Polyurethane exposure.

[34] United States Environmental Protection Agency,
Environmental Proles of Chemical Flame-Retardant
Alternatives for Low-Density Polyurethane Foam.
September 2005
[35] United States Environmental Protection Agency, Flame
Retardants Used in Flexible Polyurethane Foam - Draft
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[36] CDC - NIOSH Science Blog - Help Wanted: Spray
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[37] United States Environmental Protection Agency, Spray
Polyurethane Foam
[38] http://www.isopa.org ISOPA

[20] Technical data sheet from Dow Chemical. Retrieved

2007-09-15.
[21] Randall, David; Lee, Steve (2002). The Polyurethanes
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[22] http://www.google.com/patents/about?id=
E-McAAAAEBAJ&dq=6,503,156&ie=ISO-8859-1

[39] G. Avar, Polyurethanes (PU), Kunststoe international

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[40] Ceresana, Market Study: Polyurethanes and Isocyanates,
July 2013, http://www.ceresana.com/en/market-studies/
plastics/pur-isocyanates/

[23] Blackwell, J.; M.R. Nagarajan and T.B. Hoitink (1981).

The Structure of the Hard Segments in MDI/diol/PTMA
Polyurethane Elastomers. Washington, D.C.: American
Chemical Society. ISSN 0097-6156.

[41] Discoloration of polyurethane foam. Foamex Information sheet. Archived from the original (PDF) on 2010-0926. Retrieved 2010-09-26.

[24] Blackwell, John; Kenncorwin H. Gardner (1979). Structure of the hard segments in polyurethane elastomers.
IPC Business Press. ISSN 0032-3861.

[42] Valentine, C; Craig, T.A.; Hager, S.L (1993). Inhibition of the Discoloration of Polyurethane Foam Caused
by Ultraviolet Light. J. Cellular Plastics 29 (6): 569
590. doi:10.1177/0021955X9302900605.

[25] Grillo, D.J.; Housel, T.L. (1992). Physical Properties of Polyurethanes from Polyesters and Other Polyols.
Polyurethanes '92 Conference Proceedings. New Orleans,
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[26] Musselman, S.G.; Santosusso, T.M. and Sperling, L.H.
(1998). Structure Versus Performance Properties of Cast
Elastomers. Polyurethanes '98 Conference Proceedings.
Dallas, TX: The Society of the Plastics Industry, Inc.
[27] A Guide To Glycols. 117-00991-92HYC (The Dow
Chemical Company). 1992.
[28] Jecat Amine Catalysts for the Polyurethane Industry
(PDF). 2006. Archived from the original (PDF) on 200711-29. Retrieved 2007-10-23.
[29] Building quality with Air Products trimerisation catalysts (PDF). 2003. Retrieved 2007-10-23.
[30] FOMREZ Specialty Tin Catalysts for Polyurethane Applications. 120-074-10 (Crompton Corporation). January 2001.
[31] FOMREZ Specialty Tin Catalysts for Polyurethane Applications (leaet insert)". 120-075-10 (Crompton Corporation). January 2001.
[32] Dernehl CU. (1966). Health Hazards Associated with
Polyurethane Foams. Journal of Occupational and Environmental Medicine.

[43] Blair, G. Ron; Bob Dawe; Jim McEvoy; Roy Pask;

Marcela Rusan de Priamus; Carol Wright (2007). The
Eect of Visible Light on the Variability of Flexible Foam
Compression Sets (PDF). Orlando, Florida: Center for the
Polyurethane Industry. Retrieved 2008-01-26.
[44] Newman, C.R.; Forciniti, D. (2001).
Modeling
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Foams. Ind. Eng. Chem. Res. 40 (15): 33363352.
doi:10.1021/ie0009738.
[45] Bio degradation of Polyester Polyurethane by Endophytic
Fungi. Applied and Environmental Microbiology. July
2011.
[46] Francesca Cappitelli;
Claudia Sorlini (2008).
Microorganisms Attack Synthetic Polymers in
Items Representing Our Cultural Heritage.
Applied Environmental Microbiology 74 (3): 5649.
doi:10.1128/AEM.01768-07. PMC 2227722. PMID
18065627.
[47] Yutaka Tokiwa; Buenaventurada P. Calabia; Charles U.
Ugwu; Seiichi Aiba (September 2009). Biodegradability
of Plastics. International Journal of Molecular Science 9:
37223742. doi:10.3390/ijms10093722. PMC 2769161.
PMID 19865515.

