products of chemistry

GEORGE
6. KAUFFMAN
California State UniveniR: Fresno
Fresno, CA 93740

Polyurethanes: A Class of Modern Versatile Materials

Raymond B. ~ e ~ m o u r l
University of Southern Mississippi, Hattiesburg, MS 39406
George B. Kauffman
California State University, Fresno, Fresno, CA 93740

The myriad applications of polyurethane coatings,

foams, fibers, moldings, and elastomers demonstrate the
versatility of urethane chemistry and the creativity of
polymer scientists. Urethanes have indeed come a long
way from being a mere qualitative test for alcohols.
Simple Condensation Reactions
Before modem instrumental techniques, such as infrared spectroscopy, chemists characterized organic compounds by simple small-scale chemical reactions to form
derivatives. For example, if an unknown liquid compound
was classified as an alcohol by solubility tests, the chemist
would convert this alcohol to a solid ester or solid urethane
(N-alkylurea or alkyl carbamate) derivative by a condensation reaction with an aromatic acid chloride or an aromatic
isocyanate.

ROH + M O C l + ArCOOR + HC1

ester
ROH + ArNCO + ArNHCOOR
urethane
Similarly, an unknown amine could be characterized by
a condensation reaction with an aromatic carboxvlic acid
or an aromatic isocyanate to produce an amide or a substituted urea, respectively.
RNH2+ AICOOH + MONHR + H20
amide

RNH, + ArNCO + ArNHCONHR

urea
Then the identity of the derivative was confirmed by mixed
meltinrr ~ o i n t swith condensation derivatives of known
compounds.

-.

Early Polymer Chemistry

Polyesters and Polyamides

When Wallace Hume Carothers (18961937) was trying

to produce the world's first synthetic fiber, he repeated the
ester reaction using a difunctional alcohol, such as ethylene glycol (HOCH2CH20H),with a difunctional dicarboxylic acid, such as adipic acid (HOOC(CH2)&OOH),to form
a polyester (1, 2). Unfortunately, the chain length of the
product was too short to be classified as a polymer.
Carothers demonstrated his creative chemical ability by
recognizing the need for high-purity reactants to produce
polymers with a high degree of polymerization (DP), that
is, a large number of repeating units. Because the aliphatic
polyester softened when heated by an iron, he turned his
'Deceased November 15,1991.

attention to the higher-melting polyamides, which are now

known as nylon (3).
Polyurethane
Otto Bayer (1902-1984) became aware of Carothers'inventionof polyamides and polyesters, and in his attempt to
circumvent Carothers' patents, Bayer chose the urethane
reaction. He produced polyurethanes by the condensation
of difunctional hexane diisocyanate and 1,4-butanediol,
monomers that were not commercially available when he
undertook his polyurethane studies.
nOCN(CH,)flCO + nHO(CH2),0H +

[-CONH(CH2),NHCOO(CH2),0-I"
The fibers obtained from these polyurethanes were suitable for brush bristles because they were stiffer than nylon
and other textile fibers.
Polyurethane Foams

A major breakthrough occurred when a trace of water

was inadvertently present in the reactants. The carbon dioxide gas produced by the reaction of isocyanate and water
formed many small empty areas (cells)in the product, producing what Bayer's colleagues called "imitation Swiss
cheese". This polyurethane foam eventually became the
major polyurethane product. The United States consumption of flexible and rigid polyurethane foams in 1989 was
786 thousand tons and 392 thousand tons, respectively.
The total worldwide consumption of polyurethane in 1989
was 4.14 million tons (4).
Polyurethane foam production, which may be readily
demonstrated in the laboratory (5),is dependent on the instability of the carbamic acid, which decomposes into carbon dioxide and amine.
OCN(CH2),NC0+ H20 +
C02T+ OCN(CH2)&H,
The amine then reacts with isocyanate groups to produce
a polyurea (6).

Industrial Production of Polyurethane

A relatively small amount of polyurethane for aircraft
coatings was produced in Germany during World War 11,
but large-scale production was delayed until Bayer and
Monsauto joined to form the Mobay Corporation, which

Volume 69 Number 11 November 1992

909

produced polyurethanes by the reaction of hydroxyl-terminated polyesters or hydroxyl-terminated polyethers and

