9 Polyurethanes
Helena Janik, Maciej Sienkiewicz and Justyna Kucinska-Lipka
Polymer Technology Department, Chemical Faculty, Gdansk University of Technology, Poland
O U T L I N E
Introduction
General Characteristics of Polyurethanes
Raw Materials Used in the Synthesis of
Cross-Linked Polyurethanes
Synthesis and Cross-Linking Reactions of
Polyurethanes
Introduction
Polyurethanes of practical use
like poly(ester-
urethanes), poly(ether-urethanes), poly(urethane-
urea), and other types not mentioned here
belong
to block copolymers. In this type of copolymer,
chemically connected hard and soft blocks (seg-
ments) are present. This is a group of polymers that
is characterized by the presence of polar urethane
groups in the main backbone next to ester, ether,
urea, and other groups.
Polyurethanes were first obtained by Otto Bayer
in 1938. Since then tremendous progress has been
observed and the applications of those polymers
have been growing. The most well-known commer-
cial example of PU is the polyurethane fiber with
the name Lycra, which was introduced into the mar-
ket in 1958 by DuPont.
Continuous development in the research of those
polymers is due to the theoretical support studies of
Flory, Mark, and Tobolsky. The papers of Macosco,
MacKnight, and Cooper gave technological and
morphological support. Polyurethanes are an inter-
esting group of polymers for researchers dealing
with synthesis, physical chemistry, materials sci-
ence, and engineering.
They are obtained by step-growth polymerization
(polyaddition) from three main components: macro-
diols (macrotriols), diisocyanates (polyisocyanates),
Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00009-9
© 2014 Elsevier Inc. All rights reserved.
253 Morphology of Linear/Branched vs.
Cross-Linked Polyurethanes 275
254
Manufacturing Methods and Technical and
Functional Properties of Thermosetting
258
Polyurethanes 277
References 289
266
and small molecular weight chain extenders or
cross-linkers.
The ability to obtain those polymers at room
temperatures provides another economical aspect
for their development. Moreover, they can be syn-
thesized with various molecular weights tailored to
the desired application by changing the stoichiome-
try of the components. It is worth mentioning that
from a technological point of view, they are
obtained via waste-less technology and very often
in one-pot reactions, which is important environ-
mentally. A very popular technology is reactive
casting, in which the synthesis and shaping of the
products go together. Recently there has been big
interest in renewable raw materials developed for
PU. For the last 10
15 years around a 4
5%
growth in the production of different PU products
has been observed; this is the fifth group of poly-
mers of technical importance.
The properties of polyurethanes can be tailored in
a wide range. Some examples are as follows: elastic
or hard foams, elastomeric, thermoplastic, or thermo-
set solid products, coatings, adhesives, fibers, syn-
thetic leathers, isolated or conducting materials,
soluble or insoluble products, and biodegradable or
biostable products. From a materials science point of
view, the fundamental aspects of crystallization,
phase separation, and nano and micro morphology
are very often discussed in order to better understand
253
254 HANDBOOK OF THERMOSET PLASTICS

HO R OH + O C N R' N C O HO R O C NH R' N C O
O
+ n R(OH)2
HO R O C NH R' NH C O R O C NH R' N C O
+ n R'(NCO)2
O O n O

Figure 9.1 Reaction between isocyanate and hydroxyl group.

SS SS SS SS

HS HS HS

Where:

Macrodiol Diisocyanate Extender: diol, diamine

Figure 9.2 Segmented polyurethanes showing hard (HS) and soft segments (SS).

the correlation between the chemistry, physics, and
engineering of these materials. This was possible due
to studies of PU by transmission and scanning elec-
tron microscopy (TEM, SEM), atomic force micros-
copy (AFM), micro-Raman (μ-Raman) spectrometry,
reflected infrared spectroscopy (IR-ATR), and differ-
ential scanning calorimetry (DSC).
Lately the interest in thermoset polyurethanes
has grown as well, which gives support to the new
applications of PU. Thus, next to traditional, techni-
cal elastomeric or thermoplastic products, cross-
linked PUs are obtained as well. Cross-linked PUs
are developed as advanced coatings or membranes,
polymers with shape memory properties, materials
resistant to biodegradation for medical application,
or materials with non-elastic optical properties for
electronics.
General Characteristics of
Polyurethanes
Polyurethanes can be obtained in various ways
[1
3]. As was mentioned earlier, they are obtained
by step-growth polymerization. In this case di- or
tri-functional hydroxy compounds are used, and di-
or tri-functional isocyanate-alternating copolymers
are created (Figure 9.1).
In cases where low-molecular-weight chain exten-
ders (cross-linkers) are used next to the abovemen-
tioned compounds, segmented block copolymers
(segmented PU) are obtained in which hard segments
(An 5 HS) are reaction products of isocyanates and
chain extenders, while soft segments (Bm 5 SS) are
created as reaction products of isocyanates and
macrodiols (Figure 9.2). When using isocyanates
with polyesterdiols and small molecular diols as
chain extenders, poly(ester-urethanes) are obtained.
In the case of diamines or ureas as low-molecular-
weight chain extenders instead of diols, poly(ure-
thane-urea) (Figure 9.3) or poly(urethane-biuret) are
obtained, respectively (Figure 9.4).
In both segments there are present aNHCOOa
groups, but their concentration is different, and due to
this, they are of different flexibility, especially if aro-
matic isocyanate is used. In hard segments, urethane
groups are very closely packed next to aromatic rings,
which inhibits the change of configuration, while in
soft segments that are rich in aCH2a, the rotation
around carbon-carbon bonds is more favorable. Very
often another approach is used to describe soft seg-
ments. Simply, the macrodiols used in the synthesis
of PU are taken as soft segments. This simplifies the
calculation of hard and soft segment shares and dis-
cussion of their influence on the properties as a
whole.
9: POLYURETHANES
2 OCN R NH C O O C NH R
O O
OCN R NH C O O
O O
OCN R NH C O O
O O
Figure 9.3 Production of poly(urethane-urea).
O ready to use in small- or large-scale production of
2 OCN R NH C O O C NH R NCO + H2 N C NH2
O O
OCN R NH C O O C NH R NH C NH
O O
O C=O
OCN R NH C O O C NH R NH C NH
O O O ing from different groups. Thus, in PU we can
Figure 9.4 Production of poly(urethane-biuret).
At stoichiometric use of diisocyanates and diols
(macrodiols and chain extender taken together) lin-
ear segmented polyurethanes are created with ther-
moplastic properties (TPU). Thus, TPU products
are produced from earlier synthesized polymers in
the form of granules
The chemical structure of polyurethanes can be
built together by shaping of the products. That kind
of PU processing takes place in reaction injection
molding (RIM) or reaction casting technology.
Moreover, PU can be obtained in a one- or two-
step procedure called prepolymer one (Figure 9.5).
In that technology, in the first step we use macro-
diols with an excess of isocyanates to create so-
called prepolymer in which aNCO-terminated soft
segments and free isocyanates exist together. In that
step we can control the length of soft and hard seg-
ments by changing the stoichiometry of the process.
In the second step of the process, we add chain
extenders or cross-linkers that react with the excess
of isocyanate-built hard segments that connect with
soft segments. The second step of the process is
characterized by the isocyanate index (ICI, the ratio
of isocyanate groups in unreacted compound to
small molecular diols, triols, and diamines). The
higher the ICI, the shorter the hard segments and
the higher the probability of allophanate bond crea-
tion. In practice, one can buy prepolymer systems
255
NCO + H2N R1 NH2
C NH R NH C NH
O
R1
C NH R NH C NH
O
PU products (Table 9.1).
A very important item in the description of PU
properties is also secondary bonding, such as
hydrogen or van der Waals interactions [4,5]. The
hydrogen atom in the urethane group has a partial
positive charge and can interact with oxygen com-
have three types of hydrogen bondings [4,5] as
free oxygen electron pairs can come from ester
groups (ester-urethane interaction: SSEs-HS), ether
groups (ether-urethane interaction: SSEt-HS), or
urethane groups (urethane-urethane interaction:
HS-HS; Figure 9.6).
The properties of segmented PU are differenti-
ated depending on its structure, especially the con-
tent of hard segments [1
3]. TPUs belong to
thermoplastic elastomers when the share of HS is
in the range of 30
50%. When HS is increased (up
to 60
70%) they are hard and brittle and behave
like high-module thermoplasts [6,7].
Young’s modulus for PU is in the range of
8
2,000 MPa depending on HS content, types of
chemistry, and technology applied during their cre-
ation. The density of PU can be changed in a range
of 0.2
1.2 g/cm3 [8,9].
The tensile strength is very high (25
70 MPa) in a
wide range of hardness. It is sensitive to the molecu-
lar weight of macrodiols, their symmetry, and degree
of branching or cross-linking (Figures 9.7 and 9.8).
The hardness in Shore scale is around 50A
80D.
The most positive feature of elastomeric PUs is a
much longer time of exploitation under high level of
stress in comparison to cross-linked compounds.
The essential influence on mechanical properties
of PU is the type of isocyanate (IC) used [11].
Raush [12] showed that tensile strength (TS) grows
with the increase in the number of aromatic rings
and methylene groups in IC.
256 HANDBOOK OF THERMOSET PLASTICS

Kothandaraman [13] compared the PU properties than MDI-PU. It was explained by higher reactivity
obtained from HMDI, TDI, and MDI. The weakest of TDI than MDI with macrodiols. Isocyanate
properties were obtained in the case of HMDI- index (ICI) was very important as well, especially
based PU. It was explained by lower reactivity of in the two-step process that yielded PU. An
HMDI with IC, which leads to lower molecular increase in ICI up to 1.15 caused an increase in ten-
weight [14,15]. Desai [16] noted that TDI-PU sile strength, but led to lower molecular weight,
showed higher tensile strength and lower strain which is negative [17
19].
Kontou showed that with the increase of ICI there
were more difficulties in controlling allophanate
Macrodiol Diisocyanate
bonding levels, which influenced the mobility of the
chains, the amount of hydrogen bonding, and mor-
phology [20]. A similar effect was observed when
selective cross-linking was applied in the hard or soft
segment phase [21]. Petrovic noted that an increase in
Mixing
the amount of low-molecular-weight cross-linker
used (TMP, hard segment cross-linking) up to 50%,
I step used next to BDO chain extender, in the second step
of synthesis caused an increase of TS. Adding a high-
er amount of TMP did not change TS and strain at
Prepolymer break. Tsai [15] studied the influence on mechanical
properties of glycerin as a chain cross-linker in the
mixture (with a BDO chain extender). The superior
properties were obtained only in a narrow range ratio
Butanediol
of glycerin to MDI. All authors investigating the
influence of adding cross-linking agent in the synthe-
sis of PU claimed that mechanical properties changed
due to changes of hydrogen bond levels, various abili-
ties to crystallize, and changes in phase separation.
II step Good balance must be achieved to yield the desired
mechanical properties.
The properties of PU also depend on type, func-
tionality, molecular weight, and amount of macro-
diols or macrotriols used. Changing the molecular
Segmented polyurethane
weight of those compounds controlled the low tem-
Figure 9.5 Production of polyurethane products by perature range of PU used. The glass transition of
prepolymerization. the soft segment phase Tg(ss) was in the range of
246°C to 100°C. The decrease of molecular weight

Table 9.1 Examples of Commercial Prepolymers

Prepolymer Composition Extender Name Producer

Macrodiol Diisocyanate
PEA lub 1,5-NDI 1,4-BD Vulkollan Bayer
PEA/PBT 2,3-BD
H20
Polyester MDI 1,4-BD Multrathan F66 Mobay Chemical Co.
ED
Polyether TDI MOCA Multrathan F196 Mobay Chemical Co.
PTMO TDI MOCA Adiprene Bayer
9: POLYURETHANES 257

50
Hydrogen bondings Interaction
Hardness 60D
45
Urethane-urethane
O HS ~~~~ 40
~~~~ HS NH O C
NH HS ~~~~ HS < - > HS
35

Stress [MPa]
Hardness 85A
30

25
Urethane-ether
C SSEt ~~~~
~~~~ HS NH O 20
C SSEt ~~~~ HS < - > SSEt
15

10
Urethane-ester
O SSEs ~~~~
~~~~ HS NH O C 5
C SSEs ~~~~ HS < - > SSEs
0
0 100 200 300 400 500 600
Strain [%]
Figure 9.6 Types of hydrogen bonding in
segmented polyurethanes. Figure 9.8 Stress-strain curves for polyurethanes
with different hardness (overworked on the basis
of [10]).
1000 30% HS
40% HS
65% HS
and chain extender (cross-linker) used [26,27]. The
100
presence of domains influenced the deformation
properties of PU. Trick showed that their influence
G [MPa]

10 was the highest on hysteresis in the first cycle of

1 resistance to crack propagation at tear test is high
0.1
−100 −50 0 50
Temperature [°C]
Figure 9.7 Modulus as a function of temperature
for polyurethanes with different % of hard segment
content (overworked on the basis of [10]).
delays or inhibits the ability of soft segment for
crystallization.
Morphology is the next factor that strongly influ-
ences PU properties. According to Smith [22], high
TS for TPE-U was observed as the hard domains
were of isolated type. Paik- Sung [23,24] found
that connected domains in TPE-U led to higher hys-
teresis and lower strain at break. Bonart [25]
showed that interpenetrating domains were favored
for plastic deformation of hard segments. The size
and type of domains depended on the type of DI
stress-strain studies [28].
PUs have good abrasion properties and their
as well. They can be used in a wide range of tem-
peratures (2 40 to 80°C) for a long time. Thermal
stability of PU is strongly dependent on hydrogen
100 150 200
bonding presence and the isocyanate type used.
Hydrogen bonding dissociates at around 80°C.
Thermal stability of different ICs is as follows:
HMDI . MDI . HTDI . TDI . HDI.
Cross-linking led to higher temperature resis-
tance. It changed chemical resistance and mechani-
cal properties as well. Moreover it should be
introduced in a controlled way as Ophir found that
cross-linking at high temperature (e.g. 210°C) was
a very statistic one and cross-linking took place in
both segments, which was not favorable as Young’s
modulus and thermal stabilities decreased [29].
Russo [30] found that soft segment cross-linking
led to higher thermal stability and optical clarity of
PUs. Hard segment cross-linking in Chang’s studies
showed an increase of optical clarity, hardness, and
thermal stability, and a decrease in tensile set.
Chemical resistance and thermal degradation para-
meters were unchanged [31].
258
Petrovic analyzed cross-linked PUs in which grow-
ing amounts of TMP were added and found irregular
changes in Tgs and the linear coefficient of expansion
difficult to explain. The clear decrease in crystallinity
of hard segments was also observed [21,32].
The resistance against attack of microorganisms
was different for various types of PUs. It was found
that microorganisms attacked first free isocyanate
groups, then biurettes and urethane ones [33,34]. Poly
(ester-urethanes) were more sensitive to biological
degradation than poly(ether-urethanes), which was
explained by the higher ability for hydrolysis of ester
groups. Cross-linking increased resistance against
biodegradation [35
37].
Raw Materials Used in the
Synthesis of Cross-Linked
Polyurethanes
The basic raw materials used in the manufacture
of different varieties of urethane polymers are as
follows: [3,38
40]
(a) Aromatic or aliphatic diisocyanates.
(b) Multi-isocyanates.
(c) Polyols (oligodiols), which contain in their
structure two or more hydroxyl groups. If
they contain two hydroxyl groups, they
should be prolonged by extenders compris-
ing at least three reactive groups, that is,
cross-linking agents.
(d) Low-molecular-weight chain extenders
(especially short-chain glycols or diamines)
or cross-linkers.
(e) Catalysts.
(f) Blowing agents.
(g) Auxiliary agents.
Isocyanates
Isocyanates are compounds containing highly
reactive isocyanate groups (aNQCQO), and have
two accumulative double bonds. These groups
are available in several mesomeric structures that
can be presented as: aN(δ2)QC(δ1)QO(δ2).
From this structure results the possibility of the iso-
cyanate group reaction with groups being both
donors and acceptors of electrons.
