d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041

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journal homepage: www.intl.elsevierhealth.com/journals/dema

Synthesis, characterization, shrinkage and curing kinetics

of a new low-shrinkage urethane dimethacrylate
monomer for dental applications

Mohammad Atai a,∗ , Mehdi Ahmadi b , Samal Babanzadeh a , David C. Watts c

a Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran
b Department of Chemistry, Faculty of Science, Mazandaran University, Iran
c Biomaterials Science Research Group, School of Dentistry and Photon Science Institute, The University of Manchester,

Manchester M15 6FH, UK

a r t i c l e i n f o a b s t r a c t

Article history: Objectives. The aim of the study was to synthesize and characterize an isophorone-based
Received 14 January 2007 urethane dimethacrylate (IP-UDMA) resin-monomer and to investigate its shrinkage and
Received in revised form curing kinetics.
13 March 2007 Methods. The IP-UDMA monomer was synthesized through the reaction of polyethylene
Accepted 14 March 2007 glycol 400 and isophorone diisocyanate followed by reacting with HEMA to terminate
it with methacrylate end groups. The reaction was followed using a standard back
titration method and FTIR spectroscopy. The final product was purified and character-
1
Keywords: ized using FTIR, H NMR, elemental analysis and refractive index measurement. The
Resin-monomers shrinkage-strain of the specimens photopolymerized at circa 700 mW/cm2 was measured
UDMA using the bonded-disk technique at 23, 35, and 45 ◦ C. Initial shrinkage-strain-rates were
Shrinkage-strain obtained by numerical differentiation of shrinkage-strain data with respect to time. Degree-
Curing kinetics of-conversion of the specimens was measured using FTIR spectroscopy. The thermal
curing kinetics of the monomer were also studied by differential scanning calorimetry
(DSC).
Results. The characterization methods confirmed the suggested reaction route and the
synthesized monomer. A low shrinkage-strain of about 4% was obtained for the new
monomer. The results showed that the shrinkage-strain-rate of the monomer followed
the autocatalytic model of Kamal and Sourour [Kamal MR, Sourour S. Kinetic and ther-
mal characterization of thermoset cure. Polym Eng Sci 1973;13(1):59–64], which is used to
describe the reaction kinetics of thermoset resins. The model parameters were calculated
by linearization of the equation.
Significance. The model prediction was in a good agreement with the experimental data.
The properties of the new monomer compare favorably with properties of the commercially
available resins.
© 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

