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Polymeric Materials, 2009: 29-48 ISBN: 978-81-7895-398-4

Editor: Aleksandra B. Nastasović

Thermoplastic elastomers

2 based on poly(butylene
terephthalate) and various
siloxane prepolymers
Vesna V. Antić1, Marija V. Vučković1, Milica R. Balaban1
Milutin N. Govedarica1 and Jasna Djonlagic2
1
Polymer Department, Center of Chemistry, Institute of Chemistry
Technology and Metallurgy, Studentski trg 12-16, 11000 Belgrade, Serbia
2
Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia

Abstract
Thermoplastic poly(ester-siloxane)s (TPES)
and poly(ester-ether-siloxane)s (TPEES), based on
poly(butylene terephthalate) (PBT) as the hard
segment and different siloxane-containing prepolymers
as the soft segments were synthesized by catalyzed
two-step transesterification/polycondensation reaction.
Incorporation of disilanol- or dicarboxypropyl-
terminated poly(dimethylsiloxane)s (PDMS-OH and
PDMS-CP) into the polar poly(butylene terephthalate)
h l d
Correspondence/Reprint request: Dr. Vesna V. Antić, Polymer Department, Center of Chemistry, Institute of
Chemistry, Technology and Metallurgy, Studentski trg 12-16, 11000 Belgrade, Serbia
E-mail: vantic@chem.bg.ac.yu
30 Vesna V. Antić et al.

chains resulted in rather inhomogeneous TPES copolymers. The inhomogeneity

was a consequence of a pronounced phase separation of the polar and non-polar
reactants during the synthesis. In order to avoid or reduce phase separation,
siloxane–containing triblock prepolymers with hydrophilic terminal blocks, such
as ethylene oxide (EO), poly(propylene oxide) (PPO) or poly(caprolactone)
(PCL), were investigated in order to improve the compatibility of corresponding
prepolymer with the polar reactants, dimethyl terephthalate (DMT) and 1,4-
butanediol (BD). Homogeneity was significantly improved in the case of
copolymers with poly(caprolactone)-poly(dimethylsiloxane)-poly(caprolactone)
soft segments, but the melting temperatures and degrees of crystallinity of the
resulting copolymers were much lower in comparison with all the previous
synthesized series of copolymers. Thermal stability of the obtained copolymers
was higher in comparison with PBT homopolymer, with exception of PDMS-CP
based samples, which were somewhat less stable.

Introduction
Thermoplastic elastomers represent polymeric materials that combine the
elasticity and flexibility of chemically cross-linked elastomers and the easiness
of processability of thermoplastic materials. Combined thermoplastic and
elastomeric behavior is characteristic for block copolymers, as well as for
mixtures of elastomers and thermoplasts. Block copolymers belonging to the
class of thermoplastic elastomers consist of two types of chemically incompatible
segments: hard, glassy or crystalline blocks, which provide for physical
crosslinking, and soft, flexible blocks with a low glass transition temperature,
which provide for elasticity. The chemical incompatibility of the hard and
soft blocks leads to phase segregation and the formation of a two-phase
microstructure. Due to the two-phase microstructure, thermoplastic elastomers
possess excellent mechanical properties, such as low-temperature flexibility,
impact strength, toughness and high modules in the rubbery plateau region.
At elevated temperatures, the physical crosslinking disappears, allowing the
copolymer to soften and flow like thermoplastic materials thus enabling it to
be processed in the melt by techniques such as injection molding [1, 2].
The properties of thermoplastic elastomers depend on the chemical nature of
the two types of segments, hard and soft, as well as on their mass ratio and
respective lengths [1, 2]. Organic-siloxane block copolymers, due to the presence
of poly(siloxane) chains, show lower glass transition temperatures, higher thermal
and thermo-oxidative stability, as well as higher resistance to UV-radiation,
atomic oxygen and ozone, enhanced permeability to many gases, hydrophobicity,
biocompatibility and resistance to many solvents in comparison to common
organic polymers. As a result of the mentioned properties, organic-siloxane
Thermoplastic elastomers based on siloxane prepolymers 31

