Article

Journal of Elastomers & Plastics

2014, Vol. 46(7) 594610
Polymerization kinetics The Author(s) 2013
Reprints and permissions:

of polyurethanes sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0095244313480981

containing trisilanol jep.sagepub.com

isooctyl polyhedral
oligomeric
silsesquioxane
Rudinei Fiorio1,2, Vincius Pistor2, Ademir Jose Zattera3
and Cesar Liberato Petzhold2

Abstract
Two polyurethane model compounds obtained from 4,40 -diphenylmethane diisocyanate
(MDI) and 1,4-butanediol (BDO) or MDI and trisilanol isooctyl polyhedral oligomeric
silsesquioxane (POSS) were synthesized and characterized by Fourier transform infrared
spectroscopy and thermogravimetric analysis. Moreover, polymerization kinetics of the
samples obtained from an isocyanate-terminated prepolymer and BDO containing 0,
0.23, 0.57, 1.14 and 2.28 wt% of POSS were studied from oscillatory rheometry and dif-
ferential scanning calorimetry. A higher thermal stability was observed for MDI POSS
when compared with MDI BDO compound. The addition of 1.14 and 2.28 wt% of
POSS increased the activation energy of polymerization. The polymerization mechan-
isms observed were nucleation and growth (A2) at the beginning of synthesis and diffu-
sion controlled (Dn) at the last stage of conversion.

Keywords
Polyurethane, POSS, polymerization, kinetics, activation energy, mechanism

1
Polymer Laboratory, Instituto Federal de Eduacao, Ciencia e Tecnologia do Rio Grande do Sul (IFRS), Caxias
do Sul, Rio Grande do Sul, Brazil
2
Organic Chemistry Department, PGCIMAT, Universidade Federal do Rio Grande do Sul (UFRGS), Porto
Alegre, Rio Grande do Sul, Brazil
3
Polymer Laboratory, Universidade de Caxias do Sul (UCS), Caxias do Sul, Rio Grande do Sul, Brazil

Corresponding author:
Rudinei Fiorio, Polymer Laboratory, Instituto Federal de Eduacao, Ciencia e Tecnologia do Rio Grande do Sul
(IFRS), Mario de Boni, 2250, Bairro Floresta, Caxias do Sul 95012-580, Rio Grande do Sul, Brazil.
Email: rudinei.fiorio@caxias.ifrs.edu.br
Fiorio et al. 595

Introduction
Polyurethanes (PUs) usually are block copolymers whose blocks have different physical
and chemical characteristics and are typically immiscible. One block has flexibility at
room temperature and composes a rubber phase, and the other is hard until temperatures
near 100 C and constitutes a rigid phase.
Thermoplastic PUs (TPUs) are characterized by linear chains and absence of cross-
links. In these polymers, the rubber phase gives flexibility, while the rigid phase acts
as physical cross-linking, combining elasticity, typical of vulcanized elastomers, with
the processability of thermoplastic polymers.
Several studies were conducted in order to evaluate the kinetics of formation of PUs.
Two reaction pathways are used as the basis for the kinetic equation, a reaction catalyzed
by a Lewis acid and a reaction catalyzed by a Lewis base.1 The PU formation reactions
are always considered catalyzed, since the alcohol functional group itself acts as a
Lewis base catalyst type.1 The mechanism of catalysis by Lewis base is represented in
Figure 1 (the alcohol group acts as a base catalyst).
Regarding the kinetics of polymerization of the PU, the kinetics adopts a second-order
behavior upto 50% conversion; however, in higher conversions, different effects may
occur due to a decrease in the reaction rate. An acceleration of the reaction is mainly due
to a catalytic effect of urethane bonds. The reduction in the reaction rate is related to the
difficulty in diffusion of the reactants, especially in mass polymerizations.1,2
Composite materials formed by the combination of inorganic compounds and organic
polymers are attractive for the purpose of creating high-performance polymeric materi-
als. The combination at the molecular level of two different components can lead to the
formation of new composite materials, known as organicinorganic hybrid materials.3
Polyhedral oligomeric silsesquioxanes (POSSs) are structurally well-defined molecules,
generally formed by the hydrolysis and condensation of trialkoxy- or trichlorosilanes.4 POSS
molecules are usually closed cage-like compounds.5,6 These POSSs have an inorganic core
containing silicon atoms and are surrounded by organic groups. Because of its hybrid nature
and size (nanoscale), the POSS is a promising material for obtaining nanocomposites.68
POSS molecules can be incorporated as building blocks into other polymers to form
hybrid organicinorganic copolymers with different miscibility/compatibility and elas-
ticity properties.9
In this work, PU models derived from 4,40 -diphenylmethane diisocyanate (MDI) and 1,4-
butanediol (BDO) or MDI and trisilanol isooctyl POSS were synthesized in solution and
characterized by thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR)
spectroscopy. In addition, the kinetics and mechanism of the synthesis of TPUs containing
POSS were evaluated by differential scanning calorimetry (DSC) and oscillatory rheometry.