∗
Corresponding author. Tel.: +98 21 44580085; fax: +98 21 44580023.
E-mail address: M.Atai@ippi.ac.ir (M. Atai).
0109-5641/$ – see front matter © 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2007.03.004
 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041
1. Introduction
A wide variety of the polyurethane structure blocks, i.e.
polyols, isocyanates, chain extenders and other modifying
ingredients, has enabled the design of materials for differ-
ent applications. Urethane di(meth)acrylates (UDMAs) are a
class of materials with two (meth)acrylate end groups which
enable them to be cured either thermally or through pho-
topolymerization processes [1–3]. The latter is of more interest
because of the ease of application and lower energy con-
sumption. UDMAs have been widely used in coatings [4–9],
adhesives [10,11], pultrusion processes [12], and dental mate-
rials [13–19]. The matrix phases of dental composites, which
are now widely used in restorative dentistry, are mostly
di(meth)acrylate monomers. Although some UDMAs have
been commercialized for dental applications [16], they still
have much promise to overcome the shortcomings of the
hitherto available resins. One of the major drawbacks, espe-
cially in dental restorative materials (dental composites) is
their polymerization shrinkage which may lead to marginal
gaps and secondary caries in the restored teeth. Shrinkage
is the result of matrix-phase polymerization of composites.
Numerous studies have been performed to reduce the poly-
merization shrinkage of the dental resins which have focused
mainly on the synthesis of new monomers with reduced
shrinkage [20–29]. But in spite of the extensive studies, poly-
merization shrinkage is still a major drawback in dental
resin-monomers.
In this study a new urethane dimethacrylate (UDMA)
was synthesized and characterized with the aim of reduc-
ing polymerization shrinkage. The shrinkage kinetic of the
monomer, which is very important in understanding the
phenomena, was also investigated. The autocatalytic model
of Kamal [30,31], which was adopted and modified by Atai
and Watts [32] to describe the photopolymerization shrink-
age kinetics of dental resin-monomers, was applied to study
the curing behavior of the new monomer. As the synthe-
sized UDMA may be used for other applications in which
the resins are thermally cured, the thermal curing kinet-
ics of the resin were also studied. The photopolymerization
and thermal curing kinetic parameters of the monomer were
determined.
2. Experimental
2.1. Materials
Isophorone diisocyanate (IPDI), polyethylene glycol (PEG)
with the molecular weight of 400 g/mol, 2-hydroxyethylethyl
methacrylate (HEMA), camphorquinone (CQ), and ben-
zoyl peroxide were purchased from Merck (Germany).
Tetrahydrofuran (THF) and N,N -dimethyl aminoethyl
methacrylate (DMAEMA) were obtained from Fluka (Ger-
many). 2,2-Bis-(2-hydroxy-3-methacryloxypropoxy) phenyl]
propane (Bis-GMA) and triethyleneglycol dimethacry-
late (TEGDMA) were kindly supplied by Röhm (Degussa
group, Germany). Other solvents were obtained from
Merck.
1031
2.2. Methods
2.2.1. Instrumental analysis
Completion of the monomer synthesis reaction and the degree
of photopolymerization conversion were determined using
FTIR spectroscopy (EQUINOX 55, Bruker, Germany) at a resolu-
tion of 4 cm−1 and 32 scans in the range of 4000–400 cm−1 . 1 H
NMR spectrum of the synthesized monomer was recorded in
deuterated acetone as solvent on an AVANCE 400 MHz spec-
trometer (Bruker, Germany). Elemental analysis was carried
out using VarioEL III (Elementar Analysensysteme, Germany)
and the refractive index of the IP-UDMA resin was measured
on a DR 5000 (A. Kruss Optronic, Germany).
Rheological behavior of the resins was determined using
a MCR 300 rheometer (Anton Paar GmbH, Austria) with par-
allel plate geometry and a separation of 0.5 mm between the
plates. A strain-sweep test (SST) was performed to find the
strain range in which the viscoelastic behavior of the resins
was linear. A frequency-sweep test (FST) was then carried
out in the frequency range of 0.01–100 rad/s. Thermal curing
kinetics of the resins were studied on a Pyris 1 differential
scanning calorimeter (Perkin-Elmer, USA) at 75, 85, and 95 ◦ C
isothermal modes for 40 min. To minimize the pre-curing of
the resins containing thermal initiator, a high-speed heating
rate of 200 ◦ C/min was applied to reach the isothermal tem-
peratures. In the thermally cured specimens 1 wt.% of benzoyl
peroxide was used as the initiator.
2.2.2. Synthesis and characterization of IP-UDMA
IPDI was distillated under reduced pressure, PEG was puri-
fied through azeotropic distillation with toluene, HEMA was
dried over 4 Å molecular sieves for 2 weeks, and THF was
refluxed with metallic sodium and then distilled. To synthe-
size IP-UDMA, a urethane precursor was first synthesized via
the reaction of 2 equiv. isophorone diisocyanate (IPDI) and
1 equiv. polyethylene glycol 400 (PEG400) in THF as solvent
and with a few droplets of dibutyltin dilaurate (DBTDL) as
catalyst. The reaction was carried out in a reactor equipped
with stirrer, heating bath, reflux condenser and dropping
funnel under the N2 blanket. The reaction was continued
until the –NCO content, determined by dibutyl amine titra-
tion, reached half of the amount of the initial diisocyanate.
The unreacted terminal diisocyanate functional groups of
the precursor were then reacted with 2.2 equiv. of 2-hydroxy
ethyl methacrylate (HEMA) which was added dropwise to the
reactor during a period of 1 h. In this step a small amount
of hydroquinone (Merck, Germany) was added to the reac-
tion medium to prevent unwanted polymerization of the
methacrylate monomers. Fig. 1 shows the reaction route. The
reaction was continued until the infrared absorbance peak of
the –NCO group (at 2270 cm−1 ) disappeared in the FTIR spectra
of the samples taken from the reaction medium every 0.5 h.
The final product was washed with distillated water and
centrifuged to eliminate un-reacted HEMA and hydroquinone,
dried under reduced pressure and kept refrigerated for fur-
ther experiments. The structure and purity of the synthesized
IP-UDMA were investigated using FTIR, 1 H NMR, elemental
analysis and refractive index measurements.
1032 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041