copolymers have received special attention as elastomers, protective coatings,

photoresists, biomaterials, gas separation membranes, emulsifiers, etc [3].
Reactive, telechelic siloxane oligomers are the most important starting
material for the synthesis of siloxane-containing copolymers which behave as
thermoplastic elastomers. Step-growth polymerization is usually used for the
synthesis of such organo-siloxane copolymers, mainly due to the availability
of a wide variety of well-defined, organofunctionally terminated reactive
siloxane oligomers (α,ω-telechelic siloxanes).
The main factors determining the reactivity of telechelic siloxane oligomers
toward other reactants are the type and nature of the terminal functional groups.
Due to the fundamental differences in their structures, chemical reactivities and
overall properties, it is possible to divide functionally terminated siloxane
oligomers into two groups. The first group consists of oligomers with Si-X
terminal units and the other with Si-R-X units, where X and R represent the
reactive functional group and a short organic moiety, respectively.
In most of the published reports concerning siloxane containing
copolymers, the soft segment was almost exclusively poly(dimethylsiloxane).
Poly(dimethylsiloxane) has one of the lowest values of glass transition
temperature (Tg = -123 °C) and the largest molar volume (75.5 cm3/mol). Chain
flexibility and low intermolecular forces are also responsible for its low surface
tension, low solubility parameters and low dielectric constant. Moreover, these
properties show only a very small variation over a wide range of temperatures,
which is also an important characteristic of poly(siloxane)s [3, 4]. The
extremely non-polar nature of PDMS, together with the very low level of inter-
and intramolecular attractions, leads to the formation of thermodynamically and
mechanically incompatible blends with virtually all other polymers. This is
reflected in the very low value of the solubility parameter of PDMS [δ =15
(J/cm3)1/2] [3, 5], when compared with other polymers [δ =15.4-28.0 (J/cm3)1/2]
[6]. This is the most important driving force in the formation of a two-phase
microstructure in PDMS containing copolymers. Another very important factor
which makes the morphology and structure-property relationships of siloxane
copolymers somewhat unusual when compared with conventional organic
block copolymers is the fact that at room temperature (20-25 °C), at which
most of polymer experiments are conducted, PDMS is about 150 °C above its
glass transition temperature. At these temperatures, due to the absence of inter
and intramolecular interactions, PDMS behaves like a non-polar viscous liquid,
thus providing perfect conditions for the formation of phase separated
copolymer structures. In many cases, a siloxane molar mass as low as 500-600
g/mol (6-8 siloxane repeat units) and an organic segment having only a single
repeat unit are sufficient to obtain two-phase morphologies [3].
32 Vesna V. Antić et al.

Several studies on thermoplastic elastomers based on soft

poly(organosiloxane)-based segments and hard poly(butylene terephthalate)
segments have been presented and described in the literature since 1990 [7-
26]. Poly(organosiloxane)s exhibit many important and interesting properties,
such as low-temperature flexibility, high thermal and thermo-oxidative
stability, good biocompatibility, low surface energy, ultraviolet resistance and
high permeability to many gases [3, 4]. The incorporation of
poly(organosiloxane)-containing segments into a PBT-backbone results in
improved clarity, surface smoothness and non-sticking properties, as well as
good film, fiber and hydrophobic properties of the resulting copolymers [7-16].
Our research in the field of siloxane containing copolymers commenced with
the synthesis of poly(ester–siloxane)s (TPES) based on poly(butylene terephthalate)
(PBT) as the hard segment and poly(dimethylsiloxane) prepolymers as the soft
segments. The TPES copolymers were synthesized by catalyzed two-step
transesterification, from dimethyl terephthalate, (DMT), 1,4-butanediol, (BD) and
poly(dimethylsiloxane)s with either disilanol- (PDMS-OH) or dicarboxypropyl-
(PDMS-CP) terminal groups. Incorporation of PDMS-OH or PDMS-CP
homopolymers into the polar PBT chains resulted in rather inhomogeneous TPES
copolymers, because of the pronounced phase separation of the polar and non-
polar reactants during synthesis [21-24]. All the copolymers prepared were
partially soluble in chloroform, as a consequence of their significant structural
and compositional inhomogeneity. Siloxane-containing triblock prepolymers
with hydrophilic terminal blocks (which served as a compatibilizer between the
extremely non-polar PDMS and the polar DMT and BD), such as ethylene oxide
(EO), poly(propylene oxide) (PPO) or poly(caprolactone) (PCL) [25, 26], were
used in further investigations to avoid phase separation during copolymer
synthesis and to increase the miscibility of the polar and non-polar reactants.
The structure, composition and size of the poly(ester-siloxane)s and poly(ester-
ether-siloxane)s macromolecules were investigated by 1H NMR and 13C NMR
spectroscopy and the viscosity of dilute solutions. The thermal properties of
samples from all the synthesized series were investigated by differential
scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

Experimental
1. Siloxane-containing prepolymers
α,ω-Dicarboxypropyl-poly(dimethylsiloxane)s (PDMS-CP, M n =1030
g/mol) and their dimethyl-esters were prepared as described previously [21,
27]. α,ω-Disilanol-poly(dimethylsiloxane) (PDMS-OH, M n =2400 g/mol),
α,ω-dihydroxy-poly(ethylene oxide-dimethylsiloxane-ethylene oxide (EO-
Thermoplastic elastomers based on siloxane prepolymers 33

