CHAPTER ONE

INTRODUCTION

Linear polyurethanes (PU) are polymers in which the principal chain

structure is composed of aliphatic or aromatic sections R1 and R2 fixed
together with polar urethane groups (formula 1):
O

~ R1 NH C O R2 ~ (1)

wherein R1 makes an aliphatic, aromatic or alicyclic radical derived

from the isocyanate monomer, and R2 is a more complex group derived
from the polyol component (polyether or polyester). The commercial
manufacture of polyurethanes is nearly solely based on the polyaddition
process which involves diisocyanates and bi-functional or poly-functional
polyols with hydroxyl terminal groups (equation 2):

n OCN R1 NCO + n HO R2 OH ...

( O R2 O OC NH R1 NH CO ) n (2)
The possible presence of poly-functional components, e.g. triisocyanates
obtained from trimerisation of isocyanate monomers, or the use of
branched hydroxyl polyols, will yield polyurethanes with three-dimen-
sional cross-linking.
The structure of PU chains can be additionally diversified by the
polyaddition process regime, and in particular by the relative sequence
of charging individual feeds. It is a frequent practice that a prepoly-
mer is synthesised initially and the excess amount of one component
is used, e.g. too much diisocyanate (B) in relation to polyol (A). When
the polyol component is added to diisocyanate, the molar ratio of the
reacting substances is decisive for the obtained size of the isocyanate
prepolymer macromolecule (equation 3):
2B + A BAB
3 B + 2A BABAB
etc. (3)
2 chapter one

The synthesised urethane-isocyanate prepolymer BAB or BABAB

can be further extended at the next reaction step by means of a low
molecular weight diol, e.g. 1,4-butanediol (BD) or other compound
which has active hydrogen atom(s) in its structure. High molecular
weight polyurethanes are produced in this way, and the size of the final
macromolecule—when there are no diffusion constraints—is controlled
by the molar ratio of the reacting functional groups (equation 4):
n OCN BABAB NCO + n HO CH2 CH2 CH2 CH2 OH
(O CO
(4)
NH BABAB NH CO O CH2 CH2 CH2 CH2 ) n

It is also possible to synthesise polyurethanes in a single-stage process.

The molar ratios for diisocyanate, polyol and extender should be
carefully selected then, yet the chain structure will not be so precisely
defined in that case.
PU chains will not contain only urethane structures (formula 1),
ether groups and ester groups derived from polyols. Depending on
the specifications of feeds (i.e. purity), and on the method adopted for
the polyaddition process, one can find also urea groups, biuret groups,
allophanate groups, carbodiimide groups, aromatic hydrocarbon rings,
azaheterocyclic (isocyanurate) structures or oxazolidone structures, and
even ionic groups in some cases.
Polyurethane plastics were initially synthesised by Bayer [1], and they
have been known to users for nearly 60 years now, predominantly as
elastomers and foams. The first polyurethane, Perlon U, was obtained
in 1937, in the reaction of 1,6-diisocyanatohexane and 1,4-butanediol
[1]. Polyurethane products were introduced into the market in late
1940s and they quickly established a strong position there, mostly as
elastomers and foamed materials. The essential distinguishing criterion
for polyurethanes against other plastics is their density. Polyurethane
plastics belong now to the group of important materials applicable in
numerous fields of engineering [2]. If the volumes of polyurethane
products and raw materials needed for that production are considered,
PUs shall be put among the prime polymeric materials, and namely
they shall be ranked 5, after the unquestionably dominant polyolefins
(polyethylene, polypropylene), after PVC, after polystyrene and diene
rubber.
Very wide applicability of PUs results from the fact that their perfor-
mance properties can be extensively modified by selecting appropriate
raw materials, catalysts and auxiliary compounds, by employing various
 introduction 3

