Polymer Science

Project on Polyurethane
Submitted to Dr. John Paul

Submitted by
Harshavardhan Gorakh
Spring 2014

CHAPTER 1 SYNTHETIC ROUTES..........................................................................3

1.1

INTRODUCTION

1.2

PREPARATION................................................................................................................ 4

AND

STRUCTURE.......................................................................................3

1.2.1 Polyurethane......................................................................................................... 4
CHAPTER 2 HISTORY..........................................................................................6
CHAPTER 3 PRODUCTION STATISTICS [2].............................................................8
CHAPTER 4 PROCESSING...................................................................................13
4.1

RAW MATERIAL............................................................................................................ 13

4.2

FLEXIBLE FOAM........................................................................................................... 13

4.3

RIGID FOAMS.............................................................................................................. 16

CHAPTER 5 APPLICATION AND PROPERTIES.......................................................17

5.1

FLEXIBLE FOAM:.......................................................................................................... 17

5.2

RIGID FOAM................................................................................................................ 17

5.3

C.A.S.E. (COATINGS, ADHESIVES, SEALANTS, ELASTOMERS)................................................18

5.3.1 Coatings:............................................................................................................. 18
5.3.2 Adhesives and Sealants:......................................................................................18
5.3.3 Elastomers........................................................................................................... 19
CHAPTER 6 HEALTH AND SAFETY ISSUES...........................................................20
6.1

ISOCYANATE................................................................................................................ 20

6.2

TERTIARY AMINE CATALYST.............................................................................................22

6.3

POLYURETHANE............................................................................................................ 22

CHAPTER 7 SUMMARY:......................................................................................23
REFERENCES:............................................................................................................................ 24

Chapter 1

Synthetic Routes

1.1 Introduction and Structure

Polyurethanes are organic polymer and are well known for preparation of foams.
They are the most versatile family of polymers. They can be ELastomers, they can
be Paints they can be Fibers and they can be Adhesives. As name suggests,
urethane linkages are present in the polyurethane polymer. Figure 1 and Figure 2
shows urethane monomer and linear polyurethane polymer respectively and Figure
3 shows segmented copolymer of urethane obtained from diisocyanate, a
macroglycol and diol extender HO-(CH 2)x-OH. The marvelously unconventional
polyurethane is Spandex as shown in the Figure 4 below.

Figure 1: Urethane Monomer

Figure 2: Linear Polyurethane Polymer

Figure 3: Linear Segmented Copolymer of Urethane

Figure 4: Spandex Polymer also known as Lycra [1]

1.2 Preparation
There are different types of polyurethane

1.2.1

Polyurethane

Polyurethanes are prepared by catalyzed addition polymerization of two monomers

a diol (two alcohol groups) and diisocyanate (two isocyanate groups). Catalyst used
for controlling gelation is 1,4-diazabicyclo[2.2.2]octane also known as DABCO which
is tertiary amine.

The reaction is shown as follows: hu

Figure 5: Catalyzed Step Polymerization reaction for polyurethane

For manufacturing of flexible foam a combination of tin and tertiary amine catalysts
are used in order to balance the gelation reaction (urethane formation) and the
blowing reaction (urea formation). The tin catalyst used include dibutyltin dilaurate,
dibutylbis (laurylthio) stannate, dibutyltinbis (isooctylmercapto acetate), and
dibutyltinbis (isooctylmaleate).
Strong bases, such as potassiumacetate, potassium2-ethylhexoate, or amine
epoxide combinations are the most useful trimerization catalysts. Also, some special
tertiary amines, such as 2,4,6-tris(N,N-dimethylaminomethyl)phenol (Figure 6)
(DMT-30),

1,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine

(Figure7),

and

ammonium salts (Dabco TMR) (Figure 8) are good trimerization catalysts.

Figure 8:
ammonium salts (Dabco
TMR)

Figure 6: 2,4,6-tris(N,Ndimethylaminomethyl)phenol

Figure7:1,3,5-tris(3dimethylaminopropyl)hexahydro-striazine

Chapter 2

History

Polyurethanes can be found in liquid coatings and paints, tough elastomeric such as
roller blade wheels, rigid insulation, soft flexible foam, elastic fiber or as an integral
skin. No matter how polyurethane is transformed, the underlying chemistry is the
result of research by Dr. Otto Bayer (1902-1982). Dr. Otto Bayer is recognized as the
father of the polyurethanes industry for his invention of the basic diisocyanate
poly-addition process.
The origin of polyurethane dates back to the beginning of World War II 1937, when it
was first developed as a replacement for rubber. The versatility of this new organic
polymer and its ability to substitute for scarce materials spurred numerous
applications. During World War II, polyurethane coatings were used for the
impregnation of paper and the manufacture of mustard gas resistant garments,
high-gloss airplane finishes and chemical and corrosion-resistant coatings to protect
metal, wood and masonry.
By the end of the war, polyurethane coatings were being manufactured and used on
an industrial scale and could be custom formulated for specific applications. By the
mid-50s, polyurethanes could be found in coatings and adhesives, elastomeric and
rigid foams. It was not until the late-50s that comfortable cushioning flexible foams
were commercially available. With the development of a low-cost polyether polyol,
flexible foams opened the door to the upholstery and automotive applications we
know today.
Formulations, additives and processing techniques continue to be developed, such
as reinforced and structural moldings for exterior automotive parts and onecomponent systems. Today, polyurethanes can be found in virtually everything we
touchdesks, chairs, cars, clothes, footwear, appliances, beds as well as the
insulation in our walls and roof and moldings on our homes.