PDMS-EO), α,ω-dihydroxy-poly(propylene oxide-dimethylsiloxane-propylene

oxide) (PPO-PDMS-PPO) and α,ω-dihydroxy-poly(caprolactone-
dimethylsiloxane-caprolactone) (PCL-PDMS-PCL) were supplied from
ABCR (Germany). The number-average molar masses of the EO-PDMS-EO,
PPO-PDMS-PPO and PCL-PDMS-PCL, were determined by 1H NMR
spectroscopy. The M n of the prepolymer EO-PDMS-EO was 1200 g/mol,
the molar mass of central poly(dimethylsiloxane) (PDMS) block was
M PDMS = 1080 g/mol, and the terminal ethylene oxide, (EO) consisted of
one unit. The number-average molar mass of the PPO-PDMS-PPO was 2900
g/mol, with a molar mass of the central poly(dimethylsiloxane) (PDMS)
block of M PDMS = 1100 g/mol and a molar mass of the terminal
poly(propylene oxide) (PPO) blocks of M PPO = 900 g/mol. The M n of the
PCL-PDMS-PCL was 6100 g/mol, the molar mass of the central
poly(dimethylsiloxane) (PDMS) block was M PDMS = 2000 g/mol. The molar
mass of the terminal poly(caprolactone) (PCL) blocks was M PCL = 2050 g/mol.

2. Poly(ester-siloxane) and poly(ester-ether-siloxane) synthesis

The poly(ester-siloxane)s and poly(ester-ether-siloxane)s were
synthesized by catalyzed two-step reactions involving transesterification
and polycondenzation in the melt, under the optimal conditions [21-25].
The reactants were dimethyl terephthalate (DMT), 1,4-butanediol (BD), and
the corresponding siloxane prepolymer (PDMS-OH, PDMS-CP, EO-
PDMS-EO, PPO-PDMS-PPO or PCL-PDMS-PCL). The catalyst was tetra-
n-butyl-titanate (1.0-2.5 mmol / mol DMT), whilst the thermal stabilizer
was N,N′-diphenyl-p-phenylenediamine. The first step, transesterification,
was performed from 160 to 230-240 °C, at atmospheric pressure, whereby
the formed methanol was distilled off. The second step, polycondensation,
was performed for 1.5 to 4.5 h (depending on which prepolymer was used)
at 230-250 °C, under reduced pressure. In this manner, three series of
TPESs and two of TPEESs, with different soft segments and hard-to-soft
weight ratios in the range from 90/10 to 40/60, were obtained. The
synthesized TPESs (except for the copolymers based on PCL-PDMS-PCL)
and the TPEESs were extracted with chloroform and the obtained soluble
and insoluble fractions were analyzed by 1H NMR spectroscopy [21-26].

3. Characterization of the copolymers

1
H NMR (200 MHz) spectra were obtained on a Varian Gemini-200
instrument. The TPES samples based on PDMS-OH and PDMS-CP, as well
34 Vesna V. Antić et al.

as the TPEES samples, were measured as solutions in CF3COOD. The

solvent was simultaneously used as the internal standard. The TPES samples
based on PCL-PDMS-PCL prepolymer were measured as solutions in CDCl3.
The inherent viscosities (ηinh) of the TPES and TPEES samples were
measured in a mixture of phenol/trichloroethylene/toluene (1:1:2 by vol.) at
30 °C, using an Ubbelohde viscometer.
Gel permeation chromatography (GPC) was conducted on a Waters 600E
instrument equipped with a refractive index detector, on three Supelco Pl-Gel
columns connected in line (cross-linked polystyrene with pore sizes of 10-5,
10-6 and 10-7 m) at 30 °C. Twenty µl of a sample solution in chloroform (10 mass
%) were injected in all cases. The flow rate was 1.5 m3 min−1. The system was
calibrated with a number of high and low molecular weight siloxanes [27].
Differential scanning calorimetry (DSC) was performed using a Perkin
Elmer DSC2 thermal analyzer. The DSC scans were recorded under a dynamic
nitrogen atmosphere (flow rate 25 cm3 min−1) at a heating and cooling rate of 10
°C min−1 (two scans were run for each sample). The weight of the samples
was approximately 10 mg. The samples were analyzed between 50 and 250 °C.
Thermogravimetric analysis (TGA) was performed using a TA Instruments
SDT Q600 analyzer in the temperature range from 30 to 750 °C. The heating
rate was 10 °C min−1. The TGA scans were recorded under a dynamic nitrogen
atmosphere with a gas flow rates of 100 cm3 min−1. The sample mass was about
10 mg.

