Hyperbranched Polymer/TiO2 Hybrid Nanoparticles

Synthesized via an In Situ Sol-Gel Process

Hohe Str. 6
D-01069 Dresden
Internet: www.ipfdd.de
E-mail: ipf@ipfdd.de
Hyperbranched Polymer/TiO2 Hybrid Nanoparticles
Synthesized via an In Situ Sol-Gel Process
Macromol. Chem. Phys. 2007, 208, 76–86
Anna Di Gianni, Sondes Trabelsi, Giancarlo Rizza, Marco Sangermano, Holger Althues,
Stefan Kaskel, Brigitte Voit

A. Di Gianni, M. Sangermano
Politecnico di Torino, Dipartimento di Scienza dei Materiali eIngegneria Chimica, C.so Duca degli Abruzzi 24, 10129 Torino, Italy.

S. Trabelsi, B. Voit
Leibniz Institute of Polymer Research, Hohe Strasse 6, D-01069 Dresden, Germany

G. Rizza
Laboratoires des Solides Irradies, Ecole Polytechnique/CEA (DSM-DRECAM)/CNRS (UMR 7642), 91128 Palaiseau Cedex, France

H. Althues, S. Kaskel
Technical University of Dresden, Institute for Inorganic Chemistry, Mommsenstrasse 6, 01069 Dresden, Germany
Two different kinds of HBPs were used in the preparation of nanocomposite
materials based on TiO2 nanoparticles. One of the HBPs was characterized by the
presence of free OH end groups in its structure, while the other one was obtained via
a partial modification reaction which allowed to introduce some alkoxysilane
functional groups.

The TiO2 particles were prepared in situ in the polymer solution by means of a sol-
gel process starting from Ti(iOPr)4 as precursor. The polymer/TiO2 mixture,
subsequently coated and cured in the presence of diisocyanate, gave rise to a hard
coating.

TiO2 was found to be dispersed on nanometer scale inside the final coatings obtained
from both the polymers, and the TiO2 nanocomposite coatings were also
characterized by improved thermal and hardness properties compared to TiO2 free
systems.

Still the two different kinds of HBPs showed a different interaction with the TiO2
particles, and it has been evidenced that the modification is required to achieve a
better dispersion of the particles in the matrix and better properties for the final
coating.
The choice of the polymeric matrix and the inorganic filler depends on the field of
application and on the required final properties. In particular, polymers combined with
metal oxides nanoparticles can, as reported in the literature, lead to composites
characterized by improved chemical, thermal, optical, electronic, and mechanical
properties.

Many nanocomposites based on conventional linear polymers were prepared and

characterized so far, but still few and only very recent studies have been reported about the
use of hyperbranched polymers (HBPs) in combination with inorganic nano-objects.

HBPs belong to a group of macromolecules known as dendritic polymers. They are

characterized by a highly branched backbone and by a large number of functional groups
that can be further modified. The dense branched structure, which results in a low amount
of intra- and intermolecular entanglements, allows for good flow and processing properties.
Moreover, their synthesis is relatively easy and, in many cases, they can be obtained by only
one synthetic step.

In fact, the major problem that has to be faced in the synthesis of any composite material is
the insufficient dispersion of the metal oxide nanoparticles within the organic matrix.
However, without a full dispersion, the potential of the nanoparticles cannot be fully
exploited.
Therefore, different methods have been developed in order to achieve a better
interaction between the two phases and, as a consequence, a homogeneous dispersion on
the nanoscale of the inorganic particles inside the organic matrix. In order to achieve
this goal, compatibilizers are widely used.

In particular, the in situ sol-gel synthesis of inorganic particles inside a polymeric

matrix gave good dispersions in the case of many metal oxides such as SiO2 or TiO2.
In the present work, some HBP aliphatic-aromatic polyesters, OH terminated, have
been used as matrices for nanocomposites containing TiO2. The TiO2 nanoparticles
were synthesized via sol-gel directly in a solution containing the HBP polyester as
stabilizer, and then the polymer/TiO2 hybrid mixtures were thermally cured by
means of a curing agent to obtain a hard coating or a film.