Table 1 – Elemental analysis of the synthesized IP-UDMA

H% C% N% O%

Theorya 8.5 58.1 5.1 28.6

Experimentalb 8.77 (0.15) 60.80 (0.04) 5.41 (0.01) 25.01 (0.19)

a
Theoretical values calculated considering n = 8.7 in the chemical structure of IP-UDMA (Fig. 2).
b
Experimental values are the average of three measurements with the standard deviations quoted in the parentheses.

2.2.3. Measurement of degree-of-conversion

The degree of photopolymerization conversion of sam-
ples containing 0.5 wt.% camphorquinone (CQ) and 0.5 wt.%
DMAEMA as photoinitiator system was measured by FTIR
spectroscopy. The samples were placed between two polyethy-
lene films, pressed to form a very thin film and the absorbance
peaks of the un-cured samples were obtained. The sam-
ples were then light-cured for 40 s using a dental light
source with an irradiance of circa 700 mW/cm2 (Optilux 501,
USA) and the peaks were measured for the cured sam-
ples. Degree-of-conversion (DC%) was determined from the
ratio of absorbance intensities of aliphatic C C (peak at
1638 cm−1 ) against internal reference of carbonyl group (peak
at 1720 cm−1 ) before and after curing of the specimen. In the
case of the specimens containing Bis-GMA the aromatic C· · ·C
(peak at 1608 cm−1 ) was considered as internal reference. The
degree-of-conversion was then calculated as follows [33]:
DC%
 
(1637 cm−1 /internal reference)peak area after curing
= 1−
(1637 cm−1 /internal reference)peak area before curing
×100
2.2.4. Shrinkage measurements
0.5 wt.% camphorquinone and 0.5 wt.% N,N -dimethyl
aminoethyl methacrylate, as light-curing initiator system,
were dissolved in the resins under sub-ambient light. The
shrinkage-strain was measured using the bonded-disk tech-
Table 2 – Degree of photopolymerization conversion of
IP-UDMA, Bis-GMA and their mixtures with TEGDMA
Samples DC% (S.D.)
Bis-GMA 32.0 (3.5)
IP-UDMA 51.3 (1.7)
Bis-GMA/TEGDMA 80/20 (wt.%) 55.8 (3.8)
IP-UDMA/TEGDMA 80/20 (wt.%) 58.0 (1.2)
nique [34], with a 3 mm thick glass base-plate, at 25, 35 and
45 ◦ C. The specimens were photopolymerized for 40 s using
the same light source. Initial shrinkage-strain-rates were
obtained by numerical differentiation of shrinkage-strain
data with respect to time [32,35].
2.2.5. Statistical analysis
The results (five repeats) were analyzed and compared using
one-way ANOVA and the Tukey test at the significance level of
 0.05.
3. Results
Table 1 presents results of the elemental analysis of the
synthesized IP-UDMA. Table 2 shows the degree of the pho-
topolymerization conversion of IP-UDMA, Bis-GMA and their
mixtures with the reactive diluent TEGDMA. The neat IP-
UDMA shows much higher DC% than the neat Bis-GMA.
Table 3 shows the shrinkage-kinetic parameters for the resins
(IP-UDMA and Bis-GMA/TEGDMA 80/20 (wt.%)), containing
0.5 wt.% QC and 0.5 wt.% DMAEMA as photoinitiator system, at
different temperatures. Table 4 depicts thermal curing kinetic
parameters of the IP-UDMA resin, containing 1% benzoyl per-
oxide as initiator, at different temperatures.
Fig. 1 illustrates the reaction route for the synthesis of the
IP-UDMA. Fig. 2 illustrates the chemical structure of the IP-
UDMA. Fig. 3 illustrates the FTIR spectrum of the synthesized