Experimental
Materials
Model compounds were synthesized in dimethylformamide (DMF, Vetec, Brazil), using the
MDI (BASF, Brazil) and trisilanol isooctyl POSS (Hybrid Plastics, USA; Figure 2),
596 Journal of Elastomers & Plastics 46(7)

Figure 1. Synthesis mechanism of polyurethane with a Lewis base catalysis.1

Figure 2. Chemical structure of the trisilanol isooctyl POSS (hydrogen atoms bonded to carbon
atoms were omitted). POSS: polyhedral oligomeric silsesquioxane.

obtaining the polymer MDI POSS. Another model compound was obtained by solution
polymerization of MDI and BDO (MCassab, Brazil), obtaining the polymer MDI BDO.
The materials used for the evaluation of polymerization kinetics were a prepolymer
containing 18wt% of free isocyanate (Urecom 185, Coim, Brazil), BDO and the trisi-
lanol isooctyl POSS.
Fiorio et al. 597

Table 1. Samples of TPUs with different POSS contents.

Sample POSS content (wt%)

TPU-BDO 0.00
0.23% POSS 0.23
0.57% POSS 0.57
1.14% POSS 1.14
2.28% POSS 2.28

TPU: thermoplastic polyurethane; POSS: polyhedral oligomeric silsesquioxane; BDO: 1,4-butanediol.

Methods
Synthesis in solution. The model compounds (MDI POSS and MDI BDO) were
synthesized in DMF solution, in excess of hydroxyl groups (molar ratio 1.25/1, OH/
NCO). The MDI was preheated at 50 C in a conventional oven and then 3 g of MDI was
added to a 250-mL flask containing 100 mL of DMF. Subsequently, the POSS (5.921 g)
or BDO (0.675 g) was added. The system was kept under vacuum (650 mm Hg) with
mechanical stirring (600 r/min) at 75 + 2 C for 60 min. After synthesis, each system
was stored in sealed flasks and kept for 24 h at room temperature. The solvent was
extracted by drying at 70 C for 72 h in a conventional oven and subsequently for 72 h
in a vacuum oven, at the same temperature. The polymers of the obtained model com-
pounds were characterized by FTIR spectroscopy and TGA.

Preparation of polymers for evaluation of polymerization kinetics. To study the polymerization

kinetics, samples were prepared from the prepolymer with 18 wt% of free isocyanate and
BDO, containing different POSS contents (Table 1). All the components were condi-
tioned at 23 C for at least 48 h in closed flasks before use. Approximately 10 g of each
sample was prepared and mixed manually with the aid of a glass rod for 60 s. The
isocyanate index was kept close to 98 for all the samples. At the end of the mixing step, a
portion of each sample was transferred to the oscillatory rheometer or DSC pan for
analysis.
The isocyanate content of MDI and prepolymer was determined by the dibutylamine
method.10

FTIR spectroscopy. FTIR analysis (Nicolet iS10, Thermo Scientific, USA) was performed
in an attenuated total reflection mode. Samples were analyzed after the drying process.

Thermogravimetric analysis. TGA (TGA50Shimadzu, Japan) was realized in a nitrogen

atmosphere (50 ml min1) with approximately 20 mg of each sample, at a rate of
10 C min1, from 25 to 730 C.