HANDBOOK OF THERMOSET PLASTICS
Isocyanate groups can therefore react according
to three types of reactions:
1. Reaction with each other, which leads to the
formation of cyclic structures in the form of
uretidione and isocyanurate rings.
2. Reaction with compounds having active
hydrogen atoms in their chain.
3. Reaction with chemical compounds that do
not have active hydrogen atoms.
Each of these reactions can lead to the formation
of a polymer, however, from a technological point
of view, the most important of these reactions, in
which the aNCO group reacts with compounds
containing active hydrogen atoms, is used in poly-
urethane synthesis. From a chemical point of view
there are two types of isocyanates: aliphatic and
aromatic. Leading manufacturers of isocyanates are
BASF, Bayer Material Science AC, ICI, DOW
CHEM., Shell, and Huntsman. Table 9.2 shows
examples of the most commonly used diisocyanates
in the manufacturing technologies and synthesis of
polyurethanes [49,50].
Isocyanates
Health Hazard
Evaluations
Polyurethanes are classified as polymers, which
are not detrimental to the life and health of living
organisms. A high toxicity level, however, char-
acterized the raw materials used in polyurethane
synthesis, such as isocyanates and amine chain
extenders. Among the harmful compounds used
in the synthesis of polyurethanes are organome-
tallic and amine catalysts, as well as organic
blowing agents used in the synthesis of polyure-
thane foams [51,52].
Isocyanates, according to the classification reg-
ulation (EC) number 1272/2008, are toxic: acting
irritants to eyes, skin, mucous membranes, and
the respiratory system. The most dangerous to
health is contact with isocyanate pairs, which if
inhaled can cause allergy, asthma, or breathing
difficulties as a result of irritation of the respira-
tory tract. Isocyanate contact with the skin can
cause irritation manifested by rash, itching, hives,
or swelling. Isocyanates are not classified as
potentially cancer causing in humans or animals
[51,52].
9: POLYURETHANES 259

Table 9.2 Most Commonly Used Diisocyanates in the Synthesis of Polyurethanes [2,3,39]

Name Formula
Toluene diisocyanate (TDI), usually obtained as CH3 CH3
a mixture of isomers 2,4-TDI and 2,6-TDI, with NCO OCN NCO
mass composition: 65/35 or 80/20 (% wt.)
[41,42]

NCO
2,4-TDI 2,6-TDI
Methylene diphenyl diisocyanate in pure form NCO NCO N
(MDI) or polymeric mixture of multiisocyanates OCN CH2 NCO
(PMDI); usually used in the synthesis of
polyurethane foams [43,44] MDI n
PMDI
1,5-Naphthalene diisocyanate (NDI) [45] NCO

NDI

NCO

Hexamethylene diisocyanate (HDI) in pure form NH (CH2)6 NCO

or biuret obtained from HDI and H2O [46] C O
OCN (CH2)6 NCO
N (CH2)6 NCO
HDI
C O
NH (CH2)6 NCO

4,40 -Methylenebis(cyclohexyl isocyanate) (HMDI) OCN CH2 NCO

[47,48]
HMDI
Methylidyne-tri-p-phenylene triisocyanate [46] NCO

OCN CH NCO

The industry uses various types and varieties of
isocyanates in polyurethanes synthesis, which may
be present in different physical forms (solid, liquid,
and vapor). The level of insalubrity in humans is
caused mainly due to the vapor pressure variation
of each isocyanate. Particularly dangerous are the
diisocyanates of low molecular weight, because in
ambient temperature they have a greater capacity
to release vapor into the atmosphere. However, it
has to be remembered that isocyanates of high
molecular weight may also be released to the envi-
ronment. This is related to the exothermic nature
of the polyurethane synthesis, which provides a
sufficient amount of heat required for vapor release
of isocyanate in the atmosphere. It should be noted
that the danger of vapor release of isocyanate into
the environment is possible not only when working
with isocyanate monomers, but also with urethane
prepolymers and urethane oligomers, which con-
tain a certain amount of unreacted diisocyanates.
In addition, vapor and aerosols containing isocya-
nates may occur due to thermal degradation or
heating of un-polymerized polyurethane products,
especially in the case of high-temperature-curable
260 HANDBOOK OF THERMOSET PLASTICS

Table 9.3 Exposure Criteria for Isocyanates Created by NIOSH, ACGIH, OSHA, and UK-HSE [53,55]

Exposure Criteria
Exposure Criteria
Short Term or Ceiling

Full-Shift TWAs Limits
µg/m3 µg/m3
Isocyanate NIOSH ACGIH UK- NIOSH ACGIH UK- OSHA
REL TLV HSE REL TLV- HSE PEL
Ceiling STEL Ceiling Ceiling
TDI Toluene CA- 36 None None 140 None 140
diisocyanate LFC1
MDI 4,4’-Methylene 50 51 None 200 None None 200
diphenyl diisocyanate
HDI 1,6- 35 34 None 140 None None None
Hexamethylene
diisocyanate
HMDI Methylene bis None 54 None 210 None None None
(4-
cyclohexylisocyanate)
IPDI Isophorone 45 45 None 180 None None None
diisocyanate
NDI 1,5-naphthalene 40 None None 170 None None None
diisocyanate
TRIG Total reactive None None 20 None None 70 None
isocyanate group
ACGIH TLV is an 8-hour time-weighted average (TWA) exposure.
NIOSH REL is for time-weighted average (TWA) isocyanate exposures up to 10-hours per workday.
NIOSH RELs ceiling limit (CL) and ACGIH short-term exposure limits (STELs) are based on 10- and 15-minute time-weighted average
(TWA) exposures.
OSHA ceiling limit (CL) is a concentration that should never be exceeded during a workday.

polyurethane coatings [53,54]. In order to reduce
the hazard of isocyanate vapor inhalation, in the
technology of polyurethane production, monomeric
forms of these compounds are being replaced by
dimers, trimmers, or polymeric isocyanate deriva-
tives that have high molecular weight and a lower
tendency to release in the form of vapor [53].
Limited amounts of isocyanates in the air at the
workplace and the criteria for an acceptable time of
isocyanate impact on workers in factories producing
polyurethanes are strictly defined [53]. In the U.S.,
limits of allowable amounts of isocyanates in the air
and limitation of their exposure time were deter-
mined by the following organizations: National
Institute for Occupational Safety and Health
(NIOSH), which recommended limits of exposure to
isocyanates for an 8 or 10 h time-weighted average
exposure and/or ceiling (RELs); the American
Conference of Governmental Industrial Hygienists
(ACGIH), which was characterized by Threshold
Limit Values (TLVs®, Exposure Criteria on iso-
cyanates expressed as a time-weighted average, the
concentration of a isocyanate to which workers
can be exposed without adverse effects); the U.S.
Department of Labor, Occupational Safety and
Health Administration (OSHA), which determined
permissible exposure limits (PELs) expressed as a
time-weighted average (the concentration of isocya-
nates to which most workers can be exposed without
adverse effect averaged over a normal 8-hour work-
day or a 40-hour workweek). In Europe, the United
Kingdom’s Health and Safety Executive (UK-HSE)
created exposure criteria for isocyanates based on
the total reactive isocyanate groups from urethane
raw materials (TRIGs) in a total volume of air.
Table 9.3 summarizes the acceptable amounts of
isocyanates in the air that can affect workers in
short- and long-term exposure according to the
9: POLYURETHANES 261

Table 9.4 Polyols Commonly Used in Polyurethane Synthesis [56
62]

Name Chemical Name and Structure Manufacturer

Polios 55/20 Linear saturated polyester having an average molecular weight of Purinova
about 2000, based on ethylene glycol and 1,4-butanediol
Polios 250PA Polyester based on phthalic anhydride and diethylene glycol Purinova
G1000 Triols based on glycerol Rokita S.A
G441 Rokita S.A
G500 Rokita S.A
Rs450 Polyol based on glycol and sucrose Rokita S.A
RF 551 Sorbitol-based polyol Rokita S.A
®
PolyTHF 1000 Polytetramethyleneetherglycol 1000 BASF
®
PolyTHF 2000 Polytetramethyleneetherglycol 2000 BASF
Desmophen Polybutylene adipate diol with average molecular weight of about BAYER
2505 4,000
PCL, CAPA ε-Caprolactone Solvay

criteria set by NIOSH RELs, ACGIH TLVs, OSHA
PELs, and UK-HSE [53].
According to the manufacturer of isocyanates
and applicable European Union standards, work
with isocyanates must be done with appropriate
personal protective equipment. During exposure to
isocyanates, employees must be equipped with face
protectors (visors) and goggles to prevent eye con-
tact. In order to avoid skin contact with isocya-
nates, workers must use suitable protective gloves
(that meet the requirements of standard EN 374) as
well as protective clothing, which protect the body
from chemical contact. Workplaces that use isocya-
nates must be equipped with a special ventilation
system that removes from the working area the
vapors, mist, or dust containing isocyanates. It
should also provide absolute protection of the respi-
ratory system through the protective full-face
masks, type N100 (U.S.) or inset masks type P3
(EN 143). If the mask is the sole means of protec-
tion, there is a need to use a full-face supplied air
respirator.
Oligomerols
Oligomerols are compounds with flexible chains
and molecular weight ranges from 400 to 6000;
they are terminated with at least two hydroxyl
groups. They are usually about 2/3 of polyurethane
weight. Oligomerols give them flexibility, softness,
and resistance to low temperatures, and are usually
the cheapest polyurethane components. The most
widely used oligomerols for polyurethane synthesis
are oligoestrols, oligoetherols, and mixtures thereof;
the manufacturers of these are Purinova, Rokita
SA, BASF, Bayer, Dow Chemical Company, and
Huntsman [50,56].
Oligoestrols are usually obtained by the reaction
of anhydride acids with alkylene oxides, in lactone
polymerization or polycondensation of dicarboxylic
acids (e.g. adipic acid) with glycols (1,2-ethanediol,
1,2- or 1,3-propanediol, 1,4-butanediol, hexamethy-
lene glycol, diethylene glycol, neopentyl glycol). In
the synthesis of branched oligoestrols, mixtures of
the aforementioned glycols with triols are used
(e.g. glycerol, trimethylolpropane (TMP), or hexa-
triol). Linear oligoestrols are most often used in the
manufacture of urethane elastomers, but they can
be also used for the synthesis of cross-linked poly-
urethanes provided that the chain extender is at
least trifunctional. The most commonly used oli-
goestrols in practice are shown in Table 9.4.
Linear oligoetherols and branched oligoether-
triols are mainly obtained by polymerization of tet-
rahydrofurane (THF), in cationic polymerization or
copolymerization of alkylene oxides (e.g. propyl-
ene dioxide and ethylene dioxide with polyols).
Oligoetherols are resistant to hydrolysis and have
262
Table 9.5 Most Common Polyetherols Used in
Polyurethane Synthesis [56,59,63,64]
Name Formula
Oligo(oxy-1,4-butylene)
glycol HO (CH2)4 O H
n
Oligo(oxyethylene glycol)
HO CH2 CH2 O H
n
Oligo(oxyethylene glycol) HO CH2 CH O
n
CH3
relatively low resistant to oxidation, particularly at
elevated temperatures. Oligoetherol molecular
weight is usually in the range from 700 to 7000 and
is generally lower the higher number of hydroxyl
groups in the molecule. Oligoetherols with a molec-
ular weight above 1000 are solids. Table 9.5 shows
examples of oligoetherol structures.
Unsaturated oligomerols. In the synthesis of
thermoset polyurethanes, unsaturated monomers can
also be used, which in subsequent reaction steps
may be subjected to additional cross-linking, thus
obtaining a material with increased hardness and
resistance to water. The group of unsaturated mono-
mers also includes acrylic oligomerols obtained by
radical copolymerization of acrylic monomers, such
as acrylic or methacrylic acids and esters. The
source of hydroxyl groups in these acrylic polyols is
the use of co-monomers in the radical copolymeri-
sation reaction: hydroxyalkyl acrylates or hydro-
xyalkyl methacrylates. They can be used for the
preparation of polyurethane coatings [56,65,66].
Table 9.6 shows the most commonly used acrylic
oligomerols.
Another type of unsaturated oligomerol is oligo
(alkylene-ester-ether)diols, which are obtained by
polycondensation of adipic acid, glycols (ethylene,
propylene, or diethylene) with polyethylene glycol
and maleic anhydride. The unsaturated monomer in
a subsequent step is reacted with an isocyanate, and
that product is additionally subjected to a cross-
linking copolymerization with vinyl monomers.
The obtained materials, due to their high mechani-
cal strength and hardness, can be used in construc-
tion [67,68].
Oligomerols from renewable raw materials. A
group of oligomers received from renewable raw
materials that is gaining more popularity lately are
HANDBOOK OF THERMOSET PLASTICS
Table 9.6 Selected Acrylic Monomers Used in
Polyurethane Synthesis [56,65,66]
Name Formula
Methylmethacrylate CH2QC(CH3)COOCH3
Methylacrylate CH2QCHCOOCH3
Hydroxyethylmethacrylate CH2QC(CH3)
COOCH2CH2OH
Hydroxyethylacrylate CH2QCHCOOCH2CH2OH
Acrylic acid CH2QCHCOOH
H Methacrylic acid CH2QC(CH3)COOH
oligomerols obtained from vegetable oils. These
raw materials, in terms of chemical structure, are
esters of glycerol and higher fatty acids. The most
widespread and most commonly used oils include
canola oil [69], sunflower oil [70
72], palm oil
[73,74], and soybean oil [70
72,75].
Preparation of plant oligomers can be achieved
in several ways:
• Unsaturated fatty acids can be subjected to an
oxidation reaction in order to obtain the epoxy
derivatives; then an epoxy ring opening with
hydrogen donors, which leads to the formation
of hydroxyl groups [76,77].
• Epoxidation of vegetable oil in the reaction
with acetic acid and hydrogen peroxide or
other oxidizing agents [78].
Oligomerols derived from glycolysates. Due to
the need to reduce the consumption of valuable pet-
rochemical raw materials for polyurethanes, syn-
thetic methods have started using glycolysis
products, which are one of the leading chemical
recycling methods for the preparation of liquid pro-
ducts terminated with hydroxyl groups. The main
material subjected to the process of glycolysis on
an industrial scale is a poly(ethylene terephthalate)
(PET) that has been successfully used for the pro-
duction of porous polyurethane materials [79
82].
Polyurethanes are relatively expensive, and,
therefore, their recovery from used products in the
form of raw materials still arouses interest. Both
used elastomers and polyurethane foams are sub-
jected to glycolysis with various glycols (ethylene
glycol [83], 1,4-butanediol [84,85], diethylene gly-
col [86
88], and hexane-1,6-diol [89]). Thus, the
glycolysates obtained are characterized by hydroxyl
9: POLYURETHANES 263

Table 9.7 Examples of Low-Molecular-Weight Chain Extenders and Cross-Linking Agents Used in
Polyurethane Synthesis [3,38,39,50]

Name Formula Application

1,4-Butanediol HO 2 CH2CH2CH2CH2 2 OH Extender
Diethylene glycol HO 2 CH2CH2 2 O 2 CH2CH2 2 OH Extender
1,4-Di(hydroksoetyleno)benzen Extender
HO CH2 CH2 CH2 CH2 OH

1,6-Hexamethylenediamine NH2 2 CH2CH2CH2CH2CH2CH2 2 NH2 Extender

4 4’-Diaminodiphenylmethane Extender
NH2 CH2 NH2

Glicerol Cross-linking agent

CH2 OH
CH OH
CH2 OH

Triethylenediamine CH2 CH2 OH Cross-linking agent

HO CH2 CH2 N CH2 CH2 OH

1,1,1-Tris(hydroxymethyl)propane Cross-linking agent

CH2 OH
CH3 CH2 C CH2 OH
CH2 OH

number, water content, viscosity, and density before
using them to produce polyurethane; this is mainly
to obtain the rigid polyurethane foams.