Table 3 – Shrinkage-kinetic parameters in accordance

with Eq. (2) for the resins (IP-UDMA and
Bis-GMA/TEGDMA 80/20 (wt.%) containing a
photoinitiator system) at different temperatures
Monomer systems T (◦ C) k (s−1 ) m n

IP-UDMA 25 0.0055 0.7 2.85

35 0.0062 0.65 2.9
45 0.0068 0.57 2.9

Bis-GMA/TEGDMA (80/20) 25 0.0045 0.9 2.95

35 0.0056 0.9 2.92
45 0.0063 0.85 2.9
Fig. 1 – Reaction route of IP-UDMA synthesis.
 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041 1033

Fig. 2 – Chemical structure of the synthesized IP-UDMA.

Table 4 – Thermal-curing kinetic parameters in

accordance with Eq. (1) for the IP-UDMA resin,
containing 1% benzoyl peroxide as initiator, at different
temperatures
T (◦ C) k (s−1 ) m n

75 0.23 0.54 0.95

85 0.27 0.43 1.02
95 0.39 0.31 1.05

IP-UDMA. The following characteristic peaks are apparent in

the figure:

•  = 3341 cm−1 (>NH stretching peak),  = 2952 cm−1 (>C–H

stretching peak),
•  = 1718 cm−1 (>C O stretching peak),  = 1637 cm−1 (>C C Fig. 4 – 1 H NMR spectrum of the synthesized IP-UDMA.
stretching peak).

Fig. 4 shows the 1 H NMR spectrum of the IP-UDMA with the
following characteristic peaks:
• ı = 1–1.5 ppm [a–e], ı = 1.9 ppm [f], ı = 2.03 ppm [deuterated
acetone], ı = 2.8 ppm [h, which may also be overlapped with
the protons of H2 O], ı = 3.5–3.8 ppm [j (protons of –CH2 – in
the middle of the PEG chain), g also appears in the same
chemical shift], ı = 4.0–4.4 ppm [i and k, the protons of the
–CH2 – of PEG adjacent to the end carbonyl groups may also
overlap], ı = 5.6 ppm [m, CH trans], ı = 6.2 ppm [n, CH cis],
ı = 6.2, 6.4 ppm [o, p].

Figs. 5 and 6 depict the rheological behavior of the IP-UDMA

Fig. 3 – FTIR spectrum of the synthesized IP-UDMA.
and Bis-GMA resin at different temperatures showing con-
stant viscosities in the frequency range of 0.01–100 rad/s and
a higher G than G owing to their viscous behavior. The fig-
ures also demonstrate a decrease in the complex viscosity of
the resins with temperature. The temperature dependence of
the viscosity of the resins measured at the angular frequency
of 0.1 rad/s is shown in Fig. 7 which illustrates a dramatic
decrease in the viscosity of the resins with temperature.
Figs. 8 and 9 show the shrinkage-strains and shrinkage-strain-
rates of the IP-UDMA monomer at different temperatures.
Figs. 10 and 11 illustrate the shrinkage-strains and shrinkage-
strain-rates of the neat Bis-GMA and Figs. 12 and 13 show
those of the Bis-GMA/TEGDMA monomer mixture at dif-
1034 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041