Polymerization kinetics studied by oscillatory rheometry. The polymerization kinetics of the

samples (Table 1) were studied from isothermal experiments in an oscillatory rheometer
(Physica MCR 101, Anton Paar, Austria) at temperatures of 25, 30, 40 and 50 C. An
598 Journal of Elastomers & Plastics 46(7)

oscillation frequency of 1 Hz, shear stress of 1 Pa, parallel plates with a diameter of
25 mm, gap between plates of 0.5 mm and a nitrogen atmosphere (1 m3 h1) were used.
The isocyanate index was kept at 98 for all the samples. The activation energies of
polymerization were obtained using the Arrhenius equation (equation (1))
Ea 1
ln k ln A   1
R T
where k is a kinetic constant, A is the pre-exponential factor, Ea is the activation energy,
R is the gas constant and T is the absolute temperature. Assuming k as the time at which
the storage modulus, G0 , equals the loss modulus, G00 , a plot of lnk versus 1/T gives a
straight line with slope equals to Ea/R.1113

Polymerization kinetics studied by DSC. Polymerization kinetics of the samples were studied
using a DSC 50 (Shimadzu), at the heating rates of 5, 10, 20 and 30 C min1, under a
nitrogen atmosphere (50 mL min1), using samples of approximately 6 mg. The iso-
cyanate index was kept at 98 for all the samples.
The activation energy of polymerization was obtained by the FlynnWallOzawa
(FWO) method.1418
From DSC data, the FWO method uses the enthalpy of reaction to determine the
conversion (a) as a function of temperature, at different heating rates, as described in
equation (2).14,17 The conversion (a) was determined from the area of the exothermic
peak observed in DSC thermograms.
 
AEa Ea
logF log  loggaT  2:315  0:4567 2
R RT
where g(a(T)) is a conversion function, Ea is the activation energy, R is the gas constant,
A is a pre-exponential factor, F is the heating rate and T is the absolute temperature.
From the slope of log(F) versus 1/T at determined conversion value, it is possible to
determine the apparent activation energy.1518 The activation energy calculated using the
FWO method is called apparent activation energy, because it is the sum value of activa-
tion energies of chemical reactions and physical processes in thermal degradation.15
The mechanism of a solid-state reaction can be determined by applying the Criado
et al. method,19 using a function Z(a) (equation (3)):
 
da Ea Ea
Z a exp Q x 3
dT R RT
Ea
where x RT and Q(x) is an approximation of the temperature integral that cannot be
expressed in a simple analytical form.20 In this study, the fourth rational expression for
Q(x), proposed by Senum and Yang, gives errors lower than 105% for x > 20 was used
(equation (4)):21,22
 
ex x3 18x2 86x 96
Q x 4
x x4 20x3 120x2 240x 120
Fiorio et al. 599

Table 2. Algebraic expressions for f(a) and g(a) for the most frequently used mechanisms of solid-
state processes.

Mechanism f(a) g(a)

A2, nucleation and growth (Avrami  ln1  1=2 21   ln1  

equation (1))
A3, nucleation and growth (Avrami  ln1  1=3 31   ln1  2=3
equation (2))
A4, nucleation and growth (Avrami  ln1  1=4 41   ln1  3=4
equation (3))
R1, phase boundary-controlled a 1
reaction (one-dimensional
movement)
R2, phase boundary-controlled 1  1  1=2 21  1=2
reaction (contracting area)
R3, phase boundary-controlled 1  1  1=3 31  2=3
reaction (contracting volume)

D1, one-dimensional diffusion a2 1
1
2
D2, two-dimensional diffusion (Valensi 1   ln1    ln1  1
equation)

D3, three-dimensional diffusion (Jan- 1  1  1=3 2 3
2 1  1  1=3 1 1  2=3
der equation)


D4, three-dimensional diffusion 1  23   1  2=3 3
2 1  1  1=3 1
(GinstlingBrounshtein equation)
F1, random nucleation with one  ln1   1  
nucleus on the individual particle
F2, random nucleation with two nuclei 1=1   1  2
on the individual particle

F3, random nucleation with three 1=1  2 1
2 1  3
nuclei on the individual particle

Theoretical master curves that represent differential and integral expressions (f(a)
and g(a), respectively) can be obtained from equation (5), using the algebraic
expressions shown in Table 2.23
Z a f ag a 5
By comparing the experimental results (obtained from equation (3)) with the
theoretical master curves (equation (5)) in a plot of Z(a) versus a, the mechanism of
polymerization reaction can be identified.

