European Polymer Journal 45 (2009) 295–301

Contents lists available at ScienceDirect

European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Short communication

Ziegler–Natta catalysed polymerisation for the preparation

of copolymers with pendant sucrose moieties
Maria T. Barros *, Krasimira T. Petrova
REQUIMTE, CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal

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

Article history: The copolymerisations of the monomers 1 (10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-60 -O-crotonyl-
Received 4 July 2008 sucrose) and 2 (10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-60 -O-methacryloyl-sucrose) with styrene/
Received in revised form 8 October 2008 methyl methacrylate have been examined in the presence of Ziegler–Natta catalyst TiCl4/
Accepted 12 October 2008
AlEt3. A study of the effect of the reaction conditions, the monomer structure and the initial
Available online 21 October 2008
quantity of the comonomers on the sugar incorporation and molecular mass of the final
copolymers has been carried out. In this way, by the coordination mechanism of polymer-
isation we had obtained novel linear unbranched polymers and copolymers, potentially
Keywords:
Sucrose methacrylate
useful for biomedical applications.
Sucrose crotonate Ó 2008 Elsevier Ltd. All rights reserved.
Vinyl sucrose copolymers
Natural products copolymers
Coordination copolymerisation

1. Introduction pared hydrogels from them and showed some practical

In 1946, Haworth and coworkers [1] first reported the
preparation of polymerisation products from substituted
carbohydrates containing acrylate or methacrylate groups.
Since then, there has been extensive interest in the synthe-
sis and polymerisation of mono-functionalised carbohy-
drate monomers. In 1991 Dordick et al. reported a
poly(sucrose acrylate) and poly(sucrose adipamide) syn-
thesis with the help of an enzyme (Proleather, an alkaline
protease from a Bacillus sp.) [2]. Chen et al. have also used
the enzymatic approach [3]. Deffieux et al. have prepared
monomethacryloyl sucrose esters by two different routes
– in aqueous media and in organic solvent [4], as well as
several ethylenic acetals of sucrose [5] and have examined
their homo- and copolymerisation with styrene. Akashi
et al. have synthesised methacryloyl and acryloyl-type glu-
cose containing vinyl monomers and have shown that it is
possible to produce them on industrial scale. They also pre-
* Corresponding author. Tel.: +351 212948300; fax: +351 212948550.
E-mail addresses: mtbarros@dq.fct.unl.pt (M.T. Barros), krasimira.
petrova@dq.fct.unl.pt (K.T. Petrova).
applications for these products [6]. The synthesis of
water-soluble monomer, derived from D-gluconolactone,
is described [7]. The homopolymerisation of the vinylsugar
has been conducted in both aqueous and organic media
using free-radical initiators, forming high-molar-mass
water-soluble polymers. Sugar-based hydrogels, obtained
by non-selective modification of sucrose with the intro-
duction of vinyl groups [8], superporous fast-swelling
hydrogels [9] and the synthesis of a monomeric methacry-
late ester of D-galactopyranose and it’s copolymerisation
with ethyl acrylate has also been described [10]. Some
applications for sugar based polymers are drug delivery
systems [11], dental medicine, bio implants, contact lenses
and tissue engineering [12–14]. For these and other appli-
cations they have the advantage of being potentially biode-
gradable, as shown in the literature [15–17].
Sucrose is a carbohydrate feedstock of low molecular
weight from which new materials can be elaborated, such
as water-soluble and/or biocompatible polymers and other
new compounds [1,18–20] owing to its low price. In previ-
ous publications [21–27] we have reported the synthesis
and applications of different sucrose esters. Since sucrose