The generalized timeline is shown in following table.

Years
1937
1952-54
19561957
1960s

1967

1969
1970
1980

1983
1990
20002008
2008present

Advancement in Polyurethane
Invention of Polyurethane by Dr. Otto Bayer at I.G. Farben in Leverkusen,
Germany. Patented
Polyisocyanates became commercially available in 1952 and production
of flexible polyurethane foam began using toluene diisocyanate (TDI)
and polyester polyols.
DuPont introduced polyether polyol poly(tetramethylene ether) glycol.
Production of more than 45000 metric Tonnes of Polyurethane foams.
The availability of chlorofloroalkane blowing agents, inexpensive
polyether
polyols,
methylene
diphenyl
diisocyanate
allowed
polyurethane rigid foams to be used as high performance insulation
materials. Dupont introduced urethane based synthetic leather.
urethane modified polyisocyanurate rigid foams were introduced,
offering even better thermal stability and flammability resistance.
During the 1960s, automotive interior safety components such as
instrument
and
door
panels
were
produced
by
backfilling thermoplastic skins with semi-rigid foam.
Bayer exhibited an all plastic car in Dsseldorf, Germany
Aqueous Polyurethane dispersions (PUDs), Elastomers, foot-ware, High
resilience flex foam, urethane acrylate resins
Water-blown microcellular flexible foams were used to mold gaskets for
automotive panels and air filter seals automotive energy absorber for
safety, replacing PVC plastisol from automotive applications have
greatly increased market share. Polyurethane foams are now used in
high temperature oil filter applications.
Pontiac Fiero USA, made first plastic body automobile
Montreal Protocol restricted the use of chlorine containing blowing agent
due to ozone depletion problem. Radiation Curable PUDs
Chemical resistance co-solvent PUD/acrylic dispersion. Environmental
constraints increased, with emphasis on energy saving and
sustainability Economic crisis, slowdown in the consumption of
polyurethane.
Mitsui 40% Non edible castor oil based polyols. plant based polyols will
be price competitive with crude oil based polyols, external
contraceptives, Musical instruments like Cello are being manufactured
using polyurethane.

Chapter 3

Production Statistics [2]

As per Research and Markets, the global market for polyurethanes was estimated at
13,650.00 kilo tons in 2010 and is expected to reach 17,946.20 kilo tons by 2016,
growing at a Compound Annual Growth Rate (CAGR) of 4.7% from 2011 to 2016. In
terms of revenue, the market was estimated to be worth US$33,033 million in 2010
and is expected to reach US$55479.68 million by 2016, growing at a CAGR of 6.8%
from 2011 to 2016. North America, Asia-Pacific, and Europe dominate the
polyurethane market and together accounted for 95% of the global polyurethane
demand in 2010. North America and Western Europe are mature markets and are
expected to grow at a sluggish rate. However, Asia-Pacific, Eastern Europe and
South America are expected to drive the demand for polyurethanes in the coming
decade. The furniture and interior industry dominated the polyurethane market,
accounting for 28.01% of the total demand in 2010. The second largest end-use of
polyurethanes is in construction industry, which accounted for 24.98% of the overall
market in 2010. Electronic appliances, however, are the fastest growing market for
polyurethanes. Polyurethane demand for electronic appliances is expected to grow
at a CAGR of 7.3% to 2011.
As

per

Global

Industry

Analysts,

the

global

market

for

foamed

plastics

(polyurethane) is projected to reach 9.6 million tons by the year 2015, driven by
resurgent demand from construction, furniture and bedding, and automotive
markets. The need for low-cost and long-lasting materials and rising significance of
energy efficiency in appliances and buildings is expected to foster growth in the
foamed plastics market. The global economic meltdown led to significant decline in
demand for polyurethane (PU) foams across the globe, largely due to the
contraction

in majority of

the end-use markets including automotive and

construction. Both flexible and rigid PU foams registered decline during 2008 and
2009, with the demand for flexible PU foams registering steeper decline in the US
and Western Europe. The economic crisis forced several companies, particularly
small

manufacturers

to

shutdown

production

units

permanently,

while

manufacturers with multiple production units sought reprieve by closing down some
capacity. Europe, Asia-Pacific, and the United States dominate the world foamed
plastics (polyurethane) market, as stated by the new market research report on
8