Results and discussion

Synthesis in solution
The free isocyanate contents of MDI and prepolymer were 32.9 and 17.7%,
respectively. These results were very close to the theoretical ones, and were used
600 Journal of Elastomers & Plastics 46(7)

MDI + BDO
Transmittance (a.u.)

MDI + POSS

4000 3500 3000 2500 2000 1500 1000

1
Wave number (cm )

Figure 3. FTIR spectra of MDI BDO and MDI POSS. MDI: 4,40 -diphenylmethane diisocya-
nate; BDO: 1,4-butanediol; POSS: polyhedral oligomeric silsesquioxane.

to determine the stoichiometry between NCO and OH groups of the reaction

systems.
It was observed that the reaction system containing POSS showed a second phase after
a few minutes of reaction, indicating a chemical reaction between POSS and MDI.
Reactions between isocyanate and silanol groups form silylurethanes and were observed
previously in the reactions of isocyanates with glasses and silicas.2428 Probably, the
polymer formed from MDI and POSS presented cross-linking, since the POSS used is tri-
functional and the polymer was insoluble in DMF. The system containing MDI BDO
showed no visible phase separation at any stage of the synthesis in solution.
Figure 3 shows the FTIR spectra of MDI BDO and MDI POSS samples, where it
was possible to observe the characteristic bands of PU at 3300 cm1 (NH), 1700 cm1
(amide I; axial deformation of CO) and 1540 cm1 (amide II, NH angular deforma-
tion).29,30 However, one can observe significant differences at 28002950 cm1 (CH
stretching) and at 1700, 15001550 and 1100 cm1 (ROR and SiO stretching)31 due
to differences in the chemical composition of each compound.
An increase in the absorption at 28002950 cm1 for the MDI POSS was observed
due to the greater amount of structures such as CHn (n 1, 2 or 3) related to the isooctyl
groups present in the POSS molecules. Upon replacing the BDO by POSS in model
compounds, the peak at 1700 cm1 (amide I) is shifted to about 1650 cm1. The
absorption at 1700 cm1 for MDI BDO indicates the presence of ordered hydrogen
bonding between urethane groups.32 The shift in the amide I absorption for lower wave
number for MDI POSS may be related to an increase in the amount of hydrogen
Fiorio et al. 601

1,4-Butanediol
100 Trisilanol isooctyl POSS
MDI + BDO
MDI + POSS

80
Mass (%)

60

40

20

0
0 100 200 300 400 500 600 700
Temperature (C)

Figure 4. TGA thermograms of chain extenders and model compounds. TGA: thermogravimetric
analysis.

bonding between silylurethane groups in this sample, since the silanol groups are very
close (at the vertices of the POSS open cage). Moreover, the great flexibility of the
SiO33 could cause a shift in the absorption of amide I and amide II groups, after the
reaction of silanol with isocyanate. The largest amount of SiO in the MDI POSS
compound explains the wider absorption observed at 1100 cm1 for this sample.
Figure 4 shows the TGA thermograms of chain extenders (BDO and POSS) and
polymers obtained from synthesis in solution. The BDO showed weight loss at the lowest
temperature due to the lower molecular weight of this sample. The MDI BDO polymer
showed weight loss at lower temperature as well as at higher residual mass than the
MDI POSS compound; this may be related to the absence of cross-linking in the sam-
ple MDI BDO as well as higher weight content of aromatic rings present in
MDI BDO, respectively.
The first stage of mass loss observed for the POSS (at approximately 200 C) may be
related to the degradation of silanol groups, while the second mass loss occurs due to the
degradation of isooctyl branches and SiO cage.
Figure 5 presents the results of the first derivative of weight loss (derivative ther-
mogravimetric analysis (DTG)) of the chain extenders and model compounds. It was
observed that the sample of MDI POSS shows two main stages of degradation,
associated with the initial degradation of segments derived from MDI followed by the
decomposition of structures derived from POSS, since the second DTG peak observed in
the MDI POSS sample showed the same temperature as observed for the DTG peak of
pure POSS. Moreover, the first peak of DTG for the sample MDI POSS is at a
602 Journal of Elastomers & Plastics 46(7)

DTG (a.u.)

