Introduction
From the recent studies of a new group of
polyurethanes containing unsaturated bonds one may
extract a few trends. One of them focuses on poly(ure-
thaneacrylates) (PEUA) and poly(urethaneurea-meth-
acrylates) (PEUMA) in which the presence of
unsaturated bonds allows for their cross-linking by a
radical polymerization [1–5]. In the papers by
Oprea et al. [1–3] concerning thermal stability of
PEUA and PEUMA two maxima of mass loss in their
thermograms were revealed. Furthermore, these
authors showed that polymers containing cross-
linking bonds exhibit an increase of degradation
temperature of up to 15–25°C in comparison with
polymers containing double bonds. Their thermo-
gravimetric analysis revealed also a decrease in
activation energy of up to 20–30% for PEUA [1] and
10–15% for PEUMA [2], respectively. These
changes, in authors’ opinion, may be caused by the
dehydration of the –COO
–+
NH
3
structure and poly-
merization of double bonds.
The group of polymers containing unsaturated
bonds includes also poly(ester-siloxane)ure-
thanes [6, 7]. The presence of urethane groups and
fragments of polysiloxane chains allows for obtaining
polymers with sufficiently thermal and mechanical
properties. The studies on mechanical properties and
thermal stability of cross-linked elastomers revealed
their dependence on chemical composition and
cross-linking density. As shown in [6–8], these
properties are strongly influenced by hard segment
content in the structure of elastomers. Dynamic-
mechanical thermal analysis measurements of
poly(ester-siloxane)urethanes exhibited an influence
of chemical composition of polymers and the type of
the used cross-linking agent on their thermo-mecha-
nical properties [6].
The intercross-linked networks of siliconized
polyurethane-epoxy/unsaturated polyester coatings
also constitute an important group of cross-linked
polymers [8]. The thermal stability of these systems
was studied using a differential scanning calorimetry
and thermogravimetric analysis. The studies proved
that the presence of urethane groups in these systems
reduces their thermal stability. Moreover, the polymers
containing urethane groups have lower glass transition
temperatures (T
g
) than the unmodified ones. Urethane
groups in elastomers increase their tensile strength and
thus provide possibilities of wide application.
The present paper discusses the influence of a
chemical structure on the thermal and dynamic-
mechanical properties of cross-linked poly(esterure-
thanes). In particular, the influence of the [NCO/OH]
molar ratio and the type of the used cross-linking
monomer was studied. The obtained results show also
that the poly(esterurethanes) which contain cross-
linking agent are more stable than the reference
materials without cross-linking.
1388–6150/$20.00 Akadémiai Kiadó, Budapest, Hungary
© 2007 Akadémiai Kiadó, Budapest Springer, Dordrecht, The Netherlands
Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007) 2, 419–423
THERMAL AND DYNAMIC MECHANICAL ANALYSIS OF
CROSS-LINKED POLY(ESTERURETHANES)
Lidia JasiÕska
1*
, A. Balas
1
, J. T. Haponiuk
1
, G. Nowaczyk
2
and S. Jurga
2
1
GdaÕsk University of Technology, Faculty of Chemistry, Department of Polymer Technology, Narutowicza St 11/12
80-952 GdaÕsk, Poland
2
Adam Mickiewicz University, Faculty of Physics, Department of Macromolecular Physics, Umultowska St 85, 61-614 PoznaÕ, Poland
New cross-linked poly(esterurethanes) (PEU) based on unsaturated olygo(alkyleneester)diol (OAE), 4,4’-diphenylmethane
diisocyanate (MDI) and styrene or methyl methacrylate as curing monomers were prepared. The synthesis of PEU was performed in
two steps. In the first step OAE was obtained from adipic acid, maleic anhydride and ethylene glycol. In the second step a
prepolymer was obtained in a reaction of OAE with different amounts of 4,4’-diphenylmethane diisocyanate followed by cross-
linking using previously mentioned curing monomers. The influence of structure of the poly(esterurethanes) on thermal and
dynamic mechanical properties is studied. Thermogravimetric analysis shows that cross-linked poly(esterurethanes) demonstrate
high thermal stability. Moreover the dynamic mechanical thermal analysis shows that the presence of styrene cross-linking chains
in polymers lead to the phase separation in cross-linked poly(esterurethanes).
Keywords: dynamic-mechanical analysis, poly(esterurethanes), thermal stability
* Author for correspondence: lidia@urethan.chem.pg.gda.pl