foamed plastics (polyurethane). Buoyed by the robust Chinese, Indian and Hong
Kong markets, Asia-Pacific region represents the fastest growing PU foams market,
with a CAGR of 4.9% over the analysis period. Middle East has been witnessing
healthy growth over the past few years. Increasing investments in polyurethane
production, coupled with new encouraging regulations has largely contributed to
market growth in the region. Demand for PU foams is highly dependent on diverse
end-use applications particularly in furniture and automotive sectors. Subdued
consumer spending, slowdown in new housing starts, decline in automotive
production, and increase in the volume of imported furniture contributed to a
significant decline in PU production, particularly in the US and Canada. Despite such
adversities, the market is expected to register growth owing to the increasing
concerns about energy conservation. This is evident by the rising demand for spray
polyurethane foam in the industrial and residential applications as well as the use of
polyurethane

for

insulating

structures

such

as

tents

at

Army

bases.

Furniture/Bedding represents the largest end-use market for PU foams, globally,

with Asia-Pacific region offering enormous growth opportunities for the segment. An
ageing health conscious population is driving significant changes in the bedding
industry. Mattresses are categorized as innerspring, foam, water, and air-filled,
among which foam mattresses are likely to witness a booming growth. PU foam
plays a significant role in the construction of mattresses due to its effectiveness in
relieving pressure points. Demand for reactive polyurethane hot melt adhesives is
likely

to

increase,

which

could

displace

solvent-based

adhesives.

Global

polyurethane market is largely dominated by the four stalwarts, which include Dow,
Bayer, BASF and Huntsman, in terms of production capacity. Competitive factors
determining the player market presence include price, quality, and assortment of
products and services. Major players profiled in the report include BASF AG, Bayer
AG, British Vita Unlimited, The Dow Chemical Company, FXI - Foamex Innovations,
Huntsman Polyurethanes, Mitsui Chemicals Inc., Recticel S.A, and Woodbridge Foam
Corporation.
As per IAL Consultants, despite a challenging economy and declining production,
the polyurethane industry continued to evolve over the past two years while
addressing growing concerns over energy conservation, according to the 2008 EndUse Market Survey on the Polyurethanes Industry in the United States, Canada and
9

Mexico. Research conducted by IAL Consultants on behalf of the Center for the
Polyurethanes Industry (CPI) of the American Chemistry Council, shows that overall
production of polyurethane in NAFTA declined by 6.7% pa during the past two years.
The figure reflects a 7.7% annual decline in U.S. markets and 10.8% decline in
Canada, while Mexico has shown positive growth for the third consecutive survey.
The production of polyurethane in Mexico increased at an average annual rate of
9.6% over the past two years, partly due to increased domestic demand.
With the dip in automotive output, decreased consumer spending, high levels of
imported furniture and a drop-off of activity in new housing starts, we were
prepared to see a decline in polyurethane production in the U.S. and Canada, said
Neeva-Gayle Candelori, Director of CPI. Overall, the research shows that the
industry continues to change. While some markets are mature, new ones have
opened up. Renewable chemicals and energy efficiency continue to be important
topics. Change is essential for evolution and it would be worrying if there were no
signs of market evolution. Signs of growth in the polyurethane industry included
continued increases in spray polyurethane foam demand for residential and
industrial applications, as well as use of the material by the U.S. Army to insulate
tents and other structures at bases in the Middle East. Polyurethane also is being
used for effective wound dressings, pharmaceutical delivery media, reliable drug
delivery, comfortable mobility aids and hygienic hospital environments. The
demand for low-VOC and high-performance coatings related to product substitutions
made the decline in the production of coatings, adhesives, sealants and TPU less
severe. Though there was a sharp decrease in binder production as a result of the
decline in OSB (oriented strand board) demand by the U.S. housing sector, the
desire for safe and clean recreational areas has helped increase use of polyurethane
binders in sports tracks and playgrounds in the past two years. New applications to
improve quality of life are contributing to market evolution as well, such as new
comfort levels in golf cart seating for the growing number of elderly. Manufacturers
looking to comply with new regulations and secure certification are also finding
ways to create opportunities for growth. The survey shows a boost to the rigid
polyurethane foam market for thicker panels needed to meet new ASHRAE
(American Society of Heating, Refrigerating and Air-Conditioning Engineers)
standards. CARB (California Air Resources Board) regulation and the CertiPUR
10

program also helped to secure business in the bedding industry for flexible
polyurethane foam. The United States, representing 81% of the total polyurethane
production in NAFTA, had a market breakdown similar to NAFTA overall. Imports of
upholstered furniture continued to increase in the United States. Though statistics
from the U.S. Department of Trade and Commerce did indicate a slight drop in
overall imports during the past two years, these were a reflection of the current
state of the housing market and declining consumer demand. In Mexico, production
of rigid polyurethane foam dominated the market as new companies invested in the
country and the appliance industry continued to grow. In 2008, the Mexican
appliance industry produced 9 mln refrigerators and freezers compared to 11.3 mln
in the United States. Mexican furniture and automotive markets also grew during
2008, driven by export and domestic demand. With 2.1 mln units in 2008,
automotive

production

exceeded

Canadas.