0014-3057/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.10.013
296 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301
has eight chemically active hydroxyl groups, regioselective
derivatisation is important in the selective synthesis of su-
crose-containing linear polymers [28–30]. Using a protec-
tion–deprotection sequence to selective chemical
derivatisation of the 60 -position of the sucrose [23,26,31],
we had obtained the fully protected sucrose with only
the 60 -hydroxyl unprotected and from this intermediate
we prepared unsaturated sucrose esters in high yields
and purity [24,32]. These monomers were copolymerised
with olephine monomers by free-radical polymerisation
to yield amorphous linear copolymers [24,25]. The main
disadvantage of this approach was the undefined random
structure of the resulting materials with view to the possi-
ble applications. Ziegler–Natta catalysis [33,34] is a meth-
od of producing unbranched stereoregular vinyl polymers.
Ziegler–Natta catalysts are typically based on titanium
chlorides and organometallic trialkyl aluminium cocata-
lyst. Here, we are presenting our preliminary results for
synthesis of novel carbohydrate containing copolymers
with possible biomedical applications. By the coordination
mechanism of polymerisation we had obtained novel lin-
ear unbranched polymers and copolymers, with poten-
tially organised isotactic structure of the macromolecules,
which to give rise to interesting and valuable physical,
mechanical and thermal properties. To the best of our
knowledge, this is the first report on synthesis of linear su-
crose-containing copolymers by coordination mechanism
using Ziegler–Natta catalyst. Although an extensive work
have been done on the synthesis of glycopolymers, more
research efforts are needed to bridge the conceptual, tech-
nological and economical gap between fossil hydrocarbons
and renewable carbohydrates.
2. Results and discussion
For the copolymerisation of the monomers 1
(10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-60 -O-crotonyl-sucrose) and
2 (10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-60 -O-methacryloyl-su-
crose) (Scheme 1) with styrene or methyl methacrylate a
procedure similar to the original one discovered by Ziegler
for polyethylenes was followed [35]. The catalytic system
was a transition metal catalyst TiCl4, and a cocatalyst based
on group III metals, Al(C2H5)3, in molar ratio Ti/Al = 8:1.
The copolymerisation has been examined in the presence
OBn OBn
BnO O O
OBn
BnO O 1
BnO
O O
OBn
OBn OBn
BnO O O
OBn
BnO O gar incorporation ([sug]/[styrene] = 0.224), as well as MZ
BnO 2
O O
Bn= H2C
OBn
Scheme 1. Structures of the monomers 1 (10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-
60 -O-crotonyl-sucrose) and 2 (10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-60 -O-meth-
acryloyl-sucrose).
of TiCl4/AlEt3 in hexane as solvent at 40 °C at normal pres-
sure and conventional heating, followed by precipitation in
cold ethanol, which is miscible with the monomers, the
solvent, as well as by-products (e.g., oligomers). For most
of the samples two polymerised fractions were isolated –
higher molecular mass powder fraction, marked in the
experimental part as p and lower molecular mass, easily
soluble, solid, resinous-like fraction, marked as r. A study
of the effect of the reaction conditions, the monomer struc-
ture, and the initial quantity of the comonomers, on the su-
gar incorporation into the final copolymers has been
carried out. As a result, a number of copolymers with di-
verse protected sucrose content were obtained, having dif-
ferent chain length, reported by the weight average
molecular weight, Mw, effective diameter of the random
coils in solution and with some solution physical proper-
ties such as the diffusion coefficient and Mark–Houwink
constants.
As a first approach to the desired materials, and for
comparison of the products, homopolymers of styrene,
methyl methacrylate, a- and b-pinene [25] were prepared
under similar conditions (see Supplementary data). With
those results in hand we chose to examine the Ziegler–Nat-
ta catalysed copolymerisation of styrene and methyl meth-
acrylate with the monomers 1 and 2, as a- and b-pinene
required elevated reaction times to afford reasonable re-
sults (Tables S3 and S4, Supplementary data). A study of
copolymerisation reactions as a function of the reaction
time (24 and 72 h) was carried out. For copolymerisation
of 2 with styrene (Table 1), slightly higher incorporation
of sugar for the powder fraction and higher MZ for both
fractions at longer reaction time was observed. With
methyl methacrylate the incorporation of sugar, as well
as MZ in the resin fraction was higher at longer reaction
time. For copolymerisation of 1 with styrene (Table 3), no
significant difference in the incorporation of sugar, but
MZ 50 times higher, was observed. In all cases there was
no difference in the overall conversion of the monomers.
In general, at longer reaction time the molecular mass
and the rate of incorporation of sugar were higher, and fur-
ther experiments were conducted for 72 h.
The rate of incorporation of the sugar monomer was
studied varying the initial mole ratio sugar/alkenes in the
range 0.05–1. Copolymer composition has been deter-
mined by 1H NMR by comparing the peak areas of the aro-
matic protons in styrene, or the peak areas of the
methylene, methyl (0.8–2.2 ppm) and methoxy (3.6 ppm)
protons of methyl methacrylate, with the 14 sucrose unit
protons (3.6–5.3 ppm). The molecular masses of the poly-
mer samples were measured by GPC and dynamic light-
scattering. The later method was used as the analyses were
fast, simple and convenient, reproducible, as well as cheap
[36,37]. Analysis of the experimental data for copolymeri-
sation of 2 with styrene showed that the maximum of su-
(38000) of the resin fraction, was obtained at initial mol ra-
tio [sug]0/[styrene]0 = 0.5 (polymer 15-r, Table 1, Fig. 1).
The powder fractions, obtained by this procedure, were
very high molecular weight copolymers, with a maximum
at initial mol ratio [sug]0/[styrene]0 = 0.1 (polymer 16-p,
Table 1, Fig. 2) and even samples 14-p and 15-p ([sug]0/
 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301 297