Other types of oligomerols. Thermoset polyur-
ethanes can also be obtained by using polysiloxane
polyols, aminic polyols, novolak-based polyether
polyols, bisphenol A-based polyols, resorcinol-
based diols, and melamine-based polyols. The use
of such a wide range of polyols allows the produc-
tion of materials with a very high heat-resistance
and mechanical strength. This makes it is possible
to apply polyurethanes in many areas (automotive,
footwear, medicine, clothing, etc.) [50,56,57,90].
Low-Molecular-Weight Chain
Extenders and Cross-Linking
Agents
The use of chain extenders in the synthesis of
polyurethanes significantly affects their properties,
although their mass fraction is small. In practice, if
in the PU synthesis branched oligomerols are used,
their chains can be extended by low-molecular-
weight difunctional compounds; these possess groups
with active hydrogen atoms (especially diols and
diamines).
However, to obtain branched polyurethanes,
bifunctional oligomerols were used, and for chain
extension, tri- or polyfunctional compounds should
be used (defined as branching or cross-linking
agents). A list of typical chain extenders and cross-
linking agents used for polyurethane synthesis are
shown in Table 9.7 [3,38,39,50].
Catalysts
Acceleration of reaction time of isocyanates with
the catalysts affects not only the overall rate of poly-
mer formation. By changing the relative speed of
each reaction, it allows to adjust the structure and
properties of the finished product. Catalysts control
specific reactions, and also control the rate of chain
growth in foam (Tables 9.7 and 9.8), expansion rate
264
Table 9.8 Selected Amine Catalysts [38,91]
Name Main Compound
DABCO K-15 Potassium octavian in
glycol
DABCO TMR IV-Quaternary ammonium
salt in glycol
POLYCAT 41 Tris(dimethylaminomethyl)
triazine
POLYCAT 5 PMDETA
(Table 9.7), and polyurethane curing (Table 9.8),
allowing the preparation of polymers with optimized
properties and in an economically reasonable rate.
Often in practice are used mixtures of catalysts. The
most commonly used catalysts for the reaction with
isocyanates are the following: [3,49,91]
(a) Tertiary amines such as triethylene diamine
(diazabicyclooctane, DABCO), which
strongly catalyzes the reaction of isocyanate
groups with water (Table 9.8).
(b) Organometallic compounds such as tin com-
pounds, mainly di- and tetravalent types (tin
caprylates and laurates, and dibutyltin dilau-
rates), which strongly catalyze the reaction of
isocyanates with hydroxyl groups (Table 9.9).
(c) Trialkylphosphines and metal salts: Bi, Fe,
Sn, Co, Cd, Zn, Pb, Ti, and Sb [3,38,50].
Blowing Agents
In the technology of polyurethane foams, an
often-used blowing agent is carbon dioxide, which
is formed by the reaction of isocyanate with water.
In addition to the low cost foaming agent (which
water is) for the preparations of foamed materials,
physical blowing agents are also used to reduce the
apparent density of the foams.
Due to the fact that they are commonly used as
blowing agents, and the fact that they have a nega-
tive impact on the environment, chloro-fluorinated
hydrocarbons, under various protocols (Montreal
1987, London 1990, Copenhagen 1992, Vienna
1995, and Kyoto 1997), were strongly limited
[92,93]. Blowing agents should have a boiling point
above 25°C because the lower boiling temperature
causes their quick evaporation (before created
HANDBOOK OF THERMOSET PLASTICS
Table 9.9 Selected Organometallic Catalysts for
Polyurethane Preparation [3,49]
Name Application
Sodium bicarbonate Polyurethane foams
Tin dicaprylate Polyurethane foams,
elastomers, cross-
linked polyurethanes
Potassium acetale Cross-linked
polyurethanes
Dibenzyltindichloride Polyurethane foams,
elastomers, cross-
linked polyurethanes
structure is strong enough to stop emitting the gas),
which contributes to the collapse of polyurethane
foams. Now blowing agents are quite widely used as
saturated hydrocarbon compositions, usually with a
wide range of boiling points [49,94] (Table 9.10).
Chlorofluorohydrocarbons (HCFC), with the pres-
ence of hydrogen in the molecule, are less chemically
stable than chlorofluorocarbons (CFC, e.g. freons).
They disintegrate to inorganic compounds in lower
atmospheric layers, and they don’t pose a high risk to
the ozone layer. Their disintegration products con-
tribute to photochemical smog and to acid rain. They
are not classified as volatile organic compounds
(VOC); their use is permitted until 2030 [49,94].
Fluorohydrocarbons (HCF) don’t contain chlo-
rine, which is why their ODP is 0. There is no evi-
dence concerning their toxicity to the natural
environment. That’s why their applications are not
limited by any regulations.
The advantages of using hydrocarbons are as fol-
lows: low cost, high availability, zero halide con-
tent, and their ODP is 0. Their main disadvantage
is combustibility. They belong to the group known
as volatile organic compounds (VOCs) and they are
subject to strict regulations in many countries
around the world [49,94].
Auxiliary Agents
Auxiliary agents are added during the formulation
process of PU, which changes the specific properties
of the finished products. This is particularly impor-
tant in the production of polyurethanes applicable in
the automotive industry, medicine, and construction.
This group of agents include surfactants, flame
9: POLYURETHANES 265

Table 9.10 Selected Blowing Agents Used in Technology of Polyurethane Foams and
Their Properties [3,92,93]

Name Formula Boiling Point [°C] Ozone Depletion Potential

HCFC-141b CH3CCL2F 32 0.11
HCFC-22 CFCLF2 240.8 0.06
HCF-142b CH3CCLF2 29.2 0.07
HCF 134a CF3CH2F 226.3 0
HCF 245 ca CF2HCF2CFH2 25.4 0
HCF245 fa CF3CH2CHF2 15.3 0
C-pentane C5H10 49 0
N-pentane C5H10 36 0
Carbon dioxide CO2 287.8 0

retardants, organic pigments, reinforcing fibers,
polymer-processing aids, thixotropic compounds,
and fillers [3,38,39,49,50,95
98].
Surfactants
These are usually polyether
polysiloxane
copolymers.
Flame Retardants (Anti-Pyrines)
These are chemical compounds that inhibit the
inflammatory process and lead to a reduction in the
speed of pyrolysis or oxidation reactions of poly-
mers/plastics in contact with a flame (e.g. tetrabro-
modienes, pentabromophenol, hexabromo phthalate,
and polyols containing phosphorus or halides).
Organic Pigments (Dyes)
These are divided according to the type of chro-
mophoric systems they contain. In dyeing poly-
mers, the largest players are azo dyes (especially
red and yellow) and anthraquinone (mainly blue
and violet). In addition, the dyes based on pyrazo-
lone, benzopyran, phthalocyanine, and perylene are
also used. A special group is the polymeric dyes,
which are mostly a linear polymer with built-in
chromophoric groups.
Reinforcing Fibers
Both synthetic (polyamide, glass fiber) and natural
(jute, coconut fiber), and also glassy, metallic (e.g.
boron), ceramic whiskers (crystal fiber), carbon, and
aramid (e.g. Kevlar) are included in this category.
Polymer-Processing Aids
This group is used to improve the rheological
properties of the surface, which directly influences
the process of polymer formation. The main com-
pounds of this type include:
• Lubricants. These are strongly polar com-
pounds, especially fatty acids and their salts,
esters and amides (such as calcium and zinc
stearate), and the external lubricants of low
polarity compounds, the most important of
which are paraffin, montan waxes, polyethyl-
ene, and polypropylene.
• Fluidifying-Flow Modifiers or High-Temperature
Plasticizers. These lower softening point and
melt-flow of polymers without significant
changes in the glass transition temperature. The
basic fluidifiers include acrylic polymers, and
copolymers or terpolymers of acrylic monomers
(e.g. methyl methacrylate and acrylonitrile buta-
diene styrene).
• Anti-Adhesives. These are substances that prevent
plastic from sticking to the metal parts forming
machines, such as slot injection molds and brass
elements, and work surfaces of rolling shafts of
calenders and mills etc. Anti-adhesives can be
divided into internal and external types. Internal
anti-adhesives are added to the mass of proceed-
ing polymer. They migrate to the contact surface
of the polymer
metal and create an anti-
adhesive layer. The main parts of internal anti-
adhesives are external lubricants. External anti-
adhesives are put directly on metallic surfaces.
They reduce the adhesion strength of the mate-
rial. The best external anti-adhesive agents
include silicone formulations. External means are
usually used in the form of pastes, dispersions, or
emulsions.
266
Thixotropic Compounds
These can be used in liquid processing systems
with very low viscosity, for example, by means of
coating pastes or lamination with liquid chemo-
setting resins. The most popular thixotropic agents
are bentonite clays, diatomaceous earths, and silica
colloids.
Fillers
These are solid organic or inorganic additives in
the form of powders, spheres, fibers, sheets, and
sections used in amounts of from several to tens of
percents.
• Inert Fillers. These increase the weight and
volume of the polymer-filler composition and
reduce the price (usually with a certain decline
in the properties).
• Active Fillers (Amplifiers). These improve cer-
tain mechanical and/or physical properties.
Natural organic fillers such as wood flour, cot-
ton, vegetable fibers, and scraps of fabrics are
used mostly with thermosetting resins as mold-
ing components. Among granular mineral fil-
lers, the most important are chalk, kaolin, talc,
mica, barite, aluminum hydroxide, dolomite,
carbon black, graphite, metal powders, and
glass beads.,
• Nanofillers. Their size is nanoscopic
(1 nm 5 0.001 microns, or 0.000000001 m). They
are added in order to significantly improve many
physical and mechanical characteristics required
for new application areas. Increasing the deter-
mined specific surface area (up to 1000 times)
compared with conventional fillers corresponds to
stronger interaction with the polymer surface.
Nanofillers must have at least one dimension in
the nanoscale, such as layered silicate or clay.
They can also have two dimensions at the nano-
scale (e.g. carbon nanotubes) or three (siloxane
particles). Furthermore, to ensure contact of the
two largest surfaces, nanofillers must ultimately
be very well dispersed in the polymer matrix.
Synthesis and Cross-Linking
Reactions of Polyurethanes
The final molecular and supramolecular structure
of thermosetting polyurethanes and their macroscopic
properties, as well as their functional characteristics,
HANDBOOK OF THERMOSET PLASTICS
are formed in the cross-linking process. Effectiveness
of polyurethane cross-linking is usually characterized
by the so-called total cross-link density, which is
derived from chemical cross-linking bonds, hydrogen
bonds, and physical cross-linking bonds; this results
from the presence of various interactions formed by
van der Waals forces. Depending on the type of co-
monomers used in the polyurethane synthesis, and
also the parameters of the process (ratio of the reac-
tants, temperature, amount and type of catalysts), it is
possible to carry out the cross-linking reaction of
polyurethanes during their synthesis as well as in the
structure of already-synthesized polyurethanes.
Suitable selection of the cross-linking method and
cross-linking agents, and also catalysts, is essential in
the preparation of polyurethanes with specific proper-
ties and applications.
The process of polyurethane cross-linking can
occur in many different ways: [49,51,99,100]
(a) In soft segments by using polyols with func-
tionality higher than 2.
(b) In hard segments by using a chain extender
with functionality higher than 2 (cross-linkers).
(c) In hard segments by using an excess of iso-
cyanates and the proper catalyst, which leads
to the formation of allophanate or biuret
bonds that cause branching or cross-linking
at a particular temperature.
(d) In hard segments by using multifunctional
isocyanates.
(e) In hard segments by using products of isocya-
nate dimerization or trimerization with proper
catalysts.
(f) By the sulfur vulcanization of unsaturated
millable polyurethanes or cross-linking by
the radical copolymerization of unsaturated
polyurethanes.
Cross-Linking of Polyurethanes
via Multifunctional Polyols
The cross-linking of polyurethanes with the use
of multifunctional polyols (having a
functionality . 2) runs in the soft segments and
causes cross-linking in the main chain via urethane
bonds. Structure and properties of resulting polyur-
ethanes are strongly dependent on the functionality
(number of hydroxyl groups in the molecule) and
9: POLYURETHANES
Hard segment Soft segment
OH
+ OCN R NCO
OH
Figure 9.9 Reaction of polyurethane cross-linking by urethane bonds [102].
the molecular weight of the polyol used. The use of
multifunctional polyols for polyurethane cross-
linking has effects on the reduction of their cross-
link density in hard segment domains. This is due
to the weakening of the polyurethane cross-linking
effect via hydrogen bonds within the rigid seg-
ments, which is in turn due to the separation of the
main chains [56,101]. For the synthesis of seg-
mented polyurethanes with polyols having a func-
tionality greater than 2, a part of the side hydroxyl
groups of the polyol (excluding the terminal OH
groups, which had already reacted) reacts with the
remaining amount of diisocyanate to form urethane
flexible cross-bonds in soft segments, as shown in
Figure 9.9.
Currently, there are many known types of multi-
branched polyols used on an industrial scale for
thermoset polyurethane synthesis; they are dis-
cussed in an earlier section. For the synthesis of
cross-linked polyurethanes, typically used polyols
are those having a molecular weight in the range of
300 to 10,000 Daltons and functionality in the
range 2 , f # 8 (f- polyol functionality determined
as the number of OH groups per 1 mole of com-
pound) [56]. Polyols of low functionality (in range
2 , f # 3 hydroxyl groups/mol) and with high
molecular weight (2,000
10,000 Daltons) in the
reaction with diisocyanates give weakly cross-
linked elastic polyurethanes. They are used mainly
for the production of flexible polyurethane foams
[1,51,56,57,100,103,104]. Highly cross-linked, rigid
polyurethanes are obtained by using polyols with
high functionality (of 3
8 groups OH/mol) and a
low molecular weight (in the range from 150 to
more than 1,000 Daltons). Their cross-linking den-
sity and rigidity can be increased by using, as
monomers, multifunctional polyisocyanates with a
267
O O
C
NH
HN
R
C
O O
number of isocyanate groups from 2 to 6 NCO
groups/mol. Polyols of high functionality combined
with multifunctional polyisocyanates are used
mainly for the synthesis of rigid polyurethane
foams [49,51,100,105]. Figure 9.10 shows the
structure of the cross-linking reactions, and struc-
tures of flexible and rigid polyurethanes obtained
by using polyols with different functionality.
Currently, there are many well-known polyols
with a high degree of branching in the form of
hyperbranched polyols and dendritic polyols, which
are gaining importance in the synthesis of rigid
polyurethane foams [56,106
109]. Very interesting
is the fact that the use of hyperbranched polyols in
combination with conventional polyols provides the
ability to obtain rigid polyurethane foams with
reduced brittleness, which is not possible using
conventional branched polyols that have a function-
ality of 2
8 hydroxyl groups/mol. This is due to
the presence in hyperbranched polyols and dendritic
polyols of a structure with a special kind of internal
flexibility; it reduces the brittleness of polyur-
ethanes derived from them (Figures 9.11 and 9.12).
Cross-Linking of Polyurethanes
via Multifunctional Cross-Linkers
An important role in the synthesis and cross-
linking of polyurethanes is served by low-
molecular-weight chain extenders, which have two
functional groups capable of reacting with isocya-
nate groups (especially diols and diamines)
[1,51,56,100]. When the functionality of the chain
extender is greater than 2, it plays the role of cross-
linking agent that causes branching and cross-
linking of the polyurethane chains within the hard
segments. Cross-linking agents in the reaction with
268 HANDBOOK OF THERMOSET PLASTICS

Triol (oligo-polyol with three hydroxyl groups/mol) Octaol (oligo-polyol with eight hydroxyl groups/mol)
HO
OH HO
HO OH

HO
OH

OH OH
HO
OH

Δ + n OCN R NCO
Δ + n OCN R NCO

Cross-linked structure
of a flexible polyurethane foam

Cross-linked structure
of a rigid polyurethane foam

- Hard segment - Branching point (aliphatic,

cycloaliphatic, aromatic,
O O O heterocyclic branch chains)

O C NH R1 NH C O R2 O C O
Urethane groups
O O
NH C NH R1 NH C NH R2 NH C NH
- Oligomeric chain,
(oligoether, oligoester,
oligohydrocarbon,
O polyslioxane, etc.)