tolylene diisocyanate (TDI), using chlorofluorocarbons
(CFC's or Freons) as the foam agent (pro~ellant).More recently, the less volatile diphenyfmethane-4,4'-diisocyanate
(MDI) is being used as a monomer.
Due to the adverse effect of CFC's on the ozone layer,
nonchlorinated fluorocarbon propellants (sot%fluorocarbons) are being used instead. The use of CFC's in foam production. refrigeration, and air conditioning is being discontinued in acc&dance with an international agreement, the
Montreal Protocol (1987). Microcellular polyurethane
foam is used for shoe soles and for the reaction injection
molding (RIM) oflarge parts, such as automobile bumpers.
The tough polyur&&e coating, which was used as a
super-coating on German aircraft during World War 11, is
now produced a t an annual rate of more than 75 thousand
tons in the United States. These coatings are available as
one- and two-package systems.
One-Package Systems
Polvurethanes with unreacted isocyanate groups, which
r e a c k t h moisture in the air, are used in ~ n i - ~ a i k sysa~e
tems. The reaction product of urethane and alkyd resins
(polyester resins produced by condensing a dihydric alcohol and a dicarboxylic acid) are also used in one-package
svstems. I n another one-oackaee svstem. the terminal isocyanate groups are condensed with a monohydric compound, such as phenol (C6H50H),to produce a urethane
that is unstable a t elevated temperatures.
In the cross-linking process, which is comparable to the
vulcanization of rubber, the polymer changes from a linear
chain to a three-dimensional structure that is more like a
bed spring with additional bonds between the chains. Like
vulcanized rubber. cross-linked ~olvmersare stronger. less
soluble, and more heat-resistani than the linear poiyiers.

no-Package Systems
The reaction between the polyol and diisocyanate reactants occurs in situ in the two-package system. These twoDackaee svstems are also used to produce ~ o l w r e t h a n e
Eoatings, which can be reacted further (cross-iinked, in the
Dresence of a triethvlcnediamine catalvst (Dahcol. A more
;table three-dimeniional polymer is odtained by the crosslinking reaction.
While the use of polyurethane fibers is limited to applications where stiff fibers are acceptable, "snap back" fibers
(Spandex) are produced by joining sequences (blocks) of
stiff urethane polymers and flexible hydmxyl-terminated
polyesters. Spandex fibers are used for the stiff parts of
undergarments, socks, and surgical stockings (7).

- .

Reaction Injection Moldings

I n 1989 the United States produced 94 thousand tons of
polyurethane moldings by reaction injection molding

910

Journal of Chemical Education

(RIM) (8). This process depends on a "self-skinning" process that yields moldings of controlled densities, consisting
of a hardIshel1 exteriorand a microcellular core.
The original RIM technology, which made possible the
molding of large objects a t moderate pressures in inexpensive molds, was a slow process that required external release agents on the mold surfaces. The reaction rate in the
RIM process has been improved using aromatic diamines
in place of ethylene glycol and a solubilized zinc stearate
release agent. The molding rate of today's RIM process is
comparable to that of standard injection molding, but
much larger moldings (100 lb) can be reproduced by the
modern RIM process.
The strength of parts produced by the RIM process has
been improved by the incorporation of reinforcements,
such as glass or carbon fibers (RRIM). The properties of
these uniaue molded-in-place products have been improved by ihc fonnatlon ofhybrid copolymers of epoxy and
unsaturated polyester resins. The RIM technolorn has also
been used t~-~r;ducelarge molded articles from nylon 6
(Nyrim),. dicsclopentadiene
(Metton) polyurea-amines,
.
.
poiyester-amines, and epoxies.
Advances in Polyurethane Technology
The most dramatic advance in polyurethane technology
may be tubeless automobile tires.l'neumatic polyurethane
tires arc being produced in Czechoslovakia, and solid polyurethane tires-are beine
.. used on industrial eoui~meut.
such as forklift trucks and as automobile spare tires in the
U ~ t c dStates (9).The next advance will be a 100.000-mlle
tire with a solid urethane tread and a resilient foamed
polyurethane core.
Polyurethanes are already being used in diverse applications.

..

efficient insulation far refrigerators

cushioning materials for packaging, bedding, and upholstezy
artificial organs
support for weather-damaged utility poles (I01
fenders, fascias, and panels for Chrysler minivans (11)
sound deadeners in automobile engines (121
automotive finishes and automobile bumpers
ski boots and shoes
large satellite antennas
Literature Cited
1. &&an,
G. B. J Chem. Educ. 1988.65.803.
2. KaUmnan,G.B. CHEMTECHl988,18(121,125.
3. M-el, C. S.;Carraher, Jr,C. E. In Pioneers in Polymer Seiam; Seymour, R. B.:
Pading, L. et al., Eds.;Kluwer: Dordrrdrht, The Netherlands, 1989;Chapter 12.
4. Gupta, R. C. Chem. Bus. 1888,2(22), 107.
5 . Seymour, R. B.: Hi@na, J. E%pg?imntol Organic Chemefry;Bsmes and Noble:

NswVnrk
1911
..... ....., .
....
6 . Seymour, R. B. Infmdmdfian fo P o l p Chemistry;
~
Mffiraw Hill: NenYmk, 1911.
7. Seymour, R. 9. Eneyeloprdio of Pkyrvol &ieand
Academic: Or-

Tmhnology:

lando, ,%I

1981:Vol. 11.

8. Sheard.A.Elasfomr& 1990.12212).16.
9. stokea,'~.;
pajtas. S.
I&B,121(11.19.
10. Srnoluh, 0. R. Modem Plastics 1989,66l12),28.
11. Wipotsky,V, Plast. Eng 1963,45(91,23.
12. Eeekhsut, G.: Pham, T.: Iacknmd, R.J. ModPrn Plostiea 1988,ffi(4). 132