Flexible

molded

foam

end-use

production increased due to the manufacture of automotive components and

flexible slabstock production increased, as well. Though families currently prefer to
buy new upholstered furniture over new mattresses, the bedding market has
potential for further development. Despite a deficit of 5 million homes in Mexico,
home ownership has increased. Canadas dependence on the United States resulted
in a greater production decline than experienced in the U.S. The country was the
third market in the NAFTA region and accounted for 8.9% of total production.
Flexible foam slabstock accounted for 16% of total production, compared to 21% in
2006 and the fall in U.S. housing starts led to 54% of OSB production being idled. As
an environmentally conscious country, the population continued to buy products
marketed as eco-friendly, such as rigid polyurethane foam and flexible
polyurethane foam. Rigid polyurethane foam accounted for 39% of production in
2008 compared to 28% in 2006, another sign of interest in greater energy efficiency.
In the energy sector, components made from polyurethane cast elastomers,
technical insulation coatings and sealants received increased capital expenditure for
maintenance and development, mainly as a response to the high oil prices of 2007
and the first half of 2008.
Once again, rigid polyurethane foam products accounted for the largest share of the
6.5 billion lbs of polyurethane produced in NAFTA in 2008. The figure reflects the
relative strength in demand for rigid polyurethane foam as an insulation material.
11

The past two years have witnessed stable demand from the construction industry.
New housing starts have declined, but expenditures on remodeling and repairs
increased. This development is largely responsible for the growing demand for spray
polyurethane foam as internal wall insulation and the slower than expected decline
in CASE products like elastomers used in thermal breaks in insulated windows, solar
panels, wooden floor and turbine blade coatings, adhesives and sealants, and the
steady demand for one component spray foams. The versatility of spray
polyurethane foam also has contributed to its use in army tents and structures in
the Middle East where it has contributed to fuel savings. As part of its industry-wide
survey, IAL looked in depth at the factors affecting the declining demand for flexible
polyurethane foam in the automotive, furniture and bedding industries:
Furniture/Bedding:

United States production of flexible slabstock foam fell

sharply from 2006 - 2008. Flexible foam stock production dropped by nearly 25% in
2008 compared to 2007. The main impetus behind this decline is the decrease in
furniture production due to lack of consumer demand and imports. Imports of
upholstered furniture continued to rise until the end of 2007. The rate of imports is
not expected to change in the near future as U.S. government incentives to firsttime homebuyers will likely go towards imported goods. The bedding sector
continued to use large volumes of flexible polyurethane foam during 2008.
Mattresses manufactured in the United States used more foam per unit for deeper
mattresses with softer toppers; more hybrid mattresses were produced, as well.
Since the end of 2008, factors such as the reduced cost of lower density foams,
thinner mattresses, and customers requiring faster delivery times for mattresses
than other furniture delivery (2 -5 days), have helped protect the industry from
imports.
Transportation: While the automotive industry has experienced significant
downsizing, it has also seen an increased demand for more economical vehicles.
Production fell by 3.1 million since 2006, but there are now roughly 8 million flexible
fuel vehicles on U.S. roads and more are expected in the future. Polyurethane foam
used in automotive seating has trended toward becoming thinner, while density is
increasing, offering more cabin space above the seat and allowing the required
amortization of vibration. The decline in molded seat foam is related to the general
down market in automotive production.
12

13

Chapter 4

Processing

4.1 Raw Material

Common raw material used for manufacturing are Aromatic = Toluene Diisocyanate
(TDI), 4,40-methylenebis(phenyl isocyanate) (MDI), polymeric MDI fast reactivity,
not resistance to UV light can change color in sunlight and Aliphatic = HDI, IPDI,
H12 monomers has resistance to UV lights but slower reactivity than aromatic.
Polyols of ether or ester is used as a second reactant to react with above mentioned
isocyanate. This polyols can be obtained from petroleum. New processes have been
invented in last decade in Japan and India to prepare polyols from non-edible castor
oil. Price of polyols made by new process is cheaper than that of petroleum based
polyols.

4.2 Flexible Foam

Flexible slab or bun foam is poured by multicomponent machines at rates of >45
kg/min. One-shot pouring from traversing mixing heads is generally used. A typical
formulation for furniture-grade foam having a density of 0.024 g/cm 3 includes a
polyether triol, mol wt 3000; TDI; water; catalysts, ie, stannous octoate in
combination with a tertiary amine; and surfactant. Co-blowing agents are often used
to lower the density of the foam and to achieve a softer hand. Co-blowing agents
are methylene chloride, methyl chloroform, acetone, and CFC 11, but the last has
been eliminated because of its ozonedepletion potential. HCFC blowing agents are
replacing CFC 11. Additive systems