Urea groups

Figure 9.10 Cross-linked structures of flexible and rigid polyurethane foams [56].

the isocyanate groups of diisocyanates or macro-
diisocyanates present in urethane prepolymers
causes an increase in volume of the hard segments
and also affects the increase in hardness and brittle-
ness of polyurethanes [101]. Cross-linking agents
for polyurethanes that are primarily used are trifunc-
tional compounds. In practice, for cross-linking,
primarily triols, and to a lesser extent, triamines,
(due to their high reactivity) are used. The use of
triols in the polyurethane synthesis leads to urethane
cross-linking bonds; when trifunctional amines are
used the cross-linking takes place with the participa-
tion of urea cross-links. A polyurethane cross-
linking reaction with triols is shown in Figure 9.13.
9: POLYURETHANES 269

H3C OH HO CH3
Cross-Linking of Polyurethanes
HO OH
via Allophanate or Biuret Bonds
HO OH In addition to basic urethane bond-forming
HO OH reactions during the polyaddition of isocyanate
and hydroxyl groups leading to a polyurethane,
HO OH HO OH OH
HO OH
O
HO OH HO OH secondary reactions may occur where urethane
CH2
CH3 groups react with isocyanate groups, thus causing
HO cross-linking or branching of the main chains via
OH
allophanate bonds (Figure 9.14). In turn, the urea
H3C CH2 CH2 O
OH
group in the poly(urethane-ureas) can react with
CH2
HO an isocyanate group, which causes cross-linking
HO OH HO OH
CH3 of polyurethane with biuret bonds (Figure 9.15)
HO O OH HO OH [2,51,100,103,111
113].
HO OH HO
The condition for the formation of these
HO OH bonds leading to branching or cross-linking in
HO OH polyurethane is usage in the synthesis of poly-
urethanes of a sufficiently high temperature and
HO OH
a molar excess of isocyanate groups in relation
H3C OH HO CH3
to hydroxyl or amino groups (isocyanate index
Figure 9.11 Hyperbranched polyglycidol (fourth defined as the ratio of isocyanate groups to
generation) [56]. hydroxyl or amino groups that must be greater
than unity, INCO . 1). Cross-linking with allo-
phanate and biuret linkages may occur in whole
polyurethane mass, at the appropriate ratio of
Reactivity of cross-linking compounds in rela- the reactants, and at the proper temperature, or
tion to isocyanate groups depends on the type of on the microscale level where in the reactive
functional groups that occur in their structure, and mixture, due to the exothermic reaction of iso-
also on the placement of substitution in the main cyanate groups with hydroxyl or amine, it takes
chain [10,51,56,110]. The highest reactivity charac- place with an insufficiently fast dissipation of
terizes the amino cross-linking agents. The reactiv- heat, thus causing a local increase of tempera-
ity of amines with isocyanate groups is 1000-fold ture to about 100°C [114]. The latter case
greater than the reactivity of hydroxylic groups, refers specifically to the synthesis in the mass.
and the cross-linking reaction takes place faster the Branching causes an increase in viscosity of the
higher the alkalinity of the functional groups of the polymer (which is undesirable) due to polyure-
cross-linking agent. The position of functional thane processing at low temperatures or low
group substitution in the main chain of the cross- shear forces [115]. In general, allophanate
linking agent is also important. From the amine bonds are formed at temperatures of 120
140°C
cross-linking compounds, the highest reactivity [17], but in the literature there is also given
occurs with the primary amines (aNH2); secondary temperatures of 90°C [115]. Catalysts for the
amines react much slower, and the aromatic amines reaction are naphthenates, organolithium com-
react the slowest. In the case of cross-linking com- pounds such as n-butyllithium and 1,4-butylene
pounds containing hydroxyl groups, the quickest dilithium [18], trace metals (Pb, Co, Zn, and
reaction was observed for the primary hydroxyl Sn), water, or amines [115]. Biuret bondings are
groups, those with secondary hydroxyl groups react formed at 100
140°C [111]. Catalysts that can
more than 3-fold slower, and the tertiary aOH be used for this reaction are organometallic
group a few hundred times slower; but the phenolic compounds (Sn and Zn) and tertiary amines
groups react the slowest. Table 9.11 shows the rela- (triethylenediamine, DABCO) [111]. Cross-
tive reactivity of isocyanate groups with different linking via biuret and allophanate at elevated
types of functional groups that have active hydro- temperatures (130
150°C) undergoes partially
gen atoms. reversible dissociation.
270
HO
HO O
HO
O
HO
O O
HO O O
HO O O
OH OH
O OH
HO O
HO
Figure 9.12 Hyperbranched polyglycerol containing 20 glycidol units (pseudodendrimer) [56].
Cross-Linking of Polyurethanes
via Products of the Dimerization
or Trimerization of Isocyanates
Another variation of polyurethane cross-linking
is an introduction to their structure of cross-linking
nodes in the form of uretidione and isocyanurate
rings by the so-called self-addition of diisocyanates;
this occurs in the presence of a nucleophilic cata-
lyst [49,51,116]. This cross-linking occurs within
the rigid segments of polyurethane, and the appro-
priate control of the quantities of reactants, temper-
ature, amount, and type of catalysts determines
whether dimerization, trimerization, carbodiimiza-
tion, or polymerization of isocyanates occurs.
Dimerization of isocyanates leads to the formation
of uretidione rings. It can take place at room tem-
perature and elevated temperatures, either under the
influence of basic nucleophilic catalysts (both
acidic and alkaline) [116
120]. Its speed is greatest
when the catalysts are trialkylphosphines (PR3).
Much weaker catalysts for the dimerization of
HANDBOOK OF THERMOSET PLASTICS
OH
O OH
HO O
O OH
OH
O O
O OH
O O OH
O OH
O
O
OH
OH
OH
isocyanates are dialkylphosphines and tertiary
amines (e.g. pyridine). The most important feature
of the isocyanate dimerization reaction is that the
reaction is reversible and in equilibrium, so the ure-
tidione rings can undergo dissociation. Dimer disso-
ciation occurs without the use of catalysts at
temperatures of 150
180°C [51]. The mechanism
of isocyanate dimerization proposed by Arnold
et al. is shown in Figure 9.16 [121].
Trimerization of isocyanates that leads to the
formation of isocyanurate rings is an irreversible
reaction. Trimers of isocyanates are extremely
resistant to high temperature (150
200°C), and in
the absence of oxygen and catalysts, trimers are
resistant even to temperatures up to 500°C [51].
Therefore, cross-linking of polyurethanes with iso-
cyanurate rings is used for the manufacture of rigid
foam insulation with high thermal resistance. The
trimerization reaction is catalyzed mainly by alkali
catalysts: sodium methoxide, sodium salts of car-
boxylic acids (e.g. calcium acetate and sodium ben-
zoate), sodium carbonate, alkali metal chelates,
9: POLYURETHANES 271

Structure of polyurethanes
cross-linked by triols
O

U U U U C O
OH R R R R
U U U U NH
n
HO OH U U R
R R NH
+ U U
C O
3n OCN R NCO
U U U U
R R R R O
U U U U

U- urethane groups

Figure 9.13 Reaction of cross-linking of polyurethanes by triols [102].

Table 9.11 Relative Reactivity of Isocyanate Groups with Different Hydrogen Active Compounds [51,101,104]

Hydrogen Active Formula Relative Reaction Rate (in 25°C, without

Compounds catalyst)
Primary aliphatic amine RaCH2aNH2 2500
Secondary aliphatic amine R2CHaNH2 500
1250
Primary aromatic amine PhaNH2 5
7.5
Primary hydroxyl groups RaCH2aOH 2.5
Water HOH 2.5
Secondary hydroxyl groups R2CHaOH 0.75
Urea group RaNHaCOaNHaR 0.375
Tertiary hydroxyl groups R3CaOH 0.0125
Phenolic hydroxyl PhaOH 0.0025
0.0125
Urethane group RaNHaCOOaR 0.0025

O
O C N R
O
N C O C O
O C NH R
NH
+
O C NH R NH
N C O
O C O
O C N R
O

Figure 9.14 Cross-linking reaction of polyurethanes via allophanate bonds [40].

272 HANDBOOK OF THERMOSET PLASTICS

O
NH C N R
O
N C O C O
NH C NH R
NH
+
NH C NH R NH
N C O
O C O
NH C N R
O

Figure 9.15 Cross-linking reaction of polyurethanes via biuret bonds [40].

O
- + -
R N C O + A A C N
R

+ R N C O Uretidione ring
R
O O -
+ - -A N
A C N C N O C C O
N
R R
R

Figure 9.16 Mechanism of isocyanate dimerization reaction under the influence of a nucleophilic catalyst [121].

Fe, Mg, Hg, Ni, Cu, Zn, Al, Sn, V, Ti, and Cr,
in which the metal is linked to the chain by means
of organic oxygen, tertiary phosphines, tertiary
amines, dimethylaminopyridine, DABCO, or
Friedel-Crafts catalysts [100,116,121
123].
Isocyanates may also be subjected to trimerization
reactions under high temperature.
Trimerization reactions require an appropriate
ratio of reagents, a suitable temperature, and usage
of suitable catalysts. In addition to trimers, reaction
by-products may also be a dimer, a carbodiimide, a
polyamide, and others. Trimerization reactions with
by-reactions are shown in Figure 9.17.
Cross-Linking of Polyurethanes in
Radical Reactions
One of the possibilities for improving polyure-
thane properties is the introduction of double bonds
into the structure, which allows for additional
cross-linking by UV radiation, organic peroxides,
sulfur, or radical copolymerization of the unsatu-
rated bond-containing compounds.
There are many varieties of unsaturated polyur-
ethanes that are different in terms of their proper-
ties and structure. The main ones are:
• Unsaturated poly(ester-urethanes) and poly
(ester-ether-urethanes) [67,68,124
133].
• Poly(urethane-acrylates) [134
138].
• Polyurethanes extended with unsaturated low-
molecular-weight diols [139
142].
• Urethane elastomers obtained from polybutadi-
ene polyols [143
151].
Unsaturated poly(ester-urethanes) and poly(ester-
ether-urethanes) are created by the reaction of
unsaturated poly(esterdiols) or poly(ester-ether-
diols) (Figure 9.18) with diisocyanates or urethane
prepolymers; these have isocyanate terminated
chains. Their development was an answer to the
need for improvement of the properties of both the
unsaturated polyester and polyurethane elastomers.
Cross-linking in this case takes place within
soft segments and may be carried out using a
9: POLYURETHANES 273

The way of reaction trimerization of isocyanates

O

R N C O + A B A N C B
R

+R N C O
Uretidione ring
R
R O O
O - AB - AB N
R N C C O N C C B O C C O
N Phosphane N N
A
high temperature
R R R
100-300°C

+ R N C O

R
N C N + CO2 R
Polyamide 1
R O N O
Carbodiimide C C + R N C O O

B N R A N C B
A C Low temperature n
R
N O low content of iniciator
excess amount of
R isocyanates

- AB

R
O N O
C C
N N
R C R
O

Isocyanuric ring

Figure 9.17 Isocyanate trimerization reaction under the influence of a basic catalyst [51,116].

peroxide, or through the cross-linking copolymeri- process of poly(urethane-acrylates) uses copolymeri-

zation reaction with styrene, acrylate, 2,4,6-trially-
loxy-1,3,5-triazine, and various other compounds
such as vinyl and allyl types; these allow the crea-
tion of a strong, three-dimensional hybrid network
[67,68,124
126]. The structure of cross-linked
poly(ester-urethane) or poly(ester-ether-urethane)
with styrene is shown in Figure 9.19.
Poly(urethane-acrylates) are a variety of polyur-
ethanes that contain in their main chain structure
double bonds derived from the compounds used dur-
ing synthesis, acrylic monomers. The cross-linking
zation of acrylate moieties, which is initiated with
peroxides, UV light, or ionizing radiation
[134
138]. Poly(urethane-acrylates) possess very
good mechanical properties and chemical resistance,
thermal resistance, and they exhibit excellent optical
characteristics for polyacrylates; they are used in the
production of paints and varnishes [152
154].
Poly(urethane-acrylates) [51] are obtained mainly
as a result of the reaction of urethane prepolymers
and quasi-urethane prepolymers containing macro-
molecules, terminated with isocyanate groups, and
274 HANDBOOK OF THERMOSET PLASTICS

O O O O O O
HO CH 2CH 2 O C C O CH 2CH 2 O C CH CH C O CH 2 CH 2 O C (CH 2 ) 4 C O CH 2 CH 2 OH
m n z

Unsaturated poly(esterdiol)
O O O O
HO CH2CH2 O CH2 CH2 O C (CH2)4 C O CH2CH2 O CH2 CH2 O C CH CH C O
m n

O O O O
H O CH2CH2 O C CH CH C O CH2CH2 O C (CH2)4 C O CH2CH2
k k p k o

Unsaturated poly(ester-etherdiol)

Figure 9.18 Structure of unsaturated polyesterdiol and poly(ester-ether-diol) [67,68,124
126].

terminated with an isocyanate group and unsatu-

rated bonds (Figure 9.21).
CH In the synthesis of unsaturated polyurethanes,
CH2
oligodienols are also used (e.g. hydroxy telechelic
O
NH C O HC polybutadiene, HTPB) [143
151]. Poly(urethane-
CH O C NH
O dienols) are also called liquid rubbers. Poly(ure-
CH2
thane-dienols) are mainly used for the production
of hydrolytically stable urethane elastomers, ther-
CH moplastic polyurethanes, adhesives, paints, and
a electrical insulations. The structure of hydroxyl-
O
terminated polybutadiene, obtained by the radical
NH C O CH polymerization of butadiene initiated with hydrogen
CH O C NH
O peroxide, is shown in Figure 9.22 [1,56,100]. The
H2C majority of the structure of hydroxyl-terminated
CH polybutadiene is 1,4-trans, and the terminal
hydroxyl groups are exclusively primary hydroxyl
groups of the allylic type placed on the end of
Figure 9.19 Cross-link with styrene poly(ester- chains [155].
urethane) or poly(ester-ether urethane)
The double bond can also be introduced into the
[67,68,124
126]. polyurethane structure with unsaturated low-
molecular-weight chain extenders. One of the first
patents for this group of compounds dates back to
with acrylic monomers having at least one func- the 1960s [139,140]. It shows the ability to use a
tional group (hydroxyl or amine group) capable of wide range of compounds of the structure shown in
reacting with an isocyanate group. The product of Figure 9.23.
this reaction is shown in Figure 9.20. These compounds were used to synthesize poly-
Next to the reaction shown in Figure 9.20, poly urethane [141]. The described system was a conven-
(urethane-acrylates) can be obtained by reaction of tional polyurethane obtained from oligo(adipate
diisocyanates with derivatives of acrylic mono- ethylene-propylene) and toluene diisocyanate (TDI).
mers having one functional group (hydroxyl or The chain extender used was 3-allyloxy-1,2-propane-
amine group) capable of reacting with an isocya- diol. The unsaturated polyurethane structure is
nate group. In this reaction the adduct formed is shown in Figure 9.24.
9: POLYURETHANES 275

R1 O O O O O O R1
H2C C C O R2 O C NH R NH C O O C NH R NH C O R2 O C C CH2

R1 , R2 - Cn H2n+1 R - Ph-,CnH2n

Figure 9.20 Poly(urethane-acrylates) from urethane prepolymers and hydroxy-terminated acrylates [51].

X R Y X, Y = NH Z= CH CH2
O O R2
Z NH 2 CH2 CH CH2
OCN R NH C O R1 O C O C CH2
OH CH2 CH CH2
n
COOH
R1 , R2 - C nH2n+1 R - Ph-,CnH2n O CH2 CH CH2
SH
CH2 O CH2 CH CH2
Figure 9.21 Poly(urethane-acrylates) from S CH2 CH CH2
diisocyanate and hydroxy-terminated acrylates [51]. CH2 S CH2 CH CH2

Figure 9.23 Unsaturated low-molecular-weight

1,4-trans(60%)
1,4-cis (20%) CH2
CH CH CH CH
HO CH2 CH2 CH
HC CH2
1,2 (20%)
Figure 9.22 Polybutadiene synthesis in
polymerization of butadiene initiated with hydrogen
peroxide [56].