Results and discussion

Structure and composition of synthesized TPESs and TPEESs
Our work on thermoplastic, siloxane-containing copolymers commenced
with the synthesis and characterization of poly(ester–siloxane)s based on
PBT as the hard segment and PDMS prepolymers with either silanol- or
carboxypropyl- terminal groups as the soft segment [21]. The series of
copolymers prepared with PDMS-OH is denoted as TPES-OH, whilst the
series obtained with PDMS-CP is denoted as TPES-CP. The structures of the
employed prepolymers and the synthesized copolymers are presented in
Scheme 1 and 2, respectively. Poly(butylene terephthalate) was chosen as the
hard segment for the thermoplastic elastomers because of its high structural
regularity, rapid crystallization and high degree of the crystallinity [28, 29].
After the optimal reaction conditions had been established [21], the effect of
the length of the carboxypropyl-terminated PDMS prepolymers (550–2170
g/mol) on some characteristic properties of the TPES-CP was examined,
while the mass ratio of the hard and soft segments was kept constant (57/43)
[22]. The weight fractions of PBT segments in the poly(ester-siloxane)s were
Thermoplastic elastomers based on siloxane prepolymers 35

Scheme 1. Molecular structure of the prepolymers that were used as the soft segments
in thermoplastic poly(ester-siloxane)s and poly(ester-ether-siloxane)s

O O
C C O CH2 O
4
SOFT SEGMENT

p q n

Scheme 2. Molecular structure of the synthesized copolymers based on hard PBT

segments and different siloxane-based soft segments

in the range from 5 9 to 63 % and the average lengths of the PBT

segments lay between 3.8 and 16.9, calculated on 1 mole of the soft
segment, indicating an increase in the length of the hard segments with
increasing length of the soft poly(dimethylsiloxane) segments. As a
36 Vesna V. Antić et al.

consequence of the increase in the length of the hard PBT segments, the
melting temperature, the enthalpy of melting and the hardness of the
poly(ester-siloxane)s increased. The degree of crystallinity calculated from
DSC data was in the range from 18.5 to 22.6 %, while the degree of
crystallinity from WAXS data was from 37 to 40 %. The glass transition
temperatures of the poly(ester-siloxane)s increased with decreasing PDMS
segment length, which indicates that the amorphous domains are a mixture of
PDMS and non-crystallized PBT segments [22]. Further investigations were
related to the investigation of the effect of the mass ratio of hard and soft
segments, with a constant length of the carboxypropyl-PDMS prepolymers
(1030 g/mol) on some properties of the obtained thermoplastic poly(ester-
siloxane)s (Table 1) [23]. The mass fraction of PBT segments in poly(ester-
siloxane)s, calculated from their 1H NMR spectra, were in the range 39 to 76
%, while the average degree of the polymerization of the PBT segments
increased from 3.1 to 15.4, with respect to 1 mol of soft segments. The
inherent viscosity of the copolymers increased from 0.35 to 0.45 dl g-1, as the
molar mass of the TPES increased from 11500 to 35000 g mol-1. It appeared
that there was a pronounced molar mass maximum when the PBT content of
the copolymers was approximately 60 mass %, whereby all the samples were
considerably inhomogeneous with respect to the distribution of the lengths of
the hard segments. Extraction with chloroform confirmed the multiblock
structure of both the soluble and insoluble fractions.

Analysis of the homogeneity of the synthesized TPESs and

TPEESs
All the samples of poly(ester-siloxane)s based on PDMS-OH or PDMS-
CP prepolymers exhibited considerable inhomogeneity with respect to the
distribution of the lengths of the hard segments. Due to the high
incompatibility of the employed extremely non-polar siloxane prepolymers
with the polar reactants, DMT and BD, phase separation occurred during the
reaction in the melt. It was observed that the PDMS prepolymers floated to
the surface of the reaction mixtures when the stirring was stopped during the
first, transesterification step. Hence, it was obvious that the reaction mixture
was not homogeneous. As a consequence, the incorporation of
dicarboxypropyl- and disilanol-terminated PDMS into the polar poly(butylene
terephthalate) chains resulted in rather inhomogeneous TPES copolymers.
The effectiveness of the incorporation of PDMS prepolymers into the
copolymer chains was examined by Soxhlet extraction with chloroform. It is
well known that PBT homopolymer is insoluble, while the PDMS
prepolymers are soluble in chloroform. The obtained results showed that all
TPES-OH and TPES-CP samples were comprised of a soluble, as well as of an
Thermoplastic elastomers based on siloxane prepolymers 37