and new polyols [3]are being developed to

achieve softer low density foams. Higher density (0.045 g/cm 3) slab or bun foam,
also called high resiliency (HR) foam, is similarly produced, using polyether triols
having molecular weight of 6000. The use of polymer polyols improves the loadbearing properties. Flexible foams are three-dimensional agglomerations of gas
bubbles separated from each other by thin sections of polyurethanes and polyureas.
The microstructures observed in TDI- and MDI-based flexible foams are different. In
TDI foams monodentate urea segments form after 40% conversion, followed by a
bidentate urea phase, which is insoluble in the soft segment. As the foam cures,
annealing of the precipitated discontinuous urea phase occurs to optimize
14

alignment through hydrogen bonding [3]. Flame retardants (qv) are incorporated
into the formulations in amounts necessary to satisfy existing requirements.
Reactive-type diols, such as N,Nbis(2-hydroxyethyl) aminomethyl phosphonate are
preferred, but nonreactive phosphates are also used. Often, the necessary results
are achieved using mineral fillers, such as alumina trihydrate or melamine.
Melamine melts away from the flame and forms both a nonflammable gaseous
environment and

a molten

barrier that

helps to

isolate

the

combustible

polyurethane foam from the flame. Alumina trihydrate releases water of hydration
to cool the flame, forming a noncombustible inorganic protective char at the flame
front. Flame-resistant upholstery
fabric or liners are also used [3]. There are four main types of flexible slabstock
foam: conventional, high resiliency, filled, and high load-bearing foam. Filled
slabstock foams contain inorganic fillers to increase the foam density and improve
the load-bearing characteristics. High load-bearing formulations incorporate a
polymer polyol. Slabstock flexible foam is produced on continuous bun lines. The
bun forms while the material moves down a long conveyor. In flat-top bun lines, the
liquid chemicals are dispensed from a stationary mixing head to a manifold at the
bottom of a trough. More rectangular foams are produced by several newer
processes. However, the most popular rectangular block foam process is the
Maxfoam process. The high outputs require faster and longer conveyors. An
exception is the Vertifoam process, in which the reaction mixture is introduced at
the bottom of an enclosed expansion chamber. The chamber is lined with paper or
polyethylene film, which is drawn upward at a controlled rate. Because the
Vertifoam machine is much smaller than the horizontal machines, operational
savings can be achieved [3]. Two newer slabstock foam manufacturing processes
have been developed. A high rate of block foam production (150220 kg/min) is
required in order to obtain large slabs to minimize cutting waste. Bun widths range
from ca 1.43to 2.2 m, and typical bun heights are 0.771.25 m. In a flexible foam
plant, scrap can amount to as much as 20%. Most of it is used as carpet underlay
and in pillows and packaging (see PACKAGING MATERIALS). The finished foam blocks
are stored in a cooling area for at least 12 h before being passed to a storage area
or to slitters where the blocks are cut into sheets. In the production plant the fire
risk must be minimized. Temperatures of up to 1508C can be reached in the interior
15

of the foam blocks. Blowing of ambient air through the porous foam allows
dissipation of the heat generated in the exothermic reaction [3]. Most flexible foams
produced are based on polyether polyols. Flexible polyether foams have excellent
cushioning properties, are flexible over a wide range of temperatures, and can resist
fatigue, aging, chemicals, and mold growth. Polyester-based foams are superior in
resistance to dry cleaning and can be flamebonded to textiles. In more recent years,
molded flexible foam products are becoming more popular. The bulk of the molded
flexible urethane foam is employed in the transportation industry, where it is highly
suitable for the manufacture of seat cushions, back cushions, and bucket-seat
padding. TDI prepolymers were used in flexible foam molding in conjunction with
polyether polyols. The introduction of organotin catalysts and efficient silicone
surfactants facilitates one-shot foam molding, which is the most economical
production method. The need for heat curing has been eliminated by the
development of cold-molded or high resiliency foams. These molded HR foams are
produced from highly reactive polyols and are cured under ambient conditions. The
polyether triols used are 45006500 mol wt and are high in ethylene oxide (usually
>50%
primary hydroxyl content). Reactivity is further enhanced by triethanolamine, 12
URETHANE POLYMERS Vol. 25 liquid aromatic diamines, and aromatic diols.
Generally, PMDI, TDI, or blends of PMDITDI are used. Load-bearing characteristics
are improved by using polymer polyol. High resiliency foams exhibit relatively high
SAC (support) factors, ie, load ratio; excellent resiliency (ball rebound >60%); and
improved flammability properties. Semiflexible molded polyurethane foams are
used in other automotive applications, such as instrument panels, dashboards, arm
rests, head rests, door liners, and vibrational control devices. An important property
of semiflexible foam is low resiliency and low elasticity, which results in a slow rate
of recovery after deflection. The isocyanate used in the manufacture of semiflexible
foams is PMDI, sometimes used in combination with TDI or TDI prepolymers. Both
polyester
as well as polyether polyols are used in the production of these water-blown foams.
Sometimes integral skin molded foams are produced. Semirigid foams are also
manufactured. These foams do not fully recover after deformation; they are used in
the construction of energy-absorbing automobile bumpers. Integral skin molded
16

foams have an attached densified water skin, which

is produced during

manufacture. The preferred isocyanate for integral skin foams is carbodiimidemodified liquid MDI, which is used with ethylene oxide-capped polyols or polymer
polyols. Thicker skins are obtained by lowering mold temperatures and increasing
the percentage of overpack.