Fig. 6 – Rheological behavior of Bis-GMA at different

temperatures: (a) 23 ◦ C, (b) 28 ◦ C, and (c) 37 ◦ C. () Storage
modulus, G ; () loss modulus, G ; () complex viscosity, *.
Fig. 5 – Rheological behavior of IP-UDMA at different
temperatures: (a) 23 ◦ C, (b) 28 ◦ C, and (c) 37 ◦ C. () Storage
modulus, G ; () loss modulus, G ; () complex viscosity, *.
tion route of Fig. 1 and the structure illustrated in the Fig. 2.
The IP-UDMA was a clear monomer with a refractive index of
nD25 = 1.49103 which is close to the refractive indices of glass
ferent temperatures, respectively. The figures indicate that fillers (≈1.556) used in dental restorative materials. This pro-
the shrinkage-strain and shrinkage-strain-rate increased with vides a good appearance in restorative composites in which
increasing temperature. Fig. 14 shows the temperature depen- an esthetic appearance is of great importance.
dence of the shrinkage-strain of Bis-GMA and IP-UDMA. As Figs. 5 and 6 present, both IP-UDMA and the neat Bis-
The pre-exponential parameter and the overall activation- GMA had constant viscosities in the angular-frequency range
energy of shrinkage-strain of IP-UDMA and Bis-GMA/TEGDMA
mixture were determined from Fig. 15. Fig. 16 illustrates the
isothermal DSC scans of the IP-UDMA at different tempera-
tures with the model curves fitted onto the experimental data.
The conversion of the thermally cured IP-UDMA versus time at
different isothermal temperatures (Fig. 17) was calculated con-
sidering that the heat of polymerization at 95 ◦ C over a period
of 40 min corresponds to the maximum conversion.

4. Discussion

4.1. Synthesis and characterization of the IP-UDMA

The results of FTIR and 1 H NMR spectroscopy (Figs. 3 and 4),

and the elemental analysis (Table 1) confirm the chemical Fig. 7 – Complex viscosity of Bis-GMA vs. temperature at an
structure of the synthesized monomer according to the reac- angular frequency of 0.1 (rad/s).
 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041 1035

Fig. 8 – Shrinkage-strain of IP-UDMA at different temperatures.

of 0.01–100 (rad/s), which reveals the Newtonian rheological
behavior of the resins. The viscosity decrease of neat Bis-
GMA is slightly more than IP-UDMA at 37 ◦ C (Fig. 7) which is
probably because the high viscosity of Bis-GMA arises from
the presence of OH groups in its structure resulting in strong
hydrogen-bonding. The high viscosity of IP-UDMA arises from
its relatively high molecular-mass (1103 g/mol). Hydrogen
bonding is more temperature-dependent than the segmental
mobility; therefore the viscosity of Bis-GMA decreases more
than the new monomer with increasing temperature.
The relatively high molecular-mass of IP-UDMA results
in lower polymerization shrinkage during resin-curing. Com-
parison of Figs. 8, 10 and 12 shows that the polymerization
shrinkage of the new monomer is about 35% less than the
shrinkage of Bis-GMA/TEGDMA mixtures, suggesting that IP-
UDMA is a promising monomer with reduced shrinkage for the
matrix-phase of dental restorative materials or other applica-
tions in which the polymerization contraction is a drawback.
The shrinkage-strain of the new monomer is very close to
that of Bis-GMA at room temperature (25 ◦ C) as indicated in
the Fig. 14; but it should be considered that the degree-of-
conversion of the neat Bis-GMA at this temperature is very
low (Table 2) in comparison with the DC% of IP-UDMA. As
the viscosities of the Bis-GMA and IP-UDMA at 25 ◦ C are very
close together the higher degree-of-conversion of the new
monomer is probably due to its higher molecular mobility.
The flexible ether linkages in the polyethylene glycol back-
bone of IP-UDMA provide higher flexibility for the monomer
and access of the (macro)radicals to the methacrylate C C
bonds during the polymerization process, resulting in higher
degree-of-conversion. The shrinkage-strain of the neat Bis-
GMA increased more than that of IP-UDMA as the temperature

Fig. 9 – Shrinkage-strain-rate of IP-UDMA at different temperatures.