insoluble fraction (Table 1). The TPES-OH samples lost 6-40 %, while the
TPES-CP samples lost 19–42 % during extraction. The content of the soluble
fraction increased with increasing mass fraction of soft segments in both the
TPES-OH and TPES-CP series, however the increase was more pronounced in
the first series (Fig. 1A). This meant that the amount of soluble fraction was
higher in the TPES-OH in comparison to the TPES-CP series, at the same
hard to soft segments ratio.
The composition and structure of the soluble and insoluble fractions were
investigated by 1H NMR spectroscopy. The spectra of both fractions contained
signals of aromatic protons from the PBT segments, as well as signals of the
Si–CH3 protons from the PDMS segments. The spectra also showed that the
extracted and insoluble fractions differed in both their composition and structure,
containing considerably different amounts of PDMS and PBT segments. The
mass fraction of soft segments was significantly larger in the soluble than in
insoluble fractions in both TPES-OH and TPES-CP series (Table 1). The
calculated value of p (the average degree of butylene terephthalate units in the
hard segments, Scheme 2) was very small in the soluble fractions in both series
(psol = 1.0–2.9). In the insoluble fractions, p was much higher, especially for the
TPES-OH series (pinsol = 63–300 for TPES-OHs and pinsol = 4–32 for TPES-
CPs, Table 1). It can be concluded that both the extracted and insoluble fractions
have a segmented (multiblock) structure, but with much more shorter PBT
blocks in the soluble than in the insoluble fractions. Based on these results, it is
obvious that the TPES-OH samples were more inhomogeneous regarding their
structure and composition in comparison with the PDMS-CP samples. It seems
that the PDMS-CP prepolymers had better miscibility with DMT and BD than
the PDMS-OH ones, due to the presence of polar carboxyl-end groups.
In order to avoid or reduce phase separation during the synthesis of TPES-
OH and TPES-CP, hydroxyl-terminated triblock prepolymers of the ABA type,
with hydrophilic terminal blocks, i.e., ethylene oxide (EO), poly(propylene
oxide) (PPO) or poly(caprolactone) (PCL) and with central PDMS block, were
used in further investigations (Scheme 1). It was expected that the terminal EO,
PPO or PCL blocks would serve as a compatibilizer between the extremely
non-polar PDMS and the polar DMT and BD. The results of solubility and
extraction in chloroform, as well as analysis of the 1H NMR spectra of the
obtained fractions showed that the presence of ether chains, either EO or PPO,
did not improve the homogeneity of the prepared poly(ester-ether-siloxane)s, in
comparison with the TPES-OH and TPES-CP copolymers. The TPEES
samples from both series (TPEES-EO and TPEES-PPO) were partially soluble
in chloroform, as well as the previously synthesized TPES–OH and TPES–CP
samples. The compositions of the chloroform soluble and insoluble fractions
of the TPEES samples are also presented in Table 1.
Table 1. Inherent viscosities (ηinh) and 1H NMR analysis of the chloroform soluble and insoluble fractions of some of the TPES
38

and TPEES samples.

Vesna V. Antić et al.
Thermoplastic elastomers based on siloxane prepolymers 39

Figure 1. Change in the content of the soluble fraction with changing mass fraction of
soft segments for the poly(ester-siloxane)s based on PDMS-OH and PDMS-CP
prepolymers (A) and the poly(ester-ether-siloxane)s based on EO-PDMS-EO and
PPO-PDMS-PPO prepolymers (B).

The TPEES-EO samples lost 3–56 mass % during extraction. The soluble
fractions of the TPEES-EO samples contained 81–86 mass % of soft
segments, while the insoluble ones contained 4–24 mass %. It can be
concluded that the length of the EO block (only 1 repeating unit) was too
short to be an efficient compatibilizer between PBT and PDMS, in spite of
the high solubility parameter of poly(ethylene oxide) [δPEO = 20.2 (J/cm3)1/2]
[5], which is close to the solubility parameter of PBT [δPBT = 23.0 (J/cm3)1/2]
[6].
The TPEES-PPO samples lost 39–60 mass % during extraction. The
sample TPEES-PPO2, with a mass fraction of PBT of 52.8 %, lost 43 %
during extraction, while the sample TPEES-EO5, with a very similar
content of the hard segment (53.4 mass %), but with shorter soft segments,
lost 34 % during extraction. This result indicates a relationship between the
length of the soft segments and the amount of soluble fraction: the longer
the soft segments, the higher is the amount of extracted fraction. The
relationship between the mass fraction of soft segments and amount of the
soluble fraction for the series TPEES-EO and TPEES-PPO is presented in
Fig. 1B.
The soluble fractions of the TPEES-PPO samples contained 85–89 mass
% of soft segments, while the insoluble ones contained 19–28 mass %. In the
case of the TPES-PPO copolymers, it can be concluded that compatibilizing
effect between PBT and PDMS was not achieved, because of the rather low
solubility parameter of PPO [δPPO = 15.4 (J/cm3)1/2] [6, 30], which is very
similar to that of PDMS [δPDMS = 15 (J/cm3)1/2] [3].
40 Vesna V. Antić et al.