4.3 Rigid Foams

Rigid polyurethane foam is mainly used for insulation (qv). The configuration of the
product determines the method of production. Rigid polyurethane foam is produced
in slab or bun form on continuous lines Figure 9, or it is continuously laminated bet
ween either asphalt or tar paper, oraluminum, steel, and fiberboard, or gypsum
facings Figure 10

Figure 9: Rigid foam processing

17

Figure 10: Rigid foam processing

Chapter 5

Application and properties

5.1 Flexible Foam:

The

largest

markets

for

flexible

polyurethane

foam

are

in

the

furniture,

transportation, bedding, carpet underlay and packaging industries. Most furniture

cushioning is made of polyurethane foam, predominantly cut from slabs or buns
having a density of 0.01920.0288 g/cm3. Polyurethane viscoelastic foam is used
increasingly in bedding. High resiliency flexible foam having a density of 0.040
g/cm3 is used for seat cushions in higher priced furniture. Molded flexible
polyurethane foam is used in the automotive industry for seating, instrument
panels, head rests, and arm rests applications. Semiflexible molded polyurethane
foams are used in dashboards and door liners. Semiflexible foams are also
formulated for sound and vibrational control in automotive applications [3]. Other
foam uses include textile laminates and interior padding. Specialty applications
include reticulated foams for filtration and foams for such consumer products as
sponges, scrubbers, squeegees, and paint applicators. Foams that provide radiation

18

protection [4] and flame retardant foam that can be obtained using a generalpurpose polyol [5] have been reported.

5.2 Rigid Foam

The bulk of rigid polyurethane and polyisocyanate foam is used in insulation. There
has been a major demand for spray foams in the construction industry [6]. The use
of rigid foam continues to improve energy efficiency [6]. Laminates are used for
residential sheathing and board for flatdeck commercial roofing. Commercial
buildings are often covered with polyurethane spray foam. Pour-in-place foam is
typically integrated in large-scale assembly operations, such as aircraft carriers.
Insulation of trucks, railroad freight cars and cargo containers is performed by either
spray or pour-in-place techniques. Tank and pipe insulation is either sprayed or cut
from bun stock. Ships transporting liquid natural gas (LNG) are usually insulated
with rigid PUIR foam laminates, which provide temperature stabilities from 180 to
1508C. The main fuel tank of the National Aeronautics and Space Administration
(NASA) space shuttles is also insulated with PUIR foam. Rigid polyurethane foam is
used in engineered foamed-in-place packaging of industrial or scientific equipment
and in the molding of furniture, simulated-wood ceiling beams, and a variety of
decorative and structural furniture components. Rigid foam is also used in movie
props, for the repair of river barges, and in boat flotation applications.

5.3 C.A.S.E. (Coatings, Adhesives, Sealants, Elastomers)

5.3.1

Coatings:

Urethane coatings have been one of the fastest growing sectors of the worldwide
paint and coatings industries [7]. Polyurethane coatings are used wherever
applications require abrasion resistance, skin flexibility, fast curing, good adhesion,
and chemical resistance. The polyaddition process allows formulation of solventbased

or

solventless

liquid

two-component

systems,

waterborne

(aqueous)

dispersions, or powder coatings. Polyurethane coatings are applied to products to

improve their appearance and lifespan. Polyurethane coatings are used on
automobile exteriors, in construction where building floors, steel trusses, and
concrete supports are sprayed-coated to make them more durable and easier to
19

clean. Coatings are used in the aerospace industry to protect external parts of
aircraft from extreme temperatures, and help protect the skin from rust and pitting.
Synthetic leather products are also produced using a urethane binder. These
leather-type products are used for shoes, handbags, luggage, and apparel. Leatherlike

sheet

materials

[8].Polyurethane

films

with

excellent

having

water

oxygen

and

resistance
water

have

been

permeability

are

reported
applied

inbandages and wound dressings and as artificial skin for burn victims.

5.3.2

Adhesives and Sealants:

Polyurethane adhesives and sealants provide strong bonding and tight seals in a
variety of applications. Polyurethane adhesives provide the rapid development of
green strength, where the adhesive provides an initial bond before fully curing. This
reduces the need for clamping and holding materials, thereby reducing costs and
increasing manufacturing flexibility. Custom adhesives and sealants can be
manufactured. Adhesives are used in the assembly of shoes, automotive interiors,
windshield bonding, and as textile laminates. Conveyor belts are usually closed with
polyurethane adhesives. Polyurethane binders are mixed with wood chips or
sawdust to form fiberboard. Sealants are used in road repair, plumbing, and
construction. Polyurethane sealants provide excellent stress recovery to retain
shape after being pulled or bent, are fast curing, and adhere to non-primed
concrete. These sealants and adhesives can be painted to match surrounding
surfaces.