1036 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041
Fig. 10 – Shrinkage-strain of Bis-GMA at different temperatures.
increased (Fig. 14) which confirms the viscosity–temperature
results (Fig. 7). The greater decrease in the Bis-GMA vis-
cosity resulted in higher photopolymerization conversion
and, therefore, higher shrinkage-strain at elevated temper-
atures. Table 2 also shows that the DC% of the mixture of
IP-UDMA/TEGDMA is slightly higher than that of the Bis-
GMA/TEGDMA mixture.
4.2. Shrinkage-strain kinetics
Polymerization shrinkage is the result of conversion of inter-
molecular van der Waals distances of the resin-monomers to
the covalent bond-lengths during light-curing. As shrinkage is
a consequence of the polymerization reaction it should follow
the polymerization reaction pattern. Although in the case of
higher polymerization rates the shrinkage rate is slower than
the rate of double bond conversion [36,37], the investigation
into the shrinkage kinetics could help to understand the phe-
nomena per se and/or give an estimation of the polymerization
reaction pattern. Atai et al. [32,35] showed that the photopoly-
merization kinetics of dimethacrylate monomers follow an
Fig. 11 – Shrinkage-strain-rate of Bis-GMA at different
temperatures.
autocatalytic pattern which can be described using the phe-
nomenological model of Kamal [30,31] for thermoset resins.
The model equation is:
d˛ n
= k˛m (˛m − ˛) (1)
dt
where ˛ represents the relative conversion, k an Arrhenius-
type rate-constant, n the reaction order exponent and m is the
autocatalytic exponent. In this equation k˛m represents the
autocatalytic nature of the process [38]. ˛m is the maximum
conversion, which is considered as 1 when the assumption of
a completed reaction is made.
The autocatalytic model has also been used to describe
photo-initiated polymerization of dental resin-monomers and
composite systems and multifunctional acrylates based on
photo-DSC measurements [39–46].
As the dimethacrylate resin-monomers follow the autocat-
alytic pattern, the shrinkage-kinetics of the materials could be
used to follow the polymerization behavior. Hence, Eq. (1) was
applied to describe the shrinkage-strain-rate. The equation
can be re-written for modeling of shrinkage as follows:
dε n
= kεm (εm − ε) (2)
dt
where similarly, ε is the shrinkage-strain, εm the maxi-
mum of the shrinkage-strain measured at a given time
(here after 60 min), k the shrinkage rate-constant, m denotes
the shrinkage-strain autocatalytic exponent, and n is the
shrinkage-strain order exponent.
The kinetic parameters of k, m, and n were calculated fol-
lowing the method of Kenny for determination of the kinetic
parameters of thermoset curing [47]. Adopting the method, Eq.
(2) can be linearized as follows:
 dε 
ln = ln k + m ln ε + n ln(εmax − ε) (3)
dt
 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041 1037

Fig. 12 – Shrinkage-strain of the resin (80 wt.% Bis-GMA, 20 wt.% TEGDMA) at different temperatures.