1,4-Butanediol

Trisilanol isooctyl POSS

MDI + BDO

MDI + POSS

0 100 200 300 400 500 600 700

Temperature (C)

Figure 5. DTG curves of chain extenders and model compounds. DTG: derivative
thermogravimetric.

temperature higher than the peak observed for the MDI BDO, showing higher thermal
stability for the MDI POSS compound.

Polymerization kinetics studied by oscillatory rheometry

Figure 6 shows the results of storage modulus (G0 ) and loss modulus (G0 ) versus time for
the TPU-BDO sample synthesized in the oscillatory rheometer. The other samples
showed similar behavior. It was observed that the increase in synthesis temperature
increased the reaction rate, decreasing the time at which the modules stabilize. From Fig-
ure 6, the reaction times where G0 G00 were used to determine the activation energy
(Ea) of polymerization.
From Figure 7, the slopes obtained from linear fits of lntG0 G0 0 versus 1/T are
determined. The activation energy (Ea) of polymerization was determined using the
Arrhenius equation (equation (1)). The values of Ea of polymerization obtained from
oscillatory rheometer are listed in Table 3. The correlation coefficients (r) of linear fits
were close to unity.
It was observed that the incorporation of more than 0.57 wt% of POSS increased the
Ea of polymerization, due to a possible steric hindrance promoted by the presence of
polyhedral cages, and as well may be related to a retardant effect caused by POSS, since
it can modify the Lewis base catalysis due to restricted OH groups. Therefore, both
POSS dispersion and formation of POSS clusters can cause an increase in the Ea values.
Fiorio et al. 603

106

105

104
G, G (Pa)

103 TPU-BDO - G 25C

TPU-BDO - G 25C
TPU-BDO - G 30C
102
TPU-BDO - G 30C
TPU-BDO - G 40C
101 TPU-BDO - G 40C
TPU-BDO - G 50C
TPU-BDO - G 50C
100
0 500 1000 1500 2000 2500 3000 3500 4000
Time (S)

Figure 6. G0 and G00 versus time for the TPU-BDO sample synthesized in an oscillatory rhe-
ometer. BDO: 1,4-butanediol; TPU: thermoplastic polyurethane.

Polymerization kinetics studied by DSC

Figure 8 shows the DSC thermograms of the samples studied at a heating rate of
10 C min1. The polymerization reaction was exothermic, showing a peak close to 75 C
for samples analyzed at 10 C min1. The DSC thermograms of the samples performed at
heating rates of 5, 20 and 30 C min1 showed similar results.
From the thermograms of the samples synthesized in the DSC at different heating rates,
the conversion (a) of the polymerization process was obtained. Figure 9 shows the results
of a versus temperature for sample TPU-BDO; the other samples showed similar results.
Figure 10 presents the results of logF versus 1/T at different conversions (a) for the
TPU-BDO sample. The remaining samples showed similar behavior. The angular coef-
ficients obtained from linear fits at determined conversion values were used to evaluate
the activation energy (Ea) of polymerization in DSC (Figure 11 and Table 4). The sample
containing 2.28% of POSS was analyzed in duplicate (2.28% POSS 1 and 2.28% POSS
2). The correlation coefficients (r) of linear fits were close to unity.
It was observed that there was a significant variation between the values of Ea for the
samples containing 2.28 wt% of POSS. Therefore, one can state that practically there
was no change in the activation energy of polymerization with the incorporation of
POSS; there was only an increased trend in Ea. This behavior is related to the small
amount of POSS (until 2.28 wt%) used in this study.
In Figure 11, it was observed that all the samples had higher Ea values at the beginning of
the polymerization process and showed a decrease in Ea with the progression of conversion
upto a  0.5 due to the heat generated by the reaction and the catalytic effect of the urethane
604 Journal of Elastomers & Plastics 46(7)