5.3.3

Elastomers

Polyurethane elastomers are rubber-like materials that can be created with a wide
variety of properties and molded into almost any shape. They can provide
resistance to abrasion, impact and shock, temperature, cuts and tears, oils and
solvents, aging, mold, mildew, and fungus, and most chemicals. Polyurethane
elastomers are used almost everywhere. Snowplow blades are made of the
elastomers to reduce road damage caused by scraping, wheels for shopping carts,
skateboards, roller coasters, and heavy trash containers made with polyurethane
elastomers provide for high-load bearing capacity and abrasion resistance. Tubing
and injection molded parts are used in the medical sector. Cast and RIM elastomers
are used in auto fascia, bumper and fender extensions, printing and industrial rolls,
20

industrial tires, and agricultural parts, such as oil well plugs and grain buckets.
Elastomeric spandex fibers are a large market and these fibers are used in all types
of hosiery, undergarments, swim wear and other sports clothing. Elastomers with
improved antistatic behavior for these fiber uses have been reported [9].

21

Chapter 6

Health and safety issues

Fully cured polyurethanes present no health hazard; they are chemically inert and
insoluble in water and most organic solvents. However, dust can be generated in
fabrication, and inhalation of the dust should be avoided. Polyether-based
polyurethanes are not degraded in the human body, and are therefore used in
biomedical applications. Some of the chemicals used in the production of
polyurethanes, such as the highly reactive isocyanates and tertiary amine catalysts,
must be handled with caution. The other polyurethane ingredients, polyols and
surfactants, are relatively inert materials having low toxicity.

6.1 Isocyanate
Isocyanates in general are toxic chemicals and require great care in handling. Oral
ingestion of substantial quantities of isocyanates can be tolerated by the human
body, but acute symptoms may develop from the inhalation of much smaller
amounts. The inhalation of isocyanates presents a hazard for the people who work
with them as well as the people who live in the proximity of an isocyanate plant.
Adequate control of exposure is necessary to achieve a safe working environment.
The suppliers Material Safety Data Sheets (MSDS) have to be consulted for the most
current information on the safe handling of isocyanates. Respiratory effects are the
primary toxicological manifestations of repeated overexposure to diisocyanates
[10]. Once a person is sensitized to isocyanates, lower concentrations can trigger a
response [11]. Most of the industrial diisocyanates are also eye and skin irritants.
Controlling dermal exposure is good industrial hygiene practice. The 1997 American
Conference of Governmental Industrial Hygienists (ACGIH) exposure guideline for
TDI

is

0.005

ppm

as

TWA-TLV

(an

eight-hour

time-weighted

average

concentration); the 1997 TLV for TDI in Japan is 20 ppb. Overexposure to TDI can
cause chemical bronchitis (isocyanate asthma) in sensitized individuals. Transient
acute asymptomatic changes in respiratory function and deterioration of lung
function following long-term repeated exposure have also been encountered.
Allergic sensitization may occur within months or after years of exposure to
isocyanates. Animal studies using TDI showed no dermatological response at
exposure concentrations up to 0.5ppm. A chronic gavage study indicated tumor
22

formation in the animals, but the study was found to be of doubtful toxicological
relevance because of the method used and the excessively high dose levels. Vapor
exposure to MDI is limited by the low vapor pressure, corresponding to a saturated
atmosphere of 0.1 mg/m3 at 258C. An acute aerosol inhalation study on PMDI using
rats indicated that the 4-h LC50 is 490mg/m3 [12].The current ACGIH TLV for MDI is
0.051 mg/m3 (0.005 ppm) as a TWA. The OSHA PEL is 0.02 ppm as a ceiling limit.
The toxicity of aliphatic diisocyanates also warrants monitoring exposure to its
vapors. HDI has a moderate potential for acute systemic dermal toxicity; rabbit
dermal LD50 is 570 mL/kg [13]. However, HDI is severely irritating to the skin and
eyes. Irritation, lacrimation, rhinitis, burning sensation to throat and chest, and
coughing have all been reported in humans following acute inhalation exposure to
HDI. HMDI has a low eye and dermal irritation potential, as well as a low potential
for acute toxicity. Exposure to HMDI aerosol can cause dermal sensitization of
laboratory animals. IPDI can cause skin sensitization reactions as well as eye
irritation.