Plotting ln(dε/dt) against ln(εmax − ε), n is obtained from the The calculated parameters for the neat IP-UDMA and the
slope of the linear part of the curve. The Eq. (2) can also be resin containing 80 wt.% Bis-GMA and 20 wt.% TEGDMA, at
rearranged and linearized as follows: different temperatures, are listed in Table 3. The results
show an increase in the rate-constant, k, with increasing
  temperature and a slight tendency to decrease in the expo-
(dε/dt)
ln n = ln k + m ln ε (4) nent m. Figs. 9 and 13 show the experimental values of
(εmax − ε)
the shrinkage-strain-rate and the model curves fitted to the
experimental data according to Eq. (2), for the IP-UDMA
Having determined n in the first step, k and m were then and Bis-GMA/TEGDMA resin-monomers, respectively. As the
obtained from the intercept and slope of the linear plot based figures illustrate there is a good agreement between the exper-
on Eq. (4). imental data and values predicted by the suggested model.

Fig. 13 – Shrinkage-strain-rate of the resin (80 wt.% Bis-GMA, 20 wt.% TEGDMA) at different temperatures.
1038 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041

Fig. 14 – Temperature-dependence of the shrinkage-strain

of Bis-GMA and IP-UDMA. (The shrinkage-strains Fig. 15 – Shrinkage rate-constant variation with
measured after 600 s.) temperature: ln k vs. 1/T for calculating kinetic parameters
A and E ( IP-UDMA,  Bis-GMA/TEGDMA).

The shrinkage rate-constant, k, is a temperature-

dependant Arrhenius-type constant: and E were then calculated by plotting ln k against (1/T)
(Fig. 15).
E
E, the overall activation-energy of shrinkage-strain and A
k = A exp (5)
RT were obtained as: E = 8.37 (kJ/mol) and A = 0.16 (s−1 ) for
IP-UDMA; and E = 13.3 (kJ/mol) and A = 0.98 (s−1 ) for the Bis-
where T is temperature, R the gas constant, and E is the GMA/TEGDMA mixture.
activation-energy.
To obtain the values of A and E, Eq. (5) can be linearized as 4.3. Thermal curing kinetics
follows:

E As the multifunctional monomers are used in the applications

ln k = ln A −
RT
The shrinkage-strain of the matrix resin was determined
for different temperatures (25, 35, and 45 ◦ C) and the k val-
ues obtained using Eq. (2). The pre-exponential factor, A,
(6) in which the polymerization of the resins is performed using
heat-curing and thermal initiator systems, the thermal-curing
kinetics of the resin were also studied. In DSC measurements
it is assumed that the exothermic heat generated during
isothermal cure is proportional to the number of double bonds