Morphology of Linear/Branched
vs. Cross-Linked Polyurethanes
Linear/Branched PU
Polyurethanes are block copolymers in which
phase separation takes place. In 1966 Cooper found
for TPU (PTMO/MDI/BD) a characteristic plateau
studding correlation of modulus vs. temperature
[156
158].
Later it was explained by the presence of phase
separation at different micro and nanometer scales.
SAXS [159
166], WAXS [164
167], NMR
[168
171], IR [24,172], DSC [99,173
185], DMTA
[21,186,187], DEA [188], SALS [189
193], and
optical [187,193
198], electron [30,195,199
212],
or atomic force microscopy [99,213
221] studies
were used to follow phase separation in different
types of polyurethanes. It was established that in
amorphous, soluble TPU the nanodomains are
chain extenders [139,140].
OH
n fundamental entities of morphology (Figure 9.25).
They can be spherical [156
158], ellipsoidal
[222
225], cylindrical [226], or lamellar [226,227]
types with the diameter or cross-section of the order
of a dozen nanometers [201].
Hard segments in the first models of nanodo-
mains were postulated to be in a zig-zag conforma-
tion. That conformation is a favorite for creation of
hydrogen bondings. In that case, the domain size
was limited by the length of the hard segments. IR
studies [5,228] revealed that some hard segments
were present in the matrix of soft segments and
the phase separation degree was dependent on the
length of soft and hard segments and thermal his-
tory of the samples [229
231].
With the increase of the temperature above
60
80°C, the increase in mixing of soft and hard seg-
ments was observed and the phase separation was
weaker. Very often the domains could be crystalline,
especially in the case of MDI/BD types of hard seg-
ments. The degree of crystallinity [25,223,224] can
be changed by thermal annealing, but it takes time to
be effective (at least 12 hours at 190°C) [232]. The
newer theories claim that not only is the chemistry of
hard segments an important factor in the phase sepa-
ration of PU, but the rigidity of hard segments as
well. This is in accordance with Flory theory [233].
Moreover, it was calculated that the length of the soft
segment plays a diminishing role in phase separation
276 HANDBOOK OF THERMOSET PLASTICS

O O
NH C O CH CH2 O C NH
n
CH2 O CH2 CH CH2

Figure 9.24 Unsaturated polyurethanes from allyloxy-1,2-propenediol [141].

in comparison to the length of the hard segment (HS).

If hard segments are built of 2 MDI then at least 10%
of them are mixed with soft segments (SS). In the
case where the HS are built of 3 MDI, only 2.5% of
them are mixed with SS.
In 1994 Thao [234] postulated that the role of
hydrogen bonding is overestimated. He showed that
the decrease in the level of hydrogen bonding of
HS-HS type with the increase of temperature is not
equivalent to the change of phase separation. That
kind of approach was later confirmed by Hammond
with the use of Raman and DSC studies [235], and
explained the presence of phase separation in PU
without hydrogen bonding [236
238].
Clough and Schneider showed that in PUs there
exist morphological elements of a size larger than
domains [187,194] due to the presence of spherulitic
structures of soft or hard segments [199,227,239]. It
was possible according to the new model of crystal-
lization of hard segments in which longer segments
can be in a coiled or folded state, especially in MDI/
BD
based PU, which allows the building of long
fibrils and later spherulites [199,210,240]. TDI-PUs
do not show domain aggregation leading to crystal-
line aggregates [241].
In LPU, the morphology is created at the same time
as the polymer chain building. Due to this it is more
complicated and more sensitive to the thermal history
of the samples, temperature of the mold, prepolymeri-
zation or annealing temperature, or even time after the
synthesis [30,196,197,199,209,210,240,242
249].
Morphology of the LPU created from the same
chemical components can be very different if it
comes from a different laboratory or producer. In
LPU, the globules and two types of spherulites
(Figure 9.26) are observed in the case of higher
hard segment content (more than 30%). The spher-
ulites differ in size and kinetics of nucleation and
growth [249,250]. One type of spherulite is built
from crystalline lamellae (Figure 9.27) of hard seg-
ments of 50
70 nm in length while the other type
is built from very short lamellae (10 nm) and less
ordered entities [199,209,210].
(a)
(b)
(c)
Connected domains
Isolated domains (Interpenetrating
phases)
Figure 9.25 PU morphology: (a) Spherical
domains, (b) Ellipsoidal domains, and (c) Cylindrical
domains.
Cross-Linked PU
The morphology of a cross-linked PU system is
rarely studied. Walsh [251] claimed that there is no
phase separation if PU that are cross-linked with
low-molecular-weight triols. However, other
authors found spherulites and globules in similar
PU systems [30,99,242,243]. In Petrovic’s papers,
the phase separation was proved by DMTA studies
for those PU systems [21,32].
The morphological model for cross-linked PU
with 30% hard segment content was proposed in
which cross-linked domains are elongated while
uncross-linked ones are dispersed in soft segment
matrix. For cross-linked PU with 50% of hard seg-
ment content, the interpenetrating morphology of
hard and soft domains is postulated in which
cross-linking between domains is possible. AFM
studies of similar polyurethanes clearly show the
9: POLYURETHANES
endo
DSC Heat Flow (mW)
0
−10
−20
−75 −25 25 75 125
Temperature (°C)
Figure 9.26 Spherulites in PU under polarized
microscope and their DSC [197,245].
complexity of those morphological systems [99].
The morphology is strongly dependent on the
amount of cross-linking agent added (triols), hard
segment content, and the scale of observation
(Figure 9.28).
Adding TMP to BD (Figures 9.28 and 9.29) at
the second step of the synthesis influences the size
and amount of crystalline globules and spherulites,
which explains the increased clarity observed by
many authors of cross-linked PU systems. In
between spherulites (Figures 9.30 and 9.31), amor-
phous nanodomains are present in the images taken
with AFM. They are of very weak contrast for
higher content of hard segments.
In hard segment cross-linked thermoset PUs with
the use of TMP (PPO/MDI/TMP) having 30 or
50% HS content, the nanodomain morphology was
only revealed by AFM (well-visible when a
2.5 3 2.5 μm or 1 3 1 μm area was scanned
(Figures 9.32 and 9.33).
In both cases (thermoset PU with 30 and 50%
HS content) only isolated spherical domains were
observed with comparable size. The only difference
between them was the degree of filling by domains.
277
4μm
70 nm
Lamellae
Figure 9.27 Lamellae revealed by HVEM in hard
segment-rich phase built on micrometer scale from
178°C
205°C
spherulites [245].
175 225 275
The presence of globules was also observed by
TEM and SAXS studies in moisture-cured poly
(siloxane-urethanes) [255]. Very differentiated mor-
phology was observed depending on the siloxane
length and ICI. With the use of SAXS, lamellar
morphology was revealed of the order of 4
9 nm.
Krakowsky [256] described phase separation for
cross-linked PU in the soft segment phase. SAXS
data revealed the presence of the structure of the
order of 7
12 nm.
Manufacturing Methods and
Technical and Functional
Properties of Thermosetting
Polyurethanes
Polyurethanes are a group of polymeric materials
with very different chemical and supermolecular
structures and complex properties like elasticity and
mechanical, physical, and chemical properties (as
well as utility). Properties of polyurethanes and their
physicochemical structure can vary within a wide
range, which is possible because of the following:
• A large number of different types of monomers
and additives, which can be used in the synthe-
sis of urethane polymers. That enables virtually
unlimited chemical material composition, and
278 HANDBOOK OF THERMOSET PLASTICS

(a) (b)

0% 50%

Figure 9.28 AFM images of polyurethanes having 30% hard segment content with (PPO/MDI/BD-50% TMP)
and without (MDI/PPO/BD-0% TMP) cross-linking agent (TMP) added. Images taken at scanning of
50 3 50 μm2 [99,252,253].

0% TMP 5% TMP

15% TMP 50% TMP

Figure 9.29 AFM images of polyurethanes having 50% hard segment content with (PPO/MDI/BD-5, 15, 50%
TMP) and without (MDI/PPO/BD-0% TMP) cross-linking agent (TMP) added. Images taken at scanning of
10 3 10 μm2 [99,252].
9: POLYURETHANES 279

(a) (b)

5% TMP
50% TMP

250 250
200 200
150 150
100 100
50 50
0 0

Figure 9.30 AFM images of polyurethanes having 50% hard segment content, partially cross-linked with
different amounts of TMP (PPO/MDI/BD-5 and 50% TMP). Images taken at scanning of 1 3 1 μm2. The
contrast profile is shown as well below the images [254].

makes possible the significant changes in the
structure of the main chain, which takes place
in soft and rigid segments.
• Possibility of cross-linking urethane polymers
leading to the formation of urethane, allophanate,
biuret cross-links, or isocyanurate rings and
bonds like carbon
sulfur and carbon
carbon.
• Differentiation in polyurethane preparation
methods that are based on the principle of
reactive molding techniques in which polyure-
thane obtaining processes are directly con-
nected with simultaneous formation of the
finished product.
These factors significantly shape the urethane
polymers and their physicochemical and macro-
scopic properties, as well as their mechanical
properties and utility. This is the reason why
polyurethanes can be prepared in the form of
flexible and rigid foams, cast urethane elastomers,
solid urethane rubbers, thermoplastic microporous
polyurethane materials, polyurethane fibers, artifi-
cial leather polyurethanes, adhesives, sealants,
binders, paints, and varnishes. There is significant
impact on polyurethane properties: rigidity, cross-
linking density, mechanical strength, and the
micro- and macroscopic structure [51,56,100].
Figure 9.34 shows the effect of cross-linking den-
sity and stiffness of polyurethane on the scope of
their applications and quantity share on the poly-
urethane market.
In industrial practice, polyurethanes can be pro-
duced by two methods: one-stage (one-shot) or two-
stage (two-shot) methods (prepolymer) [1,49,51,100].
In the one-stage method all monomers (diisocyanates,
ologomerols, chain extenders) and cross-linking
agents, blowing agents (used in the synthesis of
foams), and other additives are mixed together and
poured into the mold, and the reaction rate is con-
trolled by the use of suitable catalysts. Because the
reaction of isocyanate groups with hydroxyl is exo-
thermic, the heat emitted immediately raises the tem-
perature of the reactive mixture in the form up to
280 HANDBOOK OF THERMOSET PLASTICS

1.00 1.00
(a) (b)

0.75 0.75

0.50 0.50

0.25 0.25

5% 50%
0 0
0 0.25 0.50 0.75 1.00 0 0.25 0.50 0.75 1.00
μm

250 250

200 200

150 150

100 100

50 50

0 0

Figure 9.31 AFM images of polyurethanes having 30% hard segment content, partially cross-linked with
different amounts of TMP (PPO/MDI/BD-5 and 50% TMP). Images taken at scanning of 1 3 1 μm2. The
contrast profile is shown as well below the images [254].

more than 100°C. Raw materials used for the one-
stage method are commercially available in the form
of polyurethane systems A and B. These systems are
mainly used for the preparation of polyurethane
foams, but seldom for urethane elastomers.
Component A generally has oligomerol, the cross-
linking agent or chain extender, catalyst, blowing
agents (water, blowing agents), and surfactants. Part
B most often is liquid diisocyanate. Manufacturers of
the polyurethane system determine the appropriate
ratio of the two components, which ensures that pro-
ducts with specific properties are obtained.
In the prepolymer method, initially from oligomer-
ol and a molar excess of a diisocyanate, the urethane
prepolymer is synthesized. It is a liquid mixture of
urethane oligomers terminated with isocyanate
groups and unreacted diisocyanates. Urethane oligo-
mers obtained at a moderate molar excess of isocya-
nate in relation to polyol ratio of (2
5)/1 are referred
to as urethane prepolymers, generally. When the
molar ratio of diisocyanate to polyol is greater than 5,
the obtained urethanes are so-called urethane quasi-
prepolymers [100].
Urethane prepolymer is characterized by experi-
mental examination of the unrelated isocyanate
group’s content. Due to the presence of unrelated
isocyanate group, prepolymers are sensitive to
moisture in the air, and therefore it’s required to
store them in sealed containers. The prepolymer,
for example, is stabilized with inorganic acids
such as phosphoric acid, which allows for a rela-
tively long period of storage. Storage of the prepo-
lymer at an elevated temperature causes the
deterioration of polyurethane properties. Urethane
prepolymers with a specified isocyanate content
are subjected to an extension reaction by the low-
molecular-weight chain extenders (glycol or
diamine), or cross-linking by using multifunctional
alcohols or amines. When added to the prepoly-
mer, extender, or cross-linking agent, the reactive
9: POLYURETHANES 281

1.00 1.00
30% 50%

0.75 0.75

0.50 0.50

0.25 0.25

0 0
0 0.25 0.50 0.75 1.00 0 0.25 0.50 0.75 1.00

1.00
30% 50%

0.75

0.50

0.25

0
0 0.25 0.50 0.75 1.00

Figure 9.32 AFM images of polyurethanes having 30% or 50% hard segment content, partially cross-linked
with 70% of TMP (PPO/MDI/BD-70% TMP). Images taken at scanning of 1 3 1 μm2. The binary images after
conversion are shown as well below.

mixture has a limited lifetime, and the rate of the
cross-linking reaction or the chain extension
depends on the number and type of added catalyst.
For the synthesis of polyurethane foam, reactive
mixtures additionally include blowing agents
(water, blowing agents). Figure 9.35 presents the
urethane prepolymer synthesis and its cross-
linking reaction with triol.
Reactive injection molding (RIM) technology is
very popular [51,100]. It is a fully automatic
method for rapid formation of products. It is con-
structed of four integral and interdependent compo-
nents: feedstock storage tanks, gear pumps that
provide transmission of the reactant stream, the
mixing chamber, and the formation system. In order
to ensure a constant density of the components
used in the process, and also to reduce the viscos-
ity, whole elements are heated.
The principle of polyurethane molding by the
RIM method is dosage by gear pumps of all reac-
tants (polyol and diisocyanate components are in
separate containers) into a special mixing chamber
(mixing head), in which whole reagents are mixed
precisely. Then the reaction mixture goes to the dif-
ferent forms in which the cross-linking reaction
takes place, initiated during the mixing. During the
production downtime, all substrates circulate in the
system, which ensures the maintenance of a constant
temperature and additional mixing. Special head
design allows for production of a completely homo-
geneous mixture, ensuring a constant proportion of
the quantity of mixed ingredients and elimination of
the problem of introduction of air into the mixture.
There are known two methods for polyurethane
product preparation with RIM techniques. These
differ in their method of reactant mixing: [51]
282 HANDBOOK OF THERMOSET PLASTICS

(a) 10.0 10.0

50 30

7.5 7.5

5.0 5.0

2.5 2.5

0 0
0 2.5 5.0 7.5 10.0 0 2.5 5.0 7.5 10.0

(b)
50 30%

2.00 2.00

1.00 1.00

0 0
0 1.00 2.00 0 1.00 2.00

(c)
50 30%

2.00 2.00

1.00 1.00

0 0
0 1.00 2.00 0 1.00 2.00

Figure 9.33 AFM images of thermoset poly(ether-urethanes) (PPO/MDI/TMP) having 30% and 50% HS
content: (a) 10 3 10 μm2 area scanned, (b) 2.5 3 2.5 μm2 area scanned, and (c) images after conversion to the
same degree of grayness.
9: POLYURETHANES 283

Degree of branching and cross-linking

Rigid
foams 68%
Semirigid
foams the total production
Flexible
foams of polyurethanes

Coatings 14%
the total production

Cast Leathery
elastomers polyurethan

18%
Thermoplastic Fibers Films the total production
elastomers
of polyurethanes
Millable Adhesives, Plastics
elastomers sealants

Chain stiffness, interchain attraction, crystallinity

Figure 9.34 Classification of polyurethanes in terms of cross-link density and stiffness, and quantity share of
urethane products in the global production of polyurethanes [51,56,100,257].