production methods and/or by employing various methods for further

processing and/or for shaping the final products. Resulting from their
specific microphase structure, which is formed by rigid chain segments
and flexible chain segments, polyurethanes offer very good elasticity
with reasonably high mechanical strength and abrasion resistance at
the same time, and also controllable hardness. Polyurethanes can be
available both as relatively rigid plastomers and as flexible elastomers
with compact or foamed structures. There are two inhibiting factors
for applicability of polyurethanes: their limited stability at temperatures
above 90°C and their flammability. That should be in particular referred
to foamed polyurethanes.
PUs are produced in the form of foamed plastics, structural elas-
tomers and coating elastomers, adhesives, leather-like materials and
auxiliary agents. Flexible cellular PU elastomers became inherent in
comfort-providing elements, especially in furniture making and automo-
tive industry. On the other hand, rigid foamed PUs can be converted
into lightweight elements with structural stability and superior thermal
insulation performance (closed-cell foams) and/or acoustic insulation
performance (open-cell foams).
Which is worthy of notice is that thermoplastic elastomers (PUT) are
also available. These can be processed as typical thermoplastics due to
thermal restoration of their allophanate groups [3–7].
A newer trend in application of PUs is the production of biodegrad-
able ionomers. These make the feedstocks for aqueous dispersions which
need no external emulsifiers and which find their outlets as environ-
mentally friendly lacquers [8, 9]. Combinations of emulsions of PU
ionomers with emulsions of other polymers, like poly(vinyl alcohol) or
poly(vinyl acetate), yield interpenetrating polymer networks (the so-called
semi-IPNs) with very good adhesion to metallic and ceramic substrates,
and with improved resistance to water [10].
Another interesting application is the production of typical IPNs
with the use of PUs and other chain polymers, like poly(methyl meth-
acrylate) [11], polystyrene [12], or with condensation polymers, like
unsaturated polyesters [13], epoxy resins [14] and polysiloxanes [15],
with no covalent bonds between the IPN components.
The use of vegetable raw materials: starch [16], castor oil [17],
natural rubber [18], lignin, wood flour, molasses, cellulose, glucose,
fructose or saccharose, makes it possible to obtain PUs which are rela-
tively easily biodegradable.
4 chapter one

The exceptional combination of physical properties, hydrolytic sta-

bility as well as low in-vitro protein adsorption and platelet adhesion
to PUs enables some medical applications for where the contact with
body fluids, e.g. plasma and blood, is required [19, 20]. Polyurethanes
generally offer advantageous performance properties and ease of pro-
cessing, good resistance to water, to atmospheric conditions, to oils,
greases, organic solvents, diluted acids and alkalies, and in case of
non-aromatic PUs—also resistance to photo-oxidative ageing. All that
makes them applicable in numerous fields of technology, economy and
in everyday life [21, 22].
The above advantages classify polyurethanes as modern organic
polymeric plastics and they attract considerable interest of materials
engineering, i.e. that branch of science which deals with implemen-
tation and commercialisation of new materials which satisfy more
and more sophisticated requirements reported from the automotive
industry, medicine, economy in general, and even everyday life. The
duty of polymer technology, in this context, is to design, to synthesise
and to commercially produce the materials based on high molecular
weight compounds, which in this specific case means to provide the
adequate—and more complex than for other polymers—stock of raw
materials, and to develop the efficient and cost-effective processes for
the production of polyurethanes. It should be noted that it is just the
need for modern polyurethane materials that for over 50 years has been
giving inspiration to develop new processes for the production of feed
materials, to develop new polymerisation processes, and to develop new
processing methods, like Reaction Injection Moulding (RIM) wherein
intermediates are subjected to final conversion. No progress in those
methods could be possible without many years of basic research within
kinetics, synthesis of urethane oligomers and polyaddition processes.
A number of fundamental issues for that technology could be suc-
cessfully resolved recently, owing to modern analytical and numerical
methods which made it possible to run complex kinetic research pro-
grammes [23].
The purpose of this volume is to submit a summarising outlook on
some issues of the polyurethane manufacturing processes—after 50
years of application of PUs. By necessity, it will have to be limited,
yet it has been intended to present a review which is retrospective and
possibly comprehensive at the same time. That task, which is rather
difficult to do because of vast literature sources within chemistry and
technology of polyurethanes, has not been approached to with the aim
 introduction 5

to present the history. Most attention has been focused on the problems
of synthesis, structures and properties of linear polyurethanes, i.e. final
products but in most cases intermediates for modern polyurethane mate-
rials. That presentation of the subject, with due consideration of the
difficult but fundamental points in chemical foundations and structural
constraints, which are important for that group of polymers, should
be useful also for those interested in the materials technology, who are
involved mainly in the production of final products of polyurethane
plastics. Whenever individual synthesis methods or properties of linear
polyurethanes were discusses, essential interests of potential readers
were kept in mind, hence the discussion was frequently referred to the
application issues, i.e. most important problems for materials engineer-
ing. Within that area, special attention was paid to the possible use of
the polymers in question as modern structural elastomer materials,
e.g. in medical implants, environmentally friendly lacquer coatings
and binders, and in special materials for electronics, like liquid crystal
polymers, ion exchange membranes, polymeric filling compounds for
integrated circuits, etc.