In order to determine the conditions in which it was possible to get the best dispersion
and properties for the final material, the starting HBP-OH was also partially modified
with alkoxysilane groups, enabling it to interact with the TiO2 network. Both materials
obtained were then characterized and their properties compared.
Two different HBP structures were used as matrices for the nanocomposites synthesis:
a hyperbranched aromatic-aliphatic polyester with phenolic end-groups, HBP-OH,
synthesized in a melt polycondensation from 4,40-bis(4-hydroxyphenyl)valeric acid as
described in previous papers[26] (the sample employed is characterized by an average
number of 5–20 OH functionalities per molecule, Mn ¼1 150 by NMR measurements, Mn
¼5 100 by GPC measurements, PD¼4.52, Tg¼70 8C), and an alkoxysilane modified
phenolic hyperbranched polyester HBP(OH)Si(OEt)3. The latter was synthesized using a
modification reaction conducted on the HBP-OH.
 Synthesis of the Alkoxysilane-Modified
Hyperbranched Polyester HBP(OH)Si(OEt)3

1 g of the HBP-OH[26] (0.00086 mol) was added to a flask containing 20 mL of dry

dimethylformamide (DMF) under Ar atmosphere.Then 0.075 g of (3-isocyanatopropyl)
triethoxysilane (0.625 mol) and one drop of catalyst dibutyltin dilaurate were added. The
mixture was kept under stirring and heated at 40ºC by means of an oil bath. After 2 h the
bath was removed and the reaction continued over night. The reaction mixture was poured
into cold water in order to precipitate the polymer, which was then filtered and dried under
vacuum.
 Sol-Gel Synthesis of TiO2 Nanoparticles in a
Polymeric Solution
The polymer (0.5 g) [both HBP-OH and HBP(OH)Si(OEt)3 were used] was dissolved in
10 mL of dry DMAc under Ar atmosphere. A second solution, made up of Ti(iOPr)4 (in
the amount of 7.5, 10, and 20 wt.-% with respect to the polymer) and 5 mL of DMAc,
was added very slowly for 1 h, drop by drop and under vigorous stirring at room
temperature. In the end, a mixture of water [in equimolar amount respect to the
Ti(iOPr)4] and DMAc was added dropwise for over 1 h in the reaction solution. As
result, a perfectly clear yellow solution was obtained

Preparation of Coatings
5 mL of solution containing the polymer and the TiO2 precursor was, under stirring,
supplemented with 1,6-diisocyanatohexane (in equimolar amount with respect to the OH
functionalities of the polymer), as a curing agent, and one drop of dibutyltin dilaurate,
as a catalyst. The resulting mixture was then poured into a Petri dish and cured under
vacuum at 70ºC for 2 d. The coating, which looked perfectly transparent (see Figure 2),
could be peeled off from the substrate for subsequent analysis.
 Results and Discussion
Nanocomposites Preparation

Two different kinds of hyperbranched polyesters were used as matrices in the synthesis
of polymer nanocomposites based on TiO2. One of them was an aliphatic–aromatic
having phenolic end groups (HBP-OH) whose synthesis is described elsewhere.[26] The
other one (HBP(OH)Si(OEt)3) was obtained starting from the HBP-OH, which was
subsequently partially modified with an alkoxysilane functionality using (3-
isocyanatopropyl) triethoxysilane resulting in a product with triethoxysilane as well as
phenolic end groups (Scheme 1).. Since only partial modification was attempted, the (3-
isocyanatopropyl) triethoxysilane was added as the minor component with respect to
the number of OH end groups of the HBP-OH. Thus, a modification degree of 30% was
obtained as determined by 1H NMR.
 Modification reaction

Scheme 1. Modification reaction of HBP-OH leading to the synthesis of

HBP(OH)-Si(OEt)3.