n HO
OH + m OCN CH2 NCO

Prepolymer synthesis
O
O
OCN CH2 NH C O
O C NH CH2 NCO

+
m-(n+1) OCN CH2 NCO

HO
Cross-linking prepolymer by triol
+ OH
HO
O
O C NH CH2 NH
O
O O
O NH CH2 NH C O
O
O O O

O C NH CH2 NH

Figure 9.35 Urethane prepolymer synthesis reaction and the cross-linking with triol (m . n, m . 2) [51,56,100].
284
R NCO + H2O
Figure 9.36 Reaction of isocyanate group with water [51,56,100].
O O
2R NCO + H2O R N C N R +
H H
Figure 9.37 Reaction of excess isocyanate group
with water [51,56,100].
1. The high pressure method involves mixing
liquid raw materials in the heads, which
results in head-on collisions of streams.
These are at 5
20 MPa pressure, and injec-
tion into the mold takes place at a pressure of
0.1
3 MPa. Cross-linking also occurs (initi-
ated during the mixing).
2. In the low pressure method where the compo-
nents are mixed with a high speed screw that
rotates at a speed from 1.5 to 20 thousand
rpm/min, the screw is placed in a cone-
cylindrical chamber. The mixing efficiency
depends on the length and speed of rotation,
and the mixing efficiency is adjusted by
changing the distance between the windings
of the screw and the internal wall of the
chamber.
For the industrial manufacturing of polyurethane
composites reinforced with fillers, powders, or rub-
ber granulates, the RRIM technique is used (rein-
forced reaction injection molding). This technique
requires a special mixing head aggregate, which
includes an additional dosage of fibers or granulate
to the reactive mixture. This construction was
described by Decker and Dormann; they presented
a project of the German company DESMA [258].
Polyurethane Foams
Of all known types of polyurethane products,
more than 72% of the total world uses foams.
Polyurethane foams are prepared by reaction of
foaming polyurethane, where CO2 is released dur-
ing the reaction of isocyanates with water
(Figure 9.36) [51]. The reaction of isocyanate
HANDBOOK OF THERMOSET PLASTICS
R N C OH R NH2 + CO2
ΔT
CO2 R1 N C O B R1 N C O + B H
H Blocking agent
Figure 9.38 Reaction of deblocking isocyanate
group [259,260].
groups with water is carried out in two stages with
a derivative of carbamic acid, which undergoes
decarboxylation and releases CO2 and amine (the
process may be catalyzed by teritary amines or
organo-tin compounds).
When a molar excess of isocyanate groups to
water appears in the system, the unrelated aNCO
group reacts immediately with amino groups to cre-
ate urea groups (Figure 9.37).
The polyurethane foaming process can also be
carried out with the involvement of specific foam-
ing agents, which are described in an earlier sec-
tion. With these measures it is possible to obtain a
polyurethane foam with low density, even 10 kg/
m3. The conventional process of polyurethane foam
production is composed of four basic steps
(Figure 9.38): [51,116]
1. Hidden Stage. This begins when all mono-
mers and auxiliary components, such as poly-
isocyanate, oligomerol, water, blowing
agents, catalysts, surfactants, and others, are
mixed together. It ends when the reactive
mixture volume increases, and it takes the
form of creme. This is due to the reactive
mixture saturation of the released foaming
gas and the formation of microembrions of
gas bubbles. In the hidden stage reactions of
isocyanates take place with water and polyol
or amine in reactive mixture.
2. Foam Growth Stage. This begins when the
sudden increase in volume of the reactive
mixture is visible, and ends when the reaction
mixture reaches the maximum volume. In this
step rapid growth occurs of CO2 bubbles or
other blowing agents that pass into the
9: POLYURETHANES
gaseous state under the influence of heat
evolved from exothermic reaction of isocya-
nate groups with water, hydroxyl, or amine
groups. During this time in the reactive mix-
ture, reactions of polyisocyanates with ure-
thane groups take place, which leads to the
production of allophanate bindings and reac-
tions of polyisocyanates with urea groups.
This in turn leads to the formation of biuret
bondings. At the same time, dimerization, car-
bodiimidization, and trimerization may occur.
3. Gelation Stage. During this stage transforma-
tion occurs of the liquid reactive mixture to
the solid polymer with a high molecular
weight. Also in this stage is the end of isocy-
anate group reactions with hydroxyl and
amino groups. This step is also called the
stage of vanishing the surface viscosity of
polyurethane foam.
4. Maturation Stage. This stage is associated
with the creation of spatially cross-linked
foam structure due to the formation of allo-
phanate, biuret bonds, and isocyanurate or
uretidione rings. This stage ends when maxi-
mum mechanical strength of the foam is
achieved, and it may take several hours.
Polyurethane foams are produced in many types
and varieties, and the criteria for their selection is
their rigidity, cross-link density, and cellular struc-
ture [1,51,100,101]. Polyurethane foams are pro-
duced primarily in the form of flexible, semi-rigid,
and rigid foams. They can also be divided due to
their cellular structure (open, closed, or mixed).
Polyurethane foams with closed cells have low gas
permeability and thermal insulation. Open-cell
foams have superior sound insulation and have high
water absorption capability and gas permeability.
Foams are classified due to the formation method
as well, so there can be block, douched, and com-
pressed polyurethane foams. Flexible polyurethane
foams are characterized by a low degree of cross-
linking (molecular weight of the chains between
nodes of the spatial network is between
Mc 5 2500
2500 Daltons), and a density range
from 15 to 70 kg/m3[1,51,100]. They can be pre-
pared in the form of conventional flexible polyure-
thane foams (density of 11
60 kg/m3), supersoft
polyurethane foams (obtained from polyether hav-
ing a molecular weight of 1000
3500 Daltons),
285
and flexible polyurethane foams with a high load
capacity, high elasticity, and high elongation
(350
400%). From flexible polyurethane foams are
produced mainly automotive seating and headrests,
upholstered furniture, mattresses, seating for air-
craft, buses, and trains, filters, sound absorption
materials, decorative elements, soles, sports, lei-
sure, and safety shoes, steering wheels, gearshift
knobs, headrests, and instruments panels for motor
vehicles.
The border between the flexible and rigid poly-
urethane foam is difficult to determine in that it is
related to the overlap of certain properties of both
polyurethane products. Because of this, another
class of polyurethane foams was isolated. They are
the so-called semi-rigid foams. The criterion for
the distribution of polyurethane on semi-rigid
foams is their crushing strength. If there is the
possibility to compress the polyurethane foam by
10% without destruction of the foam structure, it
is classified as semi-rigid, and when the structure
of the foam is destroyed, it belongs to the group
of rigid foams [51,100]. Semi-rigid foams are typi-
cally formed by compression and used as vibration
and impact-absorbing materials. Rigid polyure-
thane foams are characterized by low apparent
density, porous structure, and high density of
cross-links resulting from the use in synthesis of
multifunctional isocyanate, polyol and amine
monomers, and compounds containing isocyanu-
rate rings and catalysts that allow for dimerization
and trimerization of the main chain. For the syn-
thesis of the rigid foams, primarily used are poly-
meric diisocyanates, multifunctional polyols with
low molecular weight. Rigid polyurethane foams
are among the best on the market of thermal insu-
lation materials, and are used in construction and
insulation of household appliances. The thermal
conductivity (λ) of rigid polyurethane foam at a
temperature of 10°C, ranges from 0.018 to
0.025 W/m•K, and is much lower than the coeffi-
cients of thermal conductivity of other known
insulating materials (such as polystyrene and min-
eral wool) [51,100]. During compression, deforma-
tion of rigid foams is less than 10%. They have a
high glass transition temperature (above 20°C) and
they are used in the glassy state [51]. Rigid poly-
urethane foams can be prepared in a wide range of
density ratios, from 10
600 kg/m3. Foams are usu-
ally produced in blocks, plates, fittings, integral
foams, or are sprayed directly onto the surface of
286 HANDBOOK OF THERMOSET PLASTICS

the material where it is foaming. The mechanical Table 9.12 Examples of Producers and Uses of
properties and thermal insulation of rigid polyure- Polyurethane Foams [261
264]
thane foams are improved with decreasing sizes of
Producer Products
the closed pore. Rigid polyurethane foams are
used as insulating materials for industry and the Organika Malbork Products for the
construction sectors, district heating pipes, refrig- furniture industry
erators, transportation containers, headliners in car, Products for civil
and safety components (internal and external) for engineering
Products for the
vehicles (Table 9.12).
automotive industry
Future Foam Extensive Range of
Polyurethane Coatings and Conventional Foams
Adhesives Future Cell Foams
High Resilient HR
Polyurethanes, due to their high resistance to Foam
weathering, solvents, and mechanical damage, have Anti-Static Foam
been used in the manufacture of paints and Anti-Microbial Foam
varnishes [152
154]. Polyurethane paints and Colorfast Foam
varnishes are produced in the form of solvent, Visco Elastic Foam
solvent-free (high-solid paints), water, water-borne, Selena FM S.A. New generation of
and powder coatings. Drying of polyurethane coat- polyurethane foams
ings can take place physically (by evaporation of that do not emit
the solvent) at temperatures of 0°C, and rely on the harmful MDI vapor;
cross-linking process at a temperature up to 200°C. for any type of
Depending on the composition, polyurethane paints building and
and varnishes can be divided into single (1 K) or renovation task
two-component (2 K) products. The one-component NCFI Polyurethanes Flexible foams for
polyurethane paint coatings are produced from a furniture seating,
stable mixture of polyisocyanate and polyol compo- transportation
nents. One-component polyurethane paints can be seating, bedding,
carpet underlay, and
divided into the following: [152
154]
packaging
• Polyurethane paints cross-linked with the
share of atmospheric oxygen. They are mainly
urethane oils (obtained by reacting diisocya- or polyamines. Figure 9.38 shows the deblock
nates with natural unsaturated oils), and reaction of the isocyanate groups.
urethane-alkyd resins modified with unsatu- • Paints containing microcapsules of isocya-
rated oils. Drying and cross-linking of these nates. In this product, the polyisocyanates are
products takes place by oxidation (oxidative deactivated by encapsulation by coating them
cross-linking). with suitable resin (diamine or polyamine).
• Paints with blocked polyisocyanate. These pro- Obtained microcapsules of polyisocyanate are
ducts use polyisocyanates and urethane oligo- stable systems at room temperature. After
merols with blocked isocyanate groups (a application, the coating is heated up to a tem-
blocker of the isocyanate groups is most perature above 80°C, resulting in release of
often 2-butanone oxime, caprolactam, diethyl the polyisocyanates, thereby allowing the reac-
malonate, or phenol). These systems are tion of free aNCO groups with aOH groups
stable during storage under normal conditions, (or aNH2). These inks are used in paint coat-
however, under high temperature (120
200°C), ings on car chassis.
deblocking takes place, and the release of the • Waterborne paints. Polyurethane aqueous dis-
isocyanate groups which are capable of react- persions are obtained from polyurethanes hav-
ing with amine or hydroxyl groups of polyols ing ionic groups in their structure. It allows
9: POLYURETHANES
R2
R2
+H2O R1
R1 N OH
N O
OH
Open the
oxazolidone ring
Figure 9.39 Reaction of cross-linking of polyurethanes by oxazolidones [259,260].
the production of a stable dispersion of poly-
urethane in water. Polyurethane waterborne
paints are used to coat fabrics, leather, paper,
and wood flooring. However, their most
important applications are coating products for
the automotive industry
• Paints containing blocked hardeners. In these
paints, polyisocyanates are mixed with hidden
(locked) hardeners such as oxazolidone. During
storage in sealed vessels, these systems are sta-
ble. Cross-linking of the paint starts only at the
time of application for the painted object. Then,
under the influence of moisture in the air, the
hardener is activated, which in the case of oxa-
zolidone relies on tearing the ring and release
of hydroxyl and amine groups capable of react-
ing with the polyisocyanates (Figure 9.39).
Two-component polyurethane paints (2 K) are
classic film-forming products with the widest appli-
cations in practice [152]. The paint composition
comprises two reagents stored separately in the
form of a mixture of macromolecular compounds
containing hydroxyl groups, catalysts and additives
(component I), and hardener (component II), in the
form of polyisocyanate resin solutions. Paint curing
starts immediately after mixing the polyol compo-
nent with the hardener. Two-component polyure-
thane products in the cross-linking process create
flexible and hard coatings with excellent adhesion
to various substrates, resistance to chemicals and
water, as well as resistance to yellowing (products
based on aliphatic polyisocyanates). These paints
are used on cars, planes, plastics, machinery, and
high-quality furniture. Polyurethane paints and
varnishes exhibit excellent resistance to weathering
and chemical attack, high abrasion resistance,
excellent adhesion to various substrates, high gloss,
and good resistance to light (in the case of paints
287
R2 O H
2 R3 NCO R1 O C N R3
N O
O
C N R3
O H
derived from aliphatic isocyanates). Polyurethane
paints are also used on the surface of machines,
tanks, metal structures, airplanes, trains, cars, boats,
furniture, floors, glasses, and plastics.
Polyurethane adhesives are produced mainly in
the form of one-component (1 K) or two-component
systems (2 K) [1,51,100]. One-component adhesives
are solutions of aromatic multi-isocyanates or
chemo-reactive urethane prepolymers capable of
reacting with moisture in the air or functional
groups contained in the bonded surfaces. The two-
component adhesives include polyols and multi-
isocyanates or urethane prepolymers, which are
mixed just before application to the bonding sur-
faces. Polyurethane adhesives are primarily used to
connect polar materials that belong to the plastics
and ceramics or metals and their alloys (Figure 9.40,
Table 9.13). Polyurethane adhesives are character-
ized by high strength and excellent adhesion to
bonding surfaces, resulting from creating chemical
bonds and physicochemical interactions like dipo-
le
dipole, and also from hydrogen bonds.
Cross-Linked Polyurethanes in
Medicine
Polyurethanes in medicine have a very wide
range of applications, but cross-linked polyur-
ethanes, synthesized with branched monomers, are
used in a few areas of medicine, such as pressure-
sensitive adhesives [270]. They are also developed
for the cell scaffold area, especially for bone and
cardiovascular regenerative medicine [271
273].
Xia Jiang designed and synthesized a series of non-
toxic cross-linked waterborne polyurethanes with
isophorone diisocyanate (IPDI), poly(ε-caprolac-
tone) (PCL), poly(ethylene glycol) (PEG), 1,4-
butandiol (BDO), and L-lysine (without any other
organic agent involved in the whole synthetic pro-
cess) in order to obtain waterborne polyurethanes
288 HANDBOOK OF THERMOSET PLASTICS

Figure 9.40 Examples of applications of polyurethane coatings [265
267].