12

External links

Center for the Polyurethanes Industry: information

for EH&S issues related to polyurethanes developments
Polyurethane synthesis, Polymer Science Learning
Center, University of Southern Mississippi
Polyurethane Foam Association: Industry information, educational materials and resources related to
exible polyurethane foam
PU Europe: European PU insulation industry association: (Formerly BING) European voice for
the National trade associations representing the
polyurethane insulation industry.
ISOPA: European Diisocyanate & Polyol Producers
Association: ISOPA represents the manufacturers in
Europe of aromatic diisocyanates and polyols

10

13

13
13.1

TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

Text

Polyurethane Source: http://en.wikipedia.org/wiki/Polyurethane?oldid=663215910 Contributors: AxelBoldt, Magnus Manske, Bryan

Derksen, Tarquin, Andre Engels, PierreAbbat, Heron, Edward, Ixfd64, Lquilter, Paul A, SebastianHelm, , A5, Molinari, Stone,
Jeq, Sjorford, Kristof vt, Securiger, Bkell, Isopropyl, Mintleaf~enwiki, BenFrantzDale, Tom harrison, Alan Au, Karol Langner, Icairns,
Buickid, Sonett72, Noisy, Bender235, Ground, Imoen, Nrbelex, Femto, Smalljim, Hooperbloob, Pion, DreamGuy, Sobolewski, Velella,
Shoey, Peter Wllauer, Gene Nygaard, Mr. Nobody, Berserker79, Luigizanasi, Mhazard9, Abanima, LOL, Polyparadigm, Ruud Koot,
Cataclysm, Dysepsion, V8rik, BD2412, Swmcd, Rjwilmsi, Nneonneo, SLi, Avocado, FlaBot, Old Moonraker, Phatmonkey, Ewlyahoocom,
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Seegoon, Speedevil, Ducati38, RustySpear, Silverchemist, Scheinwerfermann, Sarefo, GraemeL, ChemGardener, SmackBot, Alan Pascoe, YellowMonkey, KVDP, Eskimbot, Frymaster, Edgar181, Gilliam, Andy M. Wang, Chris the speller, Bluebot, Jonlesser, Can't sleep,
clown will eat me, HarrisX, CorbinSimpson, Nakon, JanCeuleers, Smokefoot, DMacks, Just plain Bill, Acdx, Lambiam, ArglebargleIV,
Rigadoun, NewTestLeper79, Mgiganteus1, Peterlewis, Randomtime, Beetstra, Ahering@cogeco.ca, Wizard191, Iridescent, TerryE, Skorpion87, GDallimore, Mellery, NormLambert, Dlaz, Dr Zak, Oldsci, Rieman 82, Tawkerbot4, Kansas Sam, Thijs!bot, Barticus88, Siawase,
JRRobinson, J Clear, AntiVandalBot, Zedla, 2k rammerizkool, Barek, MER-C, Adjwilley, PhilKnight, Magioladitis, Appraiser, SHCarter,
Sojahseh, Adrian J. Hunter, Tlmclain, Cpl Syx, Glen, ChemNerd, R'n'B, Nono64, Rachelskit, Uncle Dick, Boskoman, P Cottontail, Perel,
Cometstyles, Industrialinfo, Sam Blacketer, Siamsens, VolkovBot, Goldcoast~enwiki, Philip Trueman, TXiKiBoT, Emailkran, Cedric dlb,
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OKBot, Chem-awb, ClueBot, Dpachterberg~enwiki, Orniphobe, The Thing That Should Not Be, Waheedulhassan1, Ithunn, ImperfectlyInformed, Yikrazuul, Mild Bill Hiccup, CrazyChemGuy, Shrampes, Phthalocyanine, StewieX, Gejan, Qwfp, DumZiBoT, P3tlab, XLinkBot,
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NG, Widr, Willbill321, Helpful Pixie Bot, Masohe, Eugbug, BG19bot, Chzxq, GraFFiX49509, Polyurethanefoamassociation, Vanischenu,
Cweisbecker, Shaun, Kiepo13, BattyBot, Tmariem, ChrisGualtieri, JesseAlanGordon, Mogism, JZNIOSH, Dradhesion, Jamesx12345,
CensoredScribe, Napy65, AresLiam, Selchem, Hawiex, Monkbot, Polyurethanewheel, Mrpejman, Hugohafner, Loltroller2300, Ace4343,
KasparBot and Anonymous: 337

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artist: ?
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Generalizedpolyurethanereaction.png License: Public domain Contributors: Own work Original artist: P Cottontail
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Contributors: Transferred from en.wikipedia to Commons by Ronhjones using CommonsHelper. Original artist: Silverchemist at English
Wikipedia
File:PUaminepolymerization.png Source: http://upload.wikimedia.org/wikipedia/commons/e/eb/PUaminepolymerization.png License:
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