The described treatment allows to complete the synthesis of the TiO2 particles through
a condensation reaction which leads to the formation of the final inorganic network. At
the same time, it allows the curing of the polymer, thanks to the reaction between the
isocyanate groups of the curing agent and the OH end groups, which are present in both
the HBP structures employed. The synthesis of the TiO2 particles, however, would have
started already in the solution due to high reactivity of the precursor Ti(iOPr)4.
Dynamic light scattering (DLS) analysis was done using a Zetasizer Nano ZS (Malvern)
instrument. Average particles diameters (z-average) were determined from intensity-
weighted size distributions. DLS measurements were performed to investigate the
formation of some primary particles in the solution before the thermal curing process
and the results are shown in Figure 1. In the case of the DMAc solution of the HBP-OH
polymer, the main peak is centered at about 1.7 nm, while after the addition of 20 wt.-%
Ti(iOPr)4 and H2O, the peak is shifted at about 8 nm. This result indicates the
formation of some primary particles which are stabilized through the interactions with
the HBP polymer functionalities.
 In Scheme 2, the sol-gel process is schematically
represented showing TiO2 preparation from the Ti
alkoxide precursor. It is well known that the
process is made up of two steps: hydrolysis and
condensation. As shown, the condensation can also
take part between a metal-OH group and a metal-
OR group as well as other suitable groups.
Therefore, when the polymer HBP(OH)-Si(OEt)3
is employed, its Si(OEt)3 functionalities can also be
involved in the formation of the inorganic TiO2
network through the condensation step.
Of course, also OH functions from the unmodified
polyester may interfere in the condensation
reaction; however, the reactivity should be
significantly lower and thus, the probability is
lower. In addition to the covalent bonds formed
between the HBPs and the titania nanoparticles,
also some physical interactions might be possible
to stabilize the metal oxide particles already in
solution and to avoid agglomeration in the bulk
phase.
Scheme 2. Schematic representation of the sol-gel process
for a titanium alkoxide.
Of course, also OH functions from the unmodified polyester may interfere in the
condensation reaction; however, the reactivity should be significantly lower and thus,
the probability is lower. In addition to the covalent bonds formed between the HBPs
and the titania nanoparticles, also some physical interactions might be possible to
stabilize the metal oxide particles already in solution and to avoid agglomeration in the
bulk phase. This should allow for both HBPs a rather good interaction and
compatibilization between the organic and the inorganic phase; however, an even more
positive effect was expected for the reactive modified HBP sample, as schematically
represented in Scheme 3.
 The AFM phase images (Figure 3)
show, thanks to the stiffness contrast,
some hard particles (bright regions) on
the surface of the HBP-OH/TiO2
composite characterized by a quite
smooth interface, while it is not
possible to clearly identify hard
particles on the surface in the case of
the HBP(OH)-Si(OEt)3/TiO2
nanocomposite. However, the AFM
images do not allow a reliable
estimation of the size of the TiO2
particles in the matrices due to the fact
that they only represent a picture of
the surface topography and its
roughness can influence the
interpretation of the pictures.

Figure 3. (a) AFM images of surface of the coating obtained from HBP-OH, (b) HBP(OH)-
Si(OEt)3, (c) HBP-OH containing 20 wt.-% of Ti(iOPr)4, and (d) HBP(OH)-Si(OEt)3 containing 20
wt.-% of Ti(iOPr)4.
 Figure 4 shows the TEM pictures
obtained for the pure matrix, and
for the unmodified and modified
polymer prepared adding 20 wt.-%
of Ti(iOPr)4. It can be clearly seen
that we obtained much smaller
particles when the modified polymer
is used as a matrix: in fact, in this
case, 6 nm average sized particles
were obtained, while in thecase of
the unmodified polymer, 15 nm
average sized particles had been
obtained. This allows to conclude
that the modification reaction
allows a better stabilization of the
TiO2 nanoparticles probably
already during the sol-gel reaction
in solution.

Figure 4. (a) TEM images of the coatings obtained from of HBP-OH matrix, (b) HBP-OH
containing 20 wt.-% of Ti(iOPr)4, and (c) HBP(OH)-Si(OEt)3 containing 20 wt.-% of Ti(iOPr)4.
 Conclusion
Two different kinds of HBPs were used as matrices for nanocomposite materials containing TiO2: an
aromatic aliphatic polyester, OH terminated, and a second polyester, bearing alkoxysilane groups and
OH groups, obtained from partial modification of the first one.

TiO2 was synthesized via an in situ sol–gel process in the presence of the polymer, and films were
prepared from the mixtures and the polymer was subsequently thermally cured by diisocyanate.

The TEM analysis, in agreement with AFM and SAXS measurements, shows that it is possible to obtain
coatings containing individual nanosized TiO2 particles in the both cases. In particular, if the matrix is
represented from the modified polymer, thanks to the strong interaction between the TiO2 precursor
with the Si(OEt)3 end groups of the hyperbranched structure, it is possible to obtain smaller particles
with an average size of only 6 nm, compared with those obtained using the unmodified hyperbranched
polyester (about 15 nm). DSC analysis also reveals a much stronger interaction between the inorganic
nanoparticles and the HBP matrix since no longer a glass transition temperature could be identified.

The presence of TiO2 inside the coating enhances the thermal properties of the coatings with better
results if modified HBP(OH)-Si(OEt)3 is used. Enhanced hardness properties are also achieved on
incorporating TiO2 in the coatings.