The calculated values of psol for the samples of both TPEES series were
very small (psol =1.0-2.4) and similar to the psol of the previous TPES-OH and
TPES-CP series. The calculated value of pinsol was much higher in the
TPEES-PPO series than in the TPEES-EO series at a similar PBT content
(pinsol was 62 for TPEES-PPO2 and 18 for TPEES-EO5). This result shows
that the length of the PBT segments in the insoluble fraction is directly
related to the length of the prepolymer used, at a fixed mass ratio of hard-to-
soft segments.
The relationships between the content of PBT segments in the
copolymers and the length of the hard segment in the insoluble fraction are
presented in Fig. 2. It is obvious that increasing the content of PBT leads to
an increase of pinsol. The longest hard segments were founded in the insoluble
fractions of the TPES-OH series. This indicates that the prepolymer most
immiscible with PBT within the prepolymers used in this work was PDMS-
OH. At a fixed PBT content, the increase of the length of pinsol in the different
series was as follows: TPEES-PPO > TPEES-EO > TPES-CP (Fig. 2). The
differences in pinsol for TPEES-EO and TPES-CP were not very pronounced,
probably because of the similar length of the soft segments (1200 and 1030
g/mol, respectively). The values of pinsol in the TPEES-PPO series were
higher, probably as a consequence of the much longer soft segment (2930
g/mol).
The series of poly(ester-siloxane)s based on PBT and poly(caprolactone)-
poly(dimethylsiloxane)-poly(caprolactone), TPES-PCL, with hard-to-soft
segment ratios in the range from 74/26 to 51/49, were completely soluble in
chloroform, which enabled their molar masses to be determined by gel-
permeation chromatography. The chromatograms showed the presence of
only one peak, the shape of which corresponded to a typical high-molecular
weight product of step-growth polymerization. The values of the number
average molar masses, M n , the weight average molar masses, M w , the
polydispersity index, M w / M n and of the molar masses which corresponded
to the maximum of the peak, M peak are given in Table 2. The values of the
inherent viscosities of the TPES-PCLs and of the number of repeating units
within the hard segments are also given in Table 2. The values of M n were
in the range from about 20000 to almost 50000 g/mol. It is obvious that the
presence of the longer (18 repeating units), polar poly(caprolactone) blocks
[δPCL = 20.0 (J/cm3)]1/2] [31, 32] played a significant role in the improvement
of the miscibility of the prepolymer with the polar reactants and PBT. The
reaction mixture was homogeneous, as were the synthesized copolymers with
respect to their structure and composition.
Thermoplastic elastomers based on siloxane prepolymers 41

Figure 2. Change in the length of the hard segment in the insoluble fraction (pinsol)
with changing mass fraction of PBT segments for the synthesized poly(ester-
siloxane)s and poly(ester-ether-siloxane)s.

Table 2. Inherent viscosities (ηinh), 1H NMR and GPC analysis of the TPES-PCL
samples, based on PCL-PDMS-PCL prepolymer ( M nPCL − PDMS − PCL = 6100 g/mol).

PBT
ηinh
M peak
Sample Soft segment p Mn Mw Mw
(NMR) (dl/g) (g/mol) (g/mol)
mass % mass % Mn
(NMR) (g/mol)

TPES-PCL1 70/30 74/26 80 0.52 22470 43200 1.9 36700

TPES-PCL2 60/40 68/32 59 0.65 21170 45160 2.1 39480
TPES-PCL2 55/45 63/37 48 0.62 22540 45830 2.0 39480
TPES-PCL4 50/50 59/41 41 0.60 26610 49850 1.9 42500
TPES-PCL5 40/60 51/49 30 0.89 49340 91890 1.9 83950

DSC analysis of the TPESs and TPEESs

The synthesized TPES and TPEES were semi-crystalline polymers. The
melting temperatures (Tm) of the hard segments were observed by DSC. The
DSC measurements were performed between 50 and 250 °C to determined
the melting temperatures (Tm), the enthalpy of melting (∆Hm) and the degree
of crystallinity (wc) of the TPES and TPEES samples.
The values of Tm of the synthesized copolymers were in the following
ranges: 224-226 °C for TPES-OH; 214-223 °C for TPEES-EO; 208-218 °C
42 Vesna V. Antić et al.