Fig. 16 – Isothermal DSC scans and model fitted curves of IP-UDMA at different temperatures.
 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041
Fig. 17 – Thermal-curing conversion vs. time for IP-UDMA
containing 1% benzoyl peroxide as initiator at different
temperatures. (Experimental data and the model fitted
curves.)
reacted in the system. Therefore, a measurement of the heat
evolved should be an indication of the degree-of-conversion.
The relative conversion is then expressed as:
Q(t)
relative conversion = ␣ =
Qtotal
where Q(t) is the partial heat of reaction developed during DSC
measurement and Qtotal represent the total heat of polymer-
ization reaction. Q(t) is measured by DSC and is the area of
the exothermic peak of reaction on the DSC curve. The total
heat of reaction (Qtotal ) is, in fact, the total heat of the con-
version of the (meth)acrylate double-bonds to single-bonds.
If the composition of the composites or resins, which are
being tested, is known the Qtotal can be calculated consider-
ing the molar heat of reaction of the meth(acrylate) groups.
If the composition is unknown, Qtotal is usually measured in
non-isothermal mode. The Qtotal will then be the peak area
in this condition. In fact the Qtotal , which is measured in this
method represent the maximum heat of reaction measured in
the non-isothermal mode. It must be noted that it is not the
‘heat of 100% reaction’ and residual unreacted double bonds
may still be present in the sample, as a consequence of caging
of unreacted monomers in the densely cross-linked network.
However from a processing point of view, Qtotal is the maxi-
mum reactivity that can be measured in this method and it is
the best choice.
In our work it is assumed that the heat generated in the
isothermal heat curing of the resin at 95 ◦ C (for 40 min) could
be a good estimation of the maximum heat of reaction (Qtotal ).
Therefore, in the Eq. (1) the total heat of reaction generated
at 95 ◦ C was considered to calculate the maximum conversion
(˛m ) for all isothermal temperatures.
To obtain the thermal-curing kinetics of the IP-UDMA, the
isothermal DSC scans of the monomer were determined at dif-
ferent temperatures: 75, 85, and 95 ◦ C. Figs. 16 and 17 show the
isothermal DCS scan and the conversion of the IP-UDMA ver-
1039
sus time at different isothermal temperatures, respectively.
The same procedure as the shrinkage-kinetic investigation
was followed and the kinetic parameters were calculated by
linearization of the Eq. (1). The kinetic parameters are listed in
the Table 4. As the results show, the rate-constant, k, increased
with increasing temperature and a decrease was observed in
exponent m. The pre-exponential factor, A, and E were then
calculated by plotting ln k against (1/T). E, the overall curing
activation-energy, and A were obtained as E = 39.9 (kJ/mol) and
A = 35.3 × 10−3 (s−1 ).
As the principle of the shrinkage measurement method
and thermal analysis (DSC) is different, it could be expected
that different values for the kinetic parameters may be obtain
from these methods.
It is observed that both in photopolymerization shrinkage
and thermal curing of the resins, the rate curves show rising
and falling parts at the early stages of the curing. These rep-
resent the auto-acceleration and auto-deceleration stages of
the polymerization reaction that is the indication of the auto-
catalytic reactions in which the reaction by-products could
accelerate the main reaction. It has been shown that the auto-
catalytic model can also explain the polymerization of mul-
tifunctional monomers [38]. Polymerization and network for-
mation of the monomers in the presence of free-radical initiat-
ing systems follows radical chain polymerization in which the
reaction rate is given by the following classical equation [48]:
 R 1/2
RP = kP [M] i
(7)
2kt
The polymerization reaction of multimethacrylates and
multiacrylates is diffusion-controlled [49]. A few seconds after
irradiation, the autoaccelerative gel effect is seen in which
the segmental movement of radicals are restricted and termi-
nation becomes diffusion-controlled, leading to an increase
in the polymerization-rate. During this stage, kt in Eq. (7)
decreases and results in a dramatic increase in Rp . Continuing
the reaction, the system becomes more viscous and restricted
so that the propagation reaction also becomes diffusion-
controlled. At this stage, kP in Eq. (7) also decreases leading
to the fall in the polymerization-rate. This decline in the rate
is called auto-deceleration or the glass effect [48–51], the latter
relating to the onset of vitrification.
5. Conclusions
A new urethane dimethacrylate was synthesized via the
reaction of isophorone diisocyanate (IPDI), polyethylene gly-
col (PEG 400) and 2-hydroxyethylethyl methacrylate (HEMA).
The chemical reaction and the generation of the product
were followed and confirmed using FTIR and 1 H NMR spec-
troscopy and elemental analysis. The new monomer showed
a lower shrinkage-strain and higher degree-of-conversion in
comparison with the commercially available resin-monomer,
Bis-GMA, suggesting that it is a feasible alternative for dental
restorative materials and other applications where minimiz-
ing polymerization shrinkage is important. Kinetic studies of
the resin-monomer confirmed that its photopolymerization
shrinkage and thermal-curing kinetics follow autocatalytic
1040 d e n t a l m a t e r i a l s 2 3 ( 2 0 0 7 ) 1030–1041
behavior and can be satisfactorily described using the phe-
nomenological model of Kamal [30,31].
The autocatalytic pattern confirmed the diffusion-
controlled mechanism of the curing reaction of the monomer.
The kinetic parameters were also determined by performing
the measurements at different temperatures.
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