There are a multitude of governmental requirements for the

manufacture and handling of isocyanates. The U.S. Environmental Protection

Agency (EPA) mandates testing and risk management for TDI and MDI under Toxic
Substance Control Administration (TSCA). Annual reports on emissions of both
isocyanates are required by the EPA under SARA 313. Thermal degradation of
isocyanates occurs on heating above 1001208C. This reaction is exothermic, and a
runaway reaction can occur at temperatures >1758C. In view of the heat sensitivity
of isocyanates, it is necessary to melt MDI with caution and to follow suppliers
recommendation. Disposal of empty containers, isocyanate waste materials, and
decontamination of spilled isocyanates are best conducted using water or alcohols
containing small amounts of ammonia or detergent. For example, a mixture of 50%
ethanol, 2-propanol, or butanol; 45% water, and 5% ammonia can be used to
neutralize isocyanate waste and spills. Spills and leaks of isocyanates should be
contained immediately, ie, by dyking with an absorbent material, such as saw dust.
The total U.S. airborne emission of volatile TDI is estimated by the International
Isocyanate Institute (III) to be <25 t, or less than 0.005% of the annual U.S.
production. Published data show that TDI has a 1/3 life of 8 s in air at 258C and 50%
rh, and a 0.5 s to 3 d half-life in water, depending on pH and agitation. Without
agitation, isocyanates sink to the bottom of the water and react slowly at the
interface. Because of this reactivity, there is no chance of bioaccumulation.
23

6.2 Tertiary Amine Catalyst

The liquid tertiary aliphatic amines used as catalysts in the manufacture of
polyurethanes can cause contact dermatitis and severe damage to the eye.
Inhalation can produce moderate to severe irritation of the upper respiratory tracts
and the lungs. Ventilation, protective clothing, and safety glasses are mandatory
when handling these chemicals.

6.3 Polyurethane
These polymers can be considered safe for human use. However, exposure to dust,
generated in finishing operations, should be avoided. Ventilation, dust masks, and
eye protection are recommended in foam fabrication operations. Polyurethane or
polyisocyanurate dust may present an explosion risk under certain conditions.
Airborne concentrations of 2530 g/m3 are required before an explosion occurs.
Inhalation of thermal decomposition products of polyurethanes should be avoided
because carbon monoxide and hydrogen cyanide are among the many products
present. When the foam is heated to decomposition, it emits acrid, toxic fumes of
CN_ and NOx [14]. The polyurethane industry has made significant contributions
towards environmental improvements by reducing VOCs and using new blowing
agents [15]. Because polyurethanes are combustible, they have to be applied in a
safe and responsible manner. At no time should exposed foam be used in building
construction. An approved fire-resistive thermal barrier must be applied over foam
insulation on interior walls and ceilings. Model U.S. building codes specify that foam
plastic used on interior walls and ceilings must have a flame-spread rating,
determined by ASTM E84, of <75, and smoke generation of <450. The foam plastic
must be covered with a fire-resistive thermal barrier either having a
finish rating of not less than 15 min or equivalent to 12.7-mm gypsum board, or
having a flame-spread rating of <25, smoke generation of <450 (if covered with
approved metal facing), and protection by automatic sprinklers. Under no
circumstances should direct flame or excessive heat be allowed to contact
polyurethane or polyisocyanurate foam. The ASTM numerical flame-spread rating is
not intended to reflect hazards presented under actual fire conditions.

24

Chapter 7

Summary:

As we have seen from the above report that market for polyurethane is ever
increasing because of its versatile uses. As we have seen in Chapter 2, economic
studies predict that market for polyurethane is expected to grow to 17,946.20 kilo
tons by 2016, growing at a Compound Annual Growth Rate (CAGR) of 4.7% from
2011 to 2016.
Advent of new technology to prepare polyols (one of the major raw material) is
environmental friendly and at the same time cheaper than before. With adequate
standards of safety regulations during processing of product in industry and
standard housekeeping operating procedure during utilization of product will
definitely boost the uses of polyurethane based goods.

25

References:
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[2] Technical Articles & Reports on Plastic Industry, "www.plastemart.com," 30
August 2011. [Online]. Available: http://www.plastemart.com/Plastic-TechnicalArticle.asp?LiteratureID=1674&Paper=global-polyurethane-market-PU-foamsthermoplastic-elastomers.
[3] C. Czekaj, Kirk Othmer Encyclopedia of Chemical Technology, vol. 4 section
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Tokyasu

and

I.

Stamada,

"Composition

for

flame-retardant

flexible

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[7] IAL Consultant, End-use Market Survey on the Polyurethane Industry, 2004.
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[9] M. Mimura and I. Shikawa., Leathery sheet object, process for producing the
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]

antistatic behavior". Patent 20060058455, 16 Mar 2006.

[11 A. W. Musk, J. M. Peters and D. H. Wegman, "Isocyanates and respiratory

]

disease: Current status," Am. J. Ind. Medicine , vol. 13, p. 331, 1988.

[12 M. H. Karol, "CRC Critical Review," Toxicology, no. 16, p. 349, 1986.
]
[13 R. P. G. J, "Report to the International Isocyanate Institute, III,," New York, 1987.
]
[14 R.

J.

Davies,

"Respiratory

hypersensitivity
26

to

diisocyanates,"

Clinics

in

Immunology and Allergy, no. 4, p. 103, 1984.

[15 R. J. Lewis, Saxs Dangerous Properties of Industrial Materials, Wiley.

]
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IAL Consultants, 2005.

27