for TPES-CP; 175-181 °C for TPEES-PPO and 103-196 °C for TPES-PCL. It

was obvious that the copolymers from the different series, with the same
mass fraction of PBT segments, have different melting temperatures in the
previously given order, as is presented in Fig. 3. From Fig. 3, it can also be
seen that with increasing mass fraction of PBT segments, the melting
temperatures mostly shifted to higher values. This phenomenon was the most
pronounced in the TPES-PCL series.
The enthalpies of melting were calculated from the corresponding
thermograms. The total degree of crystallinity, i.e., the mass fraction of
crystallities in the TPES and TPEES copolymers, were calculated from the
determined ∆Hm using the equation:

wc = ∆Hm / ∆Hmθ

where ∆Hmθ = 144.5 J/g is the enthalpy of melting of perfectly crystalline

PBT homopolymer [6].
The degree of crystallinity of the TPES and TPEES samples increased
with increasing mass fraction of the hard PBT segments in all the
investigated series, as can be seen in Fig. 4. Also, the copolymers from the
TPES-OH, TPES-CP and TPEES-PPO series have the highest degrees of
crystallinity at a fixed content of PBT (17-28, 11-23 and 10-17 %,
respectively). The trend of changing wc with mass fraction of PBT in the
copolymer was almost the same in all of these series. The samples from the
TPEES-EO series had a somewhat lower wc (3-28 %). The samples from the
TPES-PCL series (3-15 %) had the lowest degrees of crystallinity. This can
be explained by the high miscibility of PCL-PDMS-PCL prepolymer with
PBT, which leads to poor phase segregation of soft and hard segments in the
TPES-PCL copolymer, and also to the obstruction of the crystallization of the
PBT segments.
The ratio of the total degree of crystallinity and the determined mass
fraction of PBT segments (1H NMR) gave the mass fraction of hard
segments which were incorporated into the crystallites, wcPBT. The degrees of
crystallinity, wcPBT, were in the range 28 to 31 % for the synthesized TPES
and in the range 27 to 30 % for the TPEES-EO and TPEES-PPO. This means
that less than 30 mass % of the PBT segments in all the TPES and TPEES
samples crystallized. These results show that not all of the hard segments in
these segmented copolymers could crystallize completely due to their partial
incorporation into the amorphous phase. The degree of crystallinity of PBT
homopolymer was wc = wcPBT = 35.7 %.
Thermoplastic elastomers based on siloxane prepolymers 43

Figure 3. Change in the melting temperature (Tm) measured by DSC with changing
mass fraction of PBT segments for the synthesized poly(ester-siloxane)s and
poly(ester-ether-siloxane)s.

Figure 4. Change in the degree of crystallinity (wc) measured by DSC with changing
mass fraction of PBT segments for the synthesized poly(ester-siloxane)s and
poly(ester-ether-siloxane)s.

PBT homopolymer is a fast-crystallizing polymer. By comparing the

supercooling, i.e., the difference between melting and crystallization
temperature, it is possible to analyze the rate of crystallization of different
segmented copolymers. PBT has a supercooling of 32 oC. Supercooling of the
hard segments, ∆Th = Tm - Tc , of the poly(ester-siloxane)s and poly(ester-
44 Vesna V. Antić et al.

ether-siloxane)s was in the range from 38 to 45 oC, respectively, indicating

that the rate of crystallization of the copolymers TPES and TPEES was lower
than that of PBT, due to the presence of the soft polysiloxane segments. The
results show that the crystallization rates of the TPES and TPEES were
dependent both on structure and composition in the examined range.
Poly(ester-ether-siloxane)s, TPEES-PPO, exhibited two glass transition
temperatures. The glass transition temperatures of the amorphous PDMS
phase, TgPDMS, were between -121 and -124 oC, which are very close to that of
PDMS homopolymer, i.e., -123 oC. The glass transition temperatures of the
amorphous PPO phase, TgPPO, decreased from -21 to -43 oC with increasing
content of soft segments in the copolymers. PPO homopolymer has a glass
transition temperature of -75 oC, which is lower than those of the TPEESs,
and indicates that the amorphous fraction of the hard PBT segments was
mixed with PPO-PDMS-PPO segments.

Thermal stability of the TPESs and TPEESs

The results of thermogravimetric analysis under a nitrogen atmosphere
of the samples from different series, but with very similar content of PBT
segments (about 60 mass %), are given in Table 3 and shown in Figure 5.
The thermal stability and degradation behavior of the copolymers was
compared to the behavior of PBT homopolymer, synthesized in the same
way and stabilized with the same heat stabilizer [21-23]. It can be seen that
all copolymers, as well as PBT homopolymer, with exception of TPES-CP3
sample, commenced to degrade above 360 °C (Table 3). It seems that the
thermal stabilities of the TPES-OH, TPEES-EO, TPEES-PPO and TPES-
PCL copolymers were somewhat higher in comparison to that of the PBT
homopolymer. The thermal stability of the TPES-CP3 sample was lower
than those of all the other copolymers and the PBT homopolymer (Fig. 5A).
These results are in a agreement with the fact that the thermal stability of
the poly(ester-siloxane)s TPES-CPs decreased slightly with increasing
concentration of ester-bonds between the hard and soft segments, which are
the weakest bonds in the copolymer chains [23]. From Fig. 5B, it can be
seen that the temperatures of the maximal rate of degradation of the
copolymers were higher than the corresponding value for PBT
homopolymer. This means that when the degradation of the PBT
homopolymers starts, it proceeds faster than the degradation of the
copolymers. The residual masses were between 6.0 and 10.9 % at 450 °C,
originating probably from the PBT fraction, since the PDMS chains
degrade through depolymerization under a nitrogen atmosphere, with the
formation of cyclosiloxanes [4].
Thermoplastic elastomers based on siloxane prepolymers 45