8.2
TPU-BPO
8.0
0.23% POSS
7.8 0.57% POSS
7.6 1.14% POSS
2.28% POSS
7.4
Linear fit
7.2
In tG = G (S)

7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
3.110 3 3.110 3 3.210 3 3.210 3 3.310 3 3.310 3 3.410 3 3.410 3
1/T (K1)

Figure 7. lntG0 G0 0 versus 1/T for the TPU samples synthesized in oscillatory rheometer. TPU:
thermoplastic polyurethane.

Table 3. Ea of polymerization for the TPU samples synthesized in an oscillatory rheometer.

Sample Ea (kJ mol1) r

TPU-BDO 53.2 0.9993

0.23% POSS 51.5 0.9997
0.57% POSS 53.1 0.9989
1.14% POSS 61.7 0.9998
2.28% POSS 60.8 0.9997

Ea: activation energy; TPU: thermoplastic polyurethane; POSS: polyhedral oligomeric silsesquioxane; BDO: 1,4-
butanediol.

groups formed. Samples showed a trend of increasing Ea after a  0.5, due to restriction of
both movement and diffusion of molecules with the increase in system viscosity.1,2
Regardless of the variation observed between samples containing 2.28 wt% of
POSS, an increasing trend in Ea values was observed with increasing POSS content.
This behavior can be associated with the formation of POSS clusters or decreasing
molecular mobility of TPUs due to the presence of POSS. The formation of POSS
clusters can increase the Ea of polymerization, since silanol groups may remain una-
vailable to react with isocyanate groups and, consequently, modifying the polymerization
Fiorio et al. 605

0.4
TPU-BPO
0.23% POSS
0.3
0.57% POSS
1.14% POSS
0.2
2.28% POSS
Heat flux (W g1)

0.1

0.0

0.1

0.2
Endo

0.3

0 20 40 60 80 100 120 140 160 180 200 220

Temperature (C)

Figure 8. DSC thermograms of TPU samples studied (heating rate of 10 C min1). TPU: ther-
moplastic polyurethane; DSC: differential scanning calorimetry.

1.0 = 5 C min1
= 10 C min1
= 20 C min1
0.8 = 30 C min1
Conversion ()

0.6

0.4

0.2

0
0 25 50 75 100 125 150 175
Temperature (C)

Figure 9. Conversion (a) versus temperature for the TPU-BDO sample. TPU: thermoplastic
polyurethane; BDO: 1,4-butanediol.
606 Journal of Elastomers & Plastics 46(7)

1.0 0.05
0.1
0.2
1.4 0.3
0.4
0.5
0.6
1.2 0.7
0.8
Log

Linear fit
1.0

0.8

0.6

2.5510 3 2.7010 3 2.8510 3 3.0010 3 3.1510 3 3.3010 3

1/T (K1)

Figure 10. LogF versus 1/T at determined a values for the TPU-BDO sample. TPU: thermoplastic
polyurethane; BDO: 1,4-butanediol.

64
TPU-BDO
0.23% POSS
60 0.57% POSS
1.14% POSS
2.28% POSS 1
56 2.28% POSS 2
Ea (KJ mol )
1

52

48

44

40
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Conversion ()

Figure 11. Ea of polymerization for the TPU samples synthesized in DSC. DSC: differential
scanning calorimetry; TPU: thermoplastic polyurethane; Ea: activation energy.
 Table 4. Ea of polymerization for the TPU samples synthesized in DSC.