Table 9.13 Examples of Producers and Uses of available cross-linked polyester networks for
Polyurethane Coatings [265,266,268,269] designing scaffolds with desired mechanical proper-
ties. Mechanical properties and degradation rates of
Producer Products CUPEs could be controlled by varying the diol
Teknos-Oliva Sp. z o.o. Areas of ships used for synthesis, the polymerization conditions,
above the as well as the concentration of urethane bonds in
waterline, the polymer. The polymers demonstrate good
constructions in vitro and in vivo biocompatibilities as well as
exploited in hemocompatibility. CUPEs could be synthesized by
industrial and heavy
a simple and cost-effective method and have been
duty environment,
shown to be anti-thrombotic and only slightly
bridge construction
inflammatory. Good mechanical properties and
Headway Advanced Moisture curing easy processability make these materials well suited
Materials lnc. polyurethane paper for soft tissue engineering applications. The intro-
coating paint
duction of CUPEs provides new avenues to meet
Hempel Paints Varnish on interior the versatile requirements of tissue engineering and
and exterior wood other biomedical applications [54].
and other Cross-linked 3D biodegradable polyurethane
substrates
scaffolds (foams) with controlled hydrophilicity for
Jotun Paints Marine coatings bone graft substitutes were synthesized by Gorna
Protective coatings et al. They were obtained from biocompatible reac-
Powder coatings tants like hexamethylene diisocyanate (HDI), poly
Decorative coatings (ethylene oxide)diol (PEO-diol, MW 5 600, the
hydrophilic component), and poly(ε-caprolactone)
diol (PCL-diol, MW 5 2000), amine-based polyol
(MW 5 515), or sucrose-based polyol (MW 5 445,
(WBPUs) with biocompatibility, biodegradability, the hydrophobic component), water as the chain
as well as good mechanical properties [271]. extender and foaming agent, and stannous octoate,
Jagannath Dey reported synthesis and evaluation of dibutyltin dilaurate, ferric acetylacetonate, and zinc
a new class of biodegradable elastomers and cross- octoate as catalysts. Citric acid was used as a
linked urethane-doped polyesters (CUPEs) that are calcium-complexing agent, and calcium carbonate,
able to satisfy the need for soft, strong, and elastic glycerol phosphate calcium salt, and hydroxyapatite
biomaterials. CUPEs demonstrate a wide range of were used as inorganic fillers. Lecithin or solutions
mechanical and tunable degradation properties, of vitamin D3 were used as surfactants. The scaf-
and have greater processability than the currently folds have an open-pore structure with pore size
9: POLYURETHANES
Figure 9.41 Examples of PU scaffolds [274].
and geometry dependent on the material’s chemical
composition. The compressive strengths of the scaf-
folds and compressive moduli increased with
increasing content of polycaprolactone. Of the two
materials with the same amount of polycaprolac-
tone, the compressive strengths and moduli were
higher for the one containing inorganic fillers. The
scaffolds absorbed water and underwent controlled
degradation in vitro. All polyurethane scaffolds
induced the deposition of calcium phosphate crys-
tals [273]. Examples of polyurethane scaffolds
are shown in Figure 9.41 [274]. At present, it is
possible to find a commercial material for scaffolds
developed by PolyNovo Biomaterials Pty Ltd.
(Clayton South, Australia), claimed to be a novel
two-component injectable and in situ curable poly-
mer system utilizing LDI-based polyurethanes for
initial orthopedic applications [275].
References
[1] Oertel G, editor. Polyurethane handbook. New
York: Hanser; 1985.
[2] Randall D, Lee S, editors. Huntsman
International LLC
John Wiley & Sons;
2002.
289
[3] Wirpsza Z. Poliuretany. Chemia, technologia i
zastosowanie. Warszawa: WNT; 1991.
[4] Trifan DS, Terenzi JF. J Polym Sci
1958;28:443.
[5] Cooper SL, Seymour RW, Estes GM.
Macromol 1970;3:579.
[6] Zdrahala RJ, Gerkin RM, Hager SL,
Critchfield FE. J Appl Polym Sci
1979;24:2041.
[7] Abouzahr S, Wilkes LC, Ophir Z. Polymer
1982;23:1077.
[8] Goyert W, Winkler J, Wagner H, Hoppe HG.
Eur Pat Appl 15049; 1984.
[9] Goldwasser DJ. Onder K. U.S. Pat. 4376 834;
1981.
[10] Legge NR, Holden G, Schroeder HE.
Thermoplastic elastomers. A comprehensive
review. Munich-Vienna-New York: Hanser
Publishers; 1987.
[11] Bayer O. Angew Chemie 1950;62:57.
[12] Rausch Jr. KW, Sayough AR. Industr Eng
Chem Prod Res Dev 1965;4:92.
[13] Kothandaraman H, Venkatarao K, Thanoo
BC. Polymer J 1989;21:829.
[14] Lakshminarayana SN, Jaisankar K,
Panduranga K, Radhakrishnan. J Polym Mat
1996;13:133.
290
[15] Lee DK, Tsai HB. J Appl Polym Sci
2000;75:167.
[16] Desai S, Thakore IM, Sarawade BD, Devi S.
Polym Eng Sci 2000;40:1200.
[17] Muller E. Rubber Plast Age 1958;39:195.
[18] Huang CC. PU World Congress, Abstract nr
162, Amstredam; 1997.
[19] Samborska-Skowron R, Balas A. Polym Adv
Tech 2002;13:653.
[20] Kontou E, Spathis G, Niaounakis M, Kefalas
V. Coll Polym Sci 1990;268:636.
[21] Petrovic Z, Javni I, Divjakovic V. J Polym
Sci, Part B: Polym Phys 1998;36:221.
[22] Smith TL. Polym Prepr 1974;15:58.
[23] Paik-Sung CS, Smith TW, Sung NH.
Macromolecules 1979;12:538.
[24] Paik-Sung CS, Smith TW, Sung NH.
Macromolecules 1980;13:117.
[25] Bonart R. Die Angewandte Makromol Chemie
1977;58/59:259.
[26] Ahn TO, Chio IS, Lee SW. Jeoung Macromol
Chem Phys 1994;195:2559.
[27] Kim BK, Shin Y, Cho SM, Jeong HM. J
Polym Sci B: Polym Phys 2000;38:2652.
[28] Trick GS. J Polym Sci 1960;3:252.
[29] Ophir ZH, Wilkes GL. Am Chem Soc Adv
Chem Ser 1979;176:53.
[30] Russo R, Thomas EL. J Macromol Sci-Phys
1983;B-22/4:553.
[31] Chang W, Baranowski T, Karalis T. J Appl
Polym Sci 1994;51:1077.
[32] Petrovic Z, Ilavsky M, Dusek K, Vidakovic
M, Javni M, Bozo B. J Appl Polym Sci
1991;42:391.
[33] Schnaber W. Conference Proc. “Microbial
Degradation of Synthetic Polymers”, London;
1988.
[34] Huang SJ. ACS Symposium Series 172, 471;
1981.
[35] Rutkowska M, Krasowska K, Heimowska A,
Janik H, Balas A. Proc. Gordon Conference,
California; 1999.
[36] Krasowska K, Janik H, Gradys A, Rutkowska
M. Degradation of polyurethanes in compost
under natural conditions. J Appl Polym Sci
2012;125(6):4252
60.
[37] Janik H. The Resistance of Different
Polyurethanes Against Attack of Aspergillus
Niger. Proc. Polyurethane World Congress,
Amsterdam 29.IX- 1. X. 1997. p. 739.
HANDBOOK OF THERMOSET PLASTICS
[38] Reegen SL, Frisch KC. advances in urethane
science and technology, vol. 2. Westport
Conn; 1973.
[39] Woods G. The ICI polyurethane book. New
York: John Wiley & Sons; 1985.
[40] Janik H. Elastomery 2001;5(3):16
27.
[41] Kang SM, Lee SJ, Kim BK. Expr Polimer
Lett 2012;6(1):63.
[42] Tian YH, Liu ZQ, Kang SM, Zhang XJ. High
Performance Structures and Materials
Engineering, PTS 1and 2 pp. 217
18. 728; 2011.
[43] Chung YC, Choi JW, Shin SJ, Chun BC.
Fibers and Polymers 2012;13:815.
[44] Seo WJ, Park JH, Sung YT, Hwang DH, Kim
WN, Lee HS. J Appl Polym Sci 2004;93
(5):2334.
[45] Festel G, Eisenbach CD. Angewandte
Makromolekulare Chemie 1998;256:89.
[46] Vlad S, Spiridon I, Grigoras CV, Drobota M.
Nistor A. E-POLYMERS Article Number:
004; 2009.
[47] Liaw DJ. Angewandte Makromolekulare
Chemie 1997;245:89.
[48] Eisenbach CD, Steinlein C, Milius W. Colloid
Polym Sci 1994;272(3):276.
[49] Król P. Prog Mate Sci 2007;52:915.
[50] Szycher Ph.D. M. Szycher’s handbook of
polyurethanes. Florida: CRC Press; 1999.
[51] Paciorek-Sadowska J, Czupryński B,
Liszowska J, Kotarska K. Inż Ap Chem
2012;51:58.
[52] IAL Consultants the ninth edition of its report
on the markets for Polyurethane Chemicals
and Products in Europe, Middle East and
Africa (EMEA)
2012.
[53] Decker C, Dormann B. Kunststoffe Plast
Europe 2005;7:2
5.
[54] Wicks DA, Wicks Jr ZW. Prog Org Coatings
2001;41:1
83.
[55] Wicks DA, Wicks Jr ZW. Prog Org Coatings
1999;36:148
72.
[56] Wirpsza Z. Poliurethanes, chemistry,
Technology and applications. UK: Ellis
Horwood Limited; 1993.
[57] MDI and TDI: Safety, Health and the
Environment: A Source Book and Practical
Guide, Edited by Allport DC, Gilbert DS,
Outterside SM, John Wiley & Sons; 2003.
[58] Issues Related to Occupational Exposure to
Isocyanates, 1989 to 2002, Department of
9: POLYURETHANES
health and human services, Centers for
Disease Control and Prevention National
Institute for Occupational Safety and Health,
January 2004, NIOSH Publications
Dissemination, ,http://www.cdc.gov/niosh/
docs/2004-116/..
[59] Streichera RP, Rehb CM, Key-Schwartza RJ,
Schlechtc PC, Cassinellia ME, O’Connora
PF. AIHAJ - Am Ind Hyg Assoc J 2000;61
(4):544
56.
[60] Source: ,http://www.epa.gov/ttnatw01/
hlthef/methylis.html. [accessed 07.07.13].
[61] Ionescu M. Chemistry and technology of
polyols for polyurethanes. Shrewsbury, UK:
Rapra Technology; 2005.
[62] Bruins PF, editor. Polyurethane technology.
London, UK: Interscience Publishers; 1969.
[63] Source: ,http://www.purinova.com.
[accessed: 07.07.13].
[64] Source : ,http://www.pcc.rokita.pl. [accessed:
07.07.13].
[65] Source : ,http://www.bayer.com.
[accessed: 07.07.13].
[66] Source : ,http://www.basf.com. [accessed:
07.07.13].
[67] Ma Y, Shi WP, Zhao CY, Yang DM, Lu Q,
Li SM, et al. Acta Chimica Sinica 2011;69
(6):719.
[68] Gu XZ, Mather PT. Polymer 2012;53(25):5924.
[69] Gopalakrishnan S, Fernando TL. Bull Mater
Sci 2012;35(2):243.
[70] Wojcik RT. Polyurethane coating: from raw
materials to end-products. Lancaster, PA,
USA: Technomic Publishing Company, Inc.;
1999. p. 78
82.
[71] Vilar WD. Chemistry and technology of
polyurethanes. 3rd ed. Lugoa, Rio de
Janeiro: Vilar Poliuretanos Ltd.; 2002.
Available from: www.polyuretanos.com.br/.
[72] Kucińska-Lipka J, Janik H, Balas A.
Polimery 2009;54(11/12):781
6.
[73] Kucińska-Lipka J, Janik H, Balas A.
Polimery 2009;54(7
8):530
6.
[74] Kaushik A, Singh P. J Appl Polym Sci
2012;125:E51.
[75] Prociak A., Michałowski S.: Mechanika.
Czasopismo Techniczne, 3, 249 ,(2009,).
[76] Prociak A, Gaca K, Michałowski S.
Modyfikacja Polimerów. Stan i perspektywy w
roku 2009, Oficyna Wydawnicza Politechniki
Wrocławskiej, Wrocław; 2009.
291
[77] Prociak A. Polimery 2008;53:195.
[78] Pawlik H, Prociak A, Pielichowski J.
Modyfikacja Polimerów. Stan i perspektywy w
roku 2009, Oficyna Wydawnicza Politechniki
Wrocławskiej, Wrocław; 2009.
[79] Pawlik H, Prociak A, Rojek P, Bogdal D.
Materiały Polimerowe ‘2010, Wydawnictwo
Uczelniane Zachodniopomorskiego Uniwersytetu
Technologicznego, Szczecin; 2010. p. 481
84.
[80] Narine SS, Kong X, Bouzidi L, Sporns P. J
Amer Oil Chem Soc 2007;84:65.
[81] Prociak A. Poliuretanowe materiały termoi-
zolacyjne nowej generacji, Wydawnictwo
Politechniki Krakowskiej, Kraków; 2008.
[82] Prociak A. Rynek Chemiczny 2007;7
8:17.
[83] Szałajko U, Fiszer S. Przemysł Chemczny
2003;7
8:18.
[84] Rossi P, Kosior E, Iovenitti P, Massod S,
Sbarski I. Progr Rub Plast Recycl Tech
2003;19:51.
[85] Ostrysz R, Penczek P, Wieczorek D. Prace
Naukowe Instytutu Materiałoznawstwa i
Mechaniki Technicznej Politechniki
Wrocławskiej, 63, 215; 2002.
[86] Kacperski M, Spychaj T. Polym Adv
Technol 1999;10:620.
[87] Patent US 5252615; 1993.
[88] Datta J, Pasternak S. Polimery 2005;50:
346.
[89] Datta J, Pniewska K. Polimery 2008;58:27.
[90] Datta J. J Therm Anal Calorimetry 2012;109:
517.
[91] Prociak A, Pielichowski J. Polimery
2005;50: 682.
[92] Czupryński B, Paciorek-Sadowska J,
Liszkowska J, Lewandowski R. Mechanika
Czasopismo Techniczne 2009;106:77.
[93] Czupryński B, Liszkowska J, Paciorek-
Sadowska J. Polimery 2010;55:314.
[94] Datta J. J Elastomers Plastics 2010;42
(2):117.
[95] Pokropski T, Balas A. Polimery 2003;48
(6):417.
[96] Czuprynski B. Zagadnienia z chemii I techno-
logii poliuretanów, Wydawnictwo Akademii
Bydgoskiej, Bydgoszcz; 2004.
[97] Bogdan M, Williams D, Verbiest PJ. Cell
Plast 2001;37:58.
[98] Modesti M, Lorenzetti A, Dall’Acqua C.
Polym Eng Sci 2005;45:260.
[99] Frish KC. Polimery 1996;41:193.
292 HANDBOOK OF THERMOSET PLASTICS

[100] Kim BK, Seo JW, Jeong HM. Europ Polym J
2003;39:85
91.
[101] Xu R, Manias E, Snyder AJ, Runt J. [121]
Macromolecules 2001;34:337.
[102] Pattanayak A, Jana SC. Polymer 2005;46:
3275. [122]
[103] Tocha E, Janik H, De˛bowski M, Vancso GJ. [123]
J Macromol Sci, Part B: Phys 2002;B41 [124]
(4
6):1291
304.
[104] Szycher M. Szycher’s handbook of polyur- [125]
ethanes. Boca Raton, FL, USA: CRC Press [126]
Taylor & Francis Group; 2012.
[105] Clemitson I. Castable polyurethane elasto- [127]
mers. Boca Raton, FL, USA: CRC Press
Taylor & Francis Group; 2008.
[106] Janik H, Balas A. Polimery 2009;54 [128]
(3):195
201.
[107] Buist JM, Gudgeon HA, editors. Advances in [129]
polyurethane technology. Barking, UK:
Elsevier Publishing Company Limited; 1970. [130]
[108] Herrington R, Hock K, editors. Flexible
polyurethane foams. 2nd ed. Midland, MI,
USA: Dow Chemical Company; 1997.
[109] Frisch KC, Saunders JH, editors. Plastic
foams. New York, NY, USA: Marcel Dekker; [131]
1972.
[110] Gao C, Yan D. Prog Polym Sci 2004;29 [132]
(3):183
275.
[111] Schömer M, Schüll C, Frey H. Article first [133]
published online J Polym Sci 26 December
2012;.
[112] Sunder A, Hanselmann R, Frey H, Mülhaupt [134]
R. Macromolecules 1999;32(13):4240
6.
[113] Sunder A, Mülhaupt R, Haag R, Frey H. [135]
Macromolecules 2000;33(2):253
4.
[114] Allport DC, Janes WH. Block copolymers. [136]
London: Applied Science Publishers LTD;
1973. [137]
[115] Saunders JH. Rubber Chem Technol 1960;33
(5):1259
92. [138]
[116] Goodman B. Development in block copoly-
mers. London-New York: Applied Science
Publishers; 1982. [139]
[117] Dzierża S, Janáček J. Mechanical behavior
of lightly crosslinked polyurethanes. Rubber [140]
Chem Technol 1977;50(5):934
44.