Figure 5. TGA (A) and DTGA (B) curves for the TPES-CP5, TPEES-EO4, TPEES-
PPO1 and PBT homopolymer under a nitrogen atmosphere.
Table 3. Thermal gravimetric analysis data of some TPESs and TPEESs samples and
PBT homopolymer under a nitrogen atmosphere.

T for maximal rate of Residue

T for 5 % mass T for 50 %
Sample degradation (oC) at 450 oC
loss (oC) mass loss (oC)

PBT 361 389 389 10.3

TPES-OH5 364 403 407 6.0
TPES-CP3 343 389 387/398 6.0
TPEES-EO4 362 402 385/405/407 9.4
TPEES-PPO1 365 409 389/400/408 6.8
TPES-PCL4 367 404 394/407 10.9

Thermogravimetric analysis of the synthesized TPES and TPEES in

oxygen gave more pronounced differences between the samples, including
that of the PBT homopolymer. The thermo-oxidative stability of the
copolymers decreased with decreasing PBT content. Under a thermo-
oxidative atmosphere, the degradation of the PDMS chains or segments
46 Vesna V. Antić et al.

commences with the formation of peroxy structures in the side-chains, which

leads to the occurrence of different free radical reactions and results in the
formation of gaseous silicon compounds, CO, CO2, H2, H2O, HCHO and
HCOOH, leaving as a residue SiO2 [4]. Therefore, the residues at 500 oC in
oxygen for TPES and TPEESs were higher compared to PBT, due to the
increased amount of SiO2 formed.

Conclusions
Thermoplastic elastomers with hard segments based on poly(butylene
terephthalate) (PBT) and soft segment based on: a) α,ω-dicarboxypropyl-
poly(dimethylsiloxane)s (PDMS-CP); b) α,ω-disilanol-
poly(dimethylsiloxane) (PDMS-OH); c) α,ω-dihydroxy-ethylene oxide-
poly(dimethylsiloxane)-ethylene oxide (EO-PDMS-EO); d) α,ω-dihydroxy-
poly(propylene oxide-dimethylsiloxane-propylene oxide) (PPO-PDMS-PPO)
and e) α,ω-dihydroxy-poly(caprolactone-dimethylsiloxane-caprolactone)
(PCL-PDMS-PCL) were synthesized by two-step transesterification in the
melt. The obtained poly(ester–siloxane)s based on PDMS-OH (TPES-OH)
and PDMS-CP (TPES-CP) and poly(ester–ether–siloxane)s based on EO-
PDMS–EO (TPEES-EO) and PPO-PDMS–PPO (TPEES-PPO) were rather
inhomogeneous. After extraction with chloroform, soluble and insoluble
fractions of different structure and composition were obtained. Both the
soluble and insoluble fractions had multiblock structures. Due to the presence
of long, polar PCL sequences, the miscibility of the PCL-PDMS–PCL
prepolymer with the polar monomers in the reaction mixture was
significantly improved, in comparison with all the other examined systems.
As a result, the obtained PCL-PDMS–PCL based copolymers (TPES-PCL)
were structurally and compositionally homogeneous and completely soluble
in chloroform. The semi-crystalline nature of the poly(ester–siloxane)s and
poly(ester–ether–siloxane)s was confirmed by DSC analysis. With increasing
mass fraction of hard PBT segments, the melting temperature and the degree
of crystallinity of the TPES and TPEES increased. Copolymers from the
TPES-OH, TPES-CP and TPEES-PPO series had the highest degrees of
crystallinity. Copolymers from TPES-PCL series had the lowest degrees of
crystallinity. This was a consequence of the increased miscibility of PCL-
PDMS-PCL with PBT, which on the other hand led to reduced crystallization
of the hard segments in the copolymers. The thermal stability of the
copolymers was somewhat higher than that of the PBT homopolymer, with
exception of the TPES-CP samples, which were less stable due to the
presence of ester-bonds between the hard and soft segments, which are the
weakest bonds in copolymer chains.
Thermoplastic elastomers based on siloxane prepolymers 47

Acknowledgement
This work was financially supported by the Ministry of Science of the
Republic of Serbia (Project No. 142023).

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