TPU-BDO 0.23% POSS 0.57% POSS 1.14% POSS 2.28% POSS 1 2.28% POSS 2
1 1 1 1 1
a Ea (kJ mol ) r Ea (kJ mol ) r Ea (kJ mol ) r Ea (kJ mol ) r Ea (kJ mol ) r Ea (kJ mol1) r

0.05 52.2 0.9893 51.6 0.9897 56.5 0.9835 52.3 0.9902 62.6 0.9954 56.8 0.9886
0.10 48.8 0.9902 49.3 0.9929 53.9 0.9875 49.8 0.9942 58.3 0.9972 54.8 0.9933
0.20 46.7 0.9915 47.6 0.9948 52.1 0.9892 47.8 0.9967 54.4 0.9986 52.2 0.9971
0.30 45.0 0.9928 46.9 0.9958 50.5 0.9891 46.4 0.9983 52.7 0.9992 50.9 0.9983
0.40 43.9 0.9920 46.3 0.9945 49.8 0.9892 45.9 0.9994 51.5 0.9990 49.9 0.9992
0.50 43.4 0.9914 46.3 0.9934 49.1 0.9918 45.3 0.9996 51.0 0.9993 49.6 0.9995
0.60 43.4 0.9925 46.5 0.9916 48.9 0.9927 45.4 0.9998 51.2 0.9989 50.2 0.9998
0.70 43.8 0.9940 47.9 0.9884 49.8 0.9937 46.1 0.9999 52.3 0.9981 51.5 0.9995
0.80 45.4 0.9933 52.0 0.9834 51.4 0.9942 47.3 0.9996 54.5 0.9964 54.3 0.9974

Ea: activation energy; TPU: thermoplastic polyurethane; POSS: polyhedral oligomeric silsesquioxane; BDO: 1,4-butanediol; DSC: differential scanning calorimetry.

607
608 Journal of Elastomers & Plastics 46(7)

0.5 TPU-BDO
0.23% POSS
0.57% POSS
0.4 1.14% POSS
2.28% POSS 1
2.28% POSS 2
A2
0.3
A3
Z ()

A4
R1
0.2 R2
R3
D1
0.1 D2
D3
D4
0.0 F1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 F3

Conversion ()

Figure 12. Experimental and theoretical Z(a) values as a function of a for TPU samples
synthesized in DSC. DSC: differential scanning calorimetry.

kinetics. Moreover, reducing the amount of hydroxyl groups decreases the Lewis base
catalytic effect. The incidence of high dispersion of POSS molecules can cause an
increase in the Ea due to the restriction imposed by POSS cages in the system.34
Figure 12 shows the experimental and theoretical Z(a) values versus conversion for
the samples synthesized in DSC. Comparing the Z(a) values, it was observed that the
polymerization mechanisms of all the samples start as nucleation and growth (A2) passes
by phase boundary-controlled reactions (uni-, bi- and tri-dimensional; R1, R2 and R3,
respectively) and random nucleation with one nucleus in the individual particle (F1), and
at a  0.8, the mechanisms were mainly diffusion controlled (bi- and tri-dimensional dif-
fusion; D2 and D3, respectively).20,23,35 The initial mechanisms observed (A2) were
related to the formation of oligomers and the final diffusional mechanisms (D2 and
D3) were associated with the increase in viscosity at elevated conversions.
Considering the variation in the experimental Z(a) values of the samples 2.28% POSS
1 and 2.28% POSS 2, one could state that the addition of POSS promotes no significant
change in the polymerization mechanism.

Conclusions
In this study, the influence of trisilanol isooctyl POSS on polymerization kinetics of
TPUs was evaluated. It was observed that POSS molecules chemically react with iso-
cyanate and POSS containing PU could be obtained. The presence of POSS modifies the
hydrogen bond interactions between urethane and other polar groups, dislocating
Fiorio et al. 609

absorption bands observed in the FTIR spectra. Also, an increase in thermal stability was
observed for the TPU POSS model compound.
The addition of POSS promoted an increased trend in activation energy of poly-
merization, related to steric hindrance or a retardant effect caused by POSS molecules.
Polymerization mechanisms started as nucleation and growth (A2) and changed to
phase boundary-controlled reactions (Rn) and random nucleation with one nucleus in the
individual particle (F1) and were mainly diffusion controlled (Dn) at the last stage of
conversion. Also, it was observed that the addition of POSS caused no significant mod-
ifications in polymerization mechanisms.

Funding
The authors would like to thank CNPq and FAPERGS (DINTER) by financial support.

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