[118] Macosco CW. Plast Eng 1983;39:21
5. [141]
[119] Gilding DK, Dixon SA. Action for biomater-
ials profiles, Zynergy Core Technology,1999. [142]
[120] Czupryński B. Zagadnienia z chemii i tech-
nologii poliuretanów, Wydaw. Akademii
Bydgoskiej im. Kazimierza Wielkiego,
Bydgoszcz; 2004.
Laas HJ, Halpaap R, Pedain J. Journal für
Praktische Chemie/Chemiker-Zeitung
1994;336(3):185
200.
Patent US 2005/0033006 A1; 2005.
Patent US 7297752; 2007.
Ulrich H. J Polym Sci: Macromol Rev
1976;11(1):93
133.
Patent US 6635761.
Semsarzadeh MA, Navarchian AH. J Appl
Polym Sci 2003;90:963
72.
Gum WF, Ulrich H, Riese W, editors.
Reaction polymers. Munich, Germany:
Hanser Publishers; 1992.
Jasińska L, Haponiuk JT, Balas A. Therm
Anal Calorimetry 2008;3:777
81.
Jasińska L, Balas A, Haponiuk JT. e-
Polymers 2007;3:1
14.
Jasińska L, Balas A, Haponiuk JT,
Nowaczyk G, Jurga S. Thermal and dynamic
mechanical analysis of cross-linked poly
(esterurethanes). Therm Anal Calorimetry
2007;2:419
23.
Cherian Benny A, Abraham Beena T, Thachil
Elby T. J Appl Polym Sci 2006;100:449
56.
Bélan F, Bellenger V, Mortaigne B. Polym
Degradation Stability 1997;56:93
102.
Aldrighetti C, Tassone P, Ciardelli F,
Ruggeri G. Polym Degradation Stability
2005;90(2):346
53.
Ludovic V, Chin-Pin H. Polymer
1999;40:2059
70.
Ramis X, Cadenato A, Morancho JM, Salla
JM. Polymer 2001;42:9469
79.
Radenkov P, Radenkov M, Grancharov G,
Troev K. Europ Polym J 2003;39:1223
8.
Such DJ, Park OO, Yoon KH. Polymer
2000;41(2):461
6.
Oprea S, Vlad S, Stanciu A, Ciobanu C,
Macoveanu M. Europ Polym J 1999;35:
1269
77.
Oprea S, Vlad S, Stanciu A. Polymer
2001;42:7257
66.
Oprea S. Polym Degradation Stability
2002;75:9
15.
Oprea S, Vlad S, Stanciu A. Europ Polym J
2000;36:2409
16.
Oprea S, Vlad S, Stanciu A, Ciobanu C,
Macoveanu M. Europ Polym J
2000;36:373
8.
9: POLYURETHANES
[143] Patent US 3 043 807.
[144] Patent US 3 061 574.
[145] Balas A, Pałka G, Płomińska B, Rutkowska
M. Acta Polymerica 1980;31:673
9.
[146] Egboh SHO. J Macromol Sci, Part A
1983;19:1041
8.
[147] Sekkar V, Ninan KN, Krishnamurthy VN, Jain
SR. Europ Polym J 2000;36(11):2437
48.
[148] Gupta T, Adhikari B. Thermochimica Acta
2003;402(1
2):169
81.
[149] Coutinho FMB, Delpech MC, Alves TL,
Ferreira AA. Polym Degradation Stability
2003;81(1):19
27.
[150] Thomas V, Jayabalan M. Biomaterials
2002;23(1):273
82.
[151] Sarkar S, Adhikari B. Polym Degradation
Stability 2001;73(1):169
75.
[152] Sekkar V, Bhagawan SS, Prabhakaran N,
Rao MR, Ninan KN. Polymer 2000;41
(18):6773
86.
[153] Desai S, Thakore IM, Sarawade BD, Surekha
D. Europ Polym J 2000;36(4):711
25.
[154] Wingborg N. Polym Test 2002;21(3):283
7.
[155] Coutinho FMB, Delpech MC, Garcia MEF.
Polym Test 2002;21(6):719
23.
[156] Goldschmidt A, Streitberger HJ. Basf hand-
book on Basic of coating technology, BASF
Coatings AG, Münster, Vincentz Network,
Hannower; 2003.
[157] Brock T, Groteklaes M, Mischke P.
European Coatings Handbook, Curt R.
Vincentz Verlag, Hannover; 2000.
[158] Stoye D. Paints, coatings and solvents.
Weinheim: Verlagsgesellschaft mbH; 1993.
[159] Hydroxyl Terminated Polybutadiene Resins
and Derivatives - Polybd® Resins and
Krasol®, Startomer Product Bulletin; 2012,
,www.sartomer.com..
[160] Cooper SL, Tobolsky AV. J Appl Polym Sci
1966;10:1837.
[161] Cooper SL, Tobolsky AV. Text Res J
1966;36:800.
[162] Cooper SL, West JC. Encyklopedia of poly-
mer science and technology Supplement Nr
1 Wiley; 1978
[163] Stanford JL, Still RH, Wilkinson AN.
Polymer 2003;44:3985.
[164] Bonart R, Muller EH. J Macromol Sci 1974;
B10:177.
[165] Ophir Z, Wilkes GL. J Polym Sci
1980;18:1469.
293
[166] Van Bogart IW, Gibson PE, Cooper SL. J
Polym Sci Phys Ed, 21. 1983.
[167] Bonart R, Meyer H. Prog Colloid Polym Sci
1985;71:103.
[168] Privalko VP, Privalko EG, Shtompel VI.
Polym Eng Sci 1999;39:1534.
[169] Savelyev YV, Abranovich ER, Grekov AP.
Polymer 1998;39(15):3425.
[170] Koberstein JT, Galambos AF.
Macromolecules 1992;25:5618.
[171] Shirasaka H, Inoune S-I, Asai K, Okamoto
H. Macromolecules 2000;33:2776.
[172] Assink RA. J Polym Sci Phys Ed, 15. 1977.
[173] Nierzwicki W. J Appl Polym Sci 1984;29:
1203.
[174] Ishida M, Yoshinga K, Horii F.
Macromolecules 1996;29:8824
9.
[175] Yoon PJ, Han CD. Macromolecules
2000;33:2171
83.
[176] Srichatrampinuk VW, Cooper SL. Macromol
Sci Phys 1978;15:267.
[177] Moller GW, Saunders JH. J Polym Sci 1970;
A-1:1923.
[178] Vrouentaets CM. Polym Prepr 1972;13:529.
[179] Allegrezza N, Seymour RW, Cooper SL.
Polymer 1973;14:255.
[180] Samuels SL, Wilkes GL. J Polym Sci 1973;
A-2/11:807.
[181] Wilkes GL. J Polym Sci 1975;13:321.
[182] Zelener YV. Vysokomol Sojed 1978;A-
20:306.
[183] Seefried CG, Koleske JV, Gritchfield FE. J
Appl Polym Sci 1975;19:2493.
[184] Kwei TK. J Appl Polym Sci 1982;27:2891.
[185] Work JL. Macromolecules 1976;9:759.
[186] Chen TK, Shien TS, Chui JY. Macromolecules
1998;31:1312.
[187] Hong JL, Lillya P, Chien JCW. Polymer
1992;33:4347.
[188] Nakamae K, Nishino T, Asaoka S,
Sudaryanto. Int J Adhes Adhesives
1996;16:233.
[189] Seymour RW, Cooper SL. Macromolecules
1973;6:48.
[190] Cooper SL. Polym Eng Sci 1971;11:369.
[191] Clough S, Schneider N. J Macromol Sci-
Phys 1968;B2/4:353.
[192] Pissis P, Kanapitsas A, Savelyev YV, et al.
Polymer 1998;39(15):3431
5.
[193] Samuels SL, Wilkes GL. Polym Lett
1971;9:761.
294
[194] Samuels SL, Wilkes GL. Polym Preprints
1971;12:694.
[195] Wilkes GL, Samuels SL. J Polym Sci Symp
1973;43:149.
[196] Samuels SL, Wilkes GL. Polym Preprints
1972;13:999.
[197] Wilkes GL, Samuels SL, Crystal R.
Macromol Sci Phys 1974;B10:203.
[198] Clough S, Schneider N, King A. J Macromol
Sci
Phys 1968;B2/4/:641.
[199] Foks J, Janik H, Potocki A. 15th
Czechoslovak Conference on Electron
Microscopy, Prague; 1977, A, p. 491.
[200] Foks J, Janik H, Russo R. Europ Polym J
1990;26:309.
[201] Foks J, Janik H. Polym Eng Sci 1989;29:113.
[202] Janik H, Foks J. Prog Coll Polym Sci
1992;90:241.
[203] Fridman JD, Thomas EL. Polymer
1980;21:388.
[204] Foks J, Janik H. Proceeding of Europlastic
Conference, Paryż; 1982. pV-9/1.
[205] Koutsky JA, Hien NV, Cooper SL. J Polym
Sci 1970;B8:353.
[206] Schneider NS, Desper CR, Illinger JL, King
AO, Barr D. J Macromol Sci-Phys 1975;B-
11:527.
[207] Aggarwal SL. Polymer 1976;17:938.
[208] Chen CHY, Briber RM, Thomas EL, Xu M,
Mac Knight WJ. Polymer 1983;24:1333.
[209] Janik H, Foks J. Polimery 1980;25:410.
[210] Xu M, Mac Knight WJ, Chen CH, Thomas
EL. Polymer 1983;24:1327.
[211] Neff R, Adedeji A, Macosko CW, et al. J
Polym Sci Pol Phys 1998;36:573.
[212] Rutkowska M, Jastrze˛bska M, Janik H.
Compos Sci Technol 1997;57:1155.
[213] Foks J, Michler G. J Appl Polym Sci
1986;31:1281.
[214] Foks J, Michler G, Nauman J. Polymer
1987;28:2195.
[215] Eisenbach CD, Ribbe A, Goldel A. Kaaut
Gummi Kunstst 1996;49:406.
[216] Zha LS, Wu MY, Yang JJ. J Appl Polym Sci
1999;37:2895.
[217] Vanlandingham MR, McKnight SH, Palmese
GR. J Adhes 1997;64:31.
[218] Gupta T, De D, Adhikari B. Polym Int
2003;52:938.
[219] Corneillie S, Lan PN, Schacht E. Polym Int
1988;46:251.
HANDBOOK OF THERMOSET PLASTICS
[220] Karbach A, Drechsler D. Surf Interface Anal
1999;27:401.
[221] Kaushiva BD, Wilkes GL. Polymer
2000;41:6981.
[222] Garret JT, Siedlecki CA, Runt J. Macromol
2001;34:7066.
[223] Garret JT, Lin JS, Runt J. Macromol
2002;35:161.
[224] O‘Sickey MJ, Lawrey BD, Wilkes GL. J
Appl Polym Sci 2002;84:229.
[225] Yang S, Chow S, Lin D. Synth Met
2001;121:1305.
[226] Bonart R. J Macromol Sci-Phys 1968;B2
(1):115.
[227] Bonart R, Morbitzer L, Hentze G. J
Macromol Sci-Phys 1969;B3(2):337.
[228] Bonart R, Morbitzer L, Muller EH. J
Macromol Sci-Phys 1974;B9(3):447.
[229] Bonart R. Polymer 1979;20:1389.
[230] Wilkes SL, Yusek CS. J Macromol Sci Phys
1974;B9:447.
[231] Koberstein JT, Stein R. J Polym Phys Ed,
21. 1986.
[232] Ishihara H, Kimura I, Saito K, Ono H. J
Macromol Sci Phys 1974;B10:591.
[233] Paik Sung CS, Schneider NS. Macromolecules
1975;8:68.
[234] Paik Sung CS, Schneider NS. Macromolecules
1977;10:452.
[235] Schneider NS, Paik Sung CS. Polym Eng Sci
1977;17:73.
[236] Huh DS, Cooper SL. Polym Eng Sci
1971;11:369.
[237] Flory PJ. Adv Polym Sci 1984;59:1.
[238] Tao H-J, Fan CF, Mac Knight WJ, Hsu SL.
Macromolecules 1994;27:1720.
[239] Hammond PT, Rubner MF. Macromolecules
1992;25:2391.
[240] Culbertson BM, editor. Multiphase macro-
molecular systems. New York: Plenum
Publishing Corp.; 1989.
[241] Harrel Jr LL. Macromolecules 1969;2:607.
[242] Kornfield JA, Spiess HW, Nefzhger H,
Eisenbach CD. Macromolecules 1991;24: 4787.
[243] Chang YP, Wilkes GL. J Polym Sci: Polym
Phys Ed 1975;36:455.
[244] Wang G, Fang B, Zhang Z. Polymer 1994;35
(15):3178.
[245] Paik Sung CS, Schneider NS, Matton RW,
Illinger JL. Polym Prep Am Chem Soc
Polym Chem Div 1974;15:620.
9: POLYURETHANES 295

[246] Chang AL, Thomas EL. Adv Chem [261] Source: ,http://www.hempel.com. [accessed
1979;176:31. 07.07.13].
[247] Chang AL, Briber RM, Thomas EL, [262] Source: ,http://www.jotun.com. [accessed
Zdrahala RL, Critchfield FE. Polymer 07.07.13].
1982;23:1060. [263] Source: ,http://www.diegel.de. [accessed
[248] Janik H. PhD Thesis, Gdańsk University of 07.07.13].
Technology, Gdańsk; 1989. [264] Czech Z, Milker R, Malec A. Rev Adv
[249] Janik H, Foks J. In: Frisch KC, Klempner D, Mater Sci 2006;12:189.
editor. Advances in urethane science & tech- [265] Dey J, Xu H, Shen J, Thevenot P, Gondi SR,
nology, Lancaster vol. 11, 137; 1992. Nguyen KT, et al. Biomaterials
[250] Janik H, Foks J, Kwiatkowski A. Integration 2008;29:4637.
of fundamental polymer science & technol- [266] Wang H, Feng Y, Fang Z, Yuan W. Musammir
ogy -5. London: Elsevier Science Publishers Khan Mater Sci Eng C 2012;32(8):.
LTD; 1991. p. 330. [267] Bonzania IC, Adhikarib R, Houshyarb S,
[251] Janik H, Foks J, Russo R, Winiecki S. Europ Mayadunneb R, Gunatillakeb P, Stevensa
Polym J 1989;25:31. MM. Biomaterials 2007;28:423
33.
[252] Chau KW, Geil PH. Polymer 1985;26:490. [268] Jiang X, Li J, Ding M, Tan H, Ling Q,
[253] Briber RM, Thomas EL. J Macromol Sci- Zhong Y, et al. Europ Polym J
Phys 1983;B-22:509. 2007;43:1838.
[254] Briber RM, Thomas EL. J Polym Sci: Polym [269] Gorna K, Gogolewski S. J Biomed Mater
Phys Ed 1985;23:1915. Res 2003;67A:813.
[255] Walsh SJ, Higgins JS. Polym J 1979;20:951. [270] Source: ,http://www.organika.pl.
[256] Tocha E, Janik H, De˛bowski M, Vancso J. [accessed 07.07.13].
EPS European Conference on Macromol. [271] Source: ,http://www.futurefoam.com.
Physics “Morphology & Properties of [accessed 07.07.13].
Crystalline polymers”, Eger; 2001. [272] Source: ,http://www.selena.pl. [accessed
[257] Janik H, Palys B, Petrovic Z. Macromol 07.07.13].
Rapid Commun 2003;24:265. [273] Source: ,http://www.ncfi.com. [accessed
[258] Janik H, Vancso J. Polimery 2005;50 07.07.13].
(2):139
42. [274] Source: ,http://www.polyurethaneresin.net/.
[259] Kozakiewicz J, Janik H, Kwiatkowski R, [accessed 07.07.13].
Włochowicz A. Polym Adv Techn [275] Source: ,http://www.oliva.com.pl.
2000;21:82. [accessed 07.07.13].
[260] Krakovsky J, Plestil J, Baldrian J,
Wubbenhorst M. Polymer 2002;43:4989.