Table 1
Experimental results for Ziegler–Natta copolymerisation of 2 with styrene: hexane, cat. TiCl4/AlEt3, 40 °C.
½sug0 a ½sugb
Sample ½alk0 ½alk
Reaction time [h] Overall conversion (%) Physical appearance MZc [g/mol] ud [Å] ae Df [cm2/s]

13-p. 0.1 0.084 24 43.1 Powder – – – –

13-r. 0.1 0.260 24 49.2 Resin 9100 339 0.618 1.07  108
14-p. 1 0.182 72 35.3 Powder – – – –
14-r. 1 0.126 72 52.5 Resin 3200 197 0.202 1.85  108
15-p. 0.5 0.279 72 39.3 Powder – – – –
15-r. 0.5 0.224 72 51.4 Resin 38000 717 1.016 5.08  109
16-p. 0.1 0.142 72 45.8 Powder – – – –
16-r. 0.1 0.0271 72 40.6 Resin 13700 420 0.763 8.66  109
17-p. 0.05 0.031 72 54.4 Powder – – – –
17-r. 0.05 0.0065 72 38.2 Resin 4700 240 0.383 1.51  108
a
Initial mole ratio of monomers.
b
Mole ratio of comonomer units in copolymer, determined by 1H NMR.
c
Calculated from the MHS-equation from the diffusion coefficient D, measured by light-scattering. MHS-coefficients were estimated by calibration with
monodisperse polystyrene standards, a = 0.52, K = 1.245  106.
d
Effective diameter, determined by light-scattering.
e
Polydispersity (value, provided by the light-scattering method, it is close to zero for monodisperse samples, small (0.020–0.080) for narrow distri-
butions and larger for broader distributions).
f
Diffusion coefficient.

[styrene]0 = 1 an 0.5, respectively, were not soluble in con-

Fig. 1. Copolymerisation of 2 with styrene: dependence of the incorpo-
ration of sugar in the copolymers obtained on the initial monomer ratio.
Fig. 2. Copolymerisation of 2 with styrene: dependence of the molecular
masses of the copolymers obtained on the initial monomer ratio.
ventional organic solvents, which suggests even higher
molecular mass and/or compact structure.
For copolymerisation of 2 with methyl methacrylate, a
powder fraction was obtained only at initial mol ratio
[sug]0/[MM]0 = 0.1 (sample 21-p, Table 2), but it did not
have high molecular mass (MZ = 1400), unlike the case
with styrene. The incorporation of sugar in the copolymer,
as well as MZ, increased with increasing the initial ratio
[sug]0/[MM]0 in the range 0.1–1.0 (Figs. 3 and 4). The rela-
tion between the molecular weights and the incorporation
of the sugar monomer 1 in the copolymer with styrene was
inversely proportional, as expected (Fig. 5). This could be
explained by the fact that the sugar monomer was less
reactive in the polymerisation reaction, and also contained
more functional groups, providing more possibilities for
chain transfer reactions in the reaction mixture. Compar-
ing the behaviour of alkene monomers styrene and methyl
methacrylate, the copolymers with styrene had signifi-
cantly higher molecular masses (up to 9.6  105) and were
more promising for developing new materials.
The majority of the results obtained for the copolymer-
isation of sucrose derivatives 1 and 2 showed that we got
polymers with a lower incorporation of sucrose than al-
kene, as it was expected. Comparing the behaviour of su-
crose derivatives, the compound with a terminal double
bond (2), which was expected to be more reactive, readily
gave copolymers with a considerable molecular weight (up
to 9.6  105) and incorporation of sugar ([sug]/[sty-
rene] = 0.279, polymer 15-p, Table 1), while the crotonoyl
sucrose (1) was less reactive, the highest molecular mass
was 2.9  105 (polymer 27-r, Table 3), the highest incorpo-
ration of sugar was [sug]/[styrene] = 0.026 (polymer 26-r,
Table 3), and did not afford powder materials.
The GPC chromatograms revealed monomodal distribu-
tion of the molecular weights of copolymers with different
chain lengths for all samples, which confirms that copoly-
mers have been obtained. The NMR spectroscopy is a pow-
erful tool to give information on the microstructure of
polymers [38], but in our case, due to the complexity of
298 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301

Table 2
Experimental results for Ziegler–Natta copolymerisation of 2 with methyl methacrylate: hexane, cat. TiCl4/AlEt3, 40 °C.
½sug0 a ½sugb
Sample ½alk0 ½alk
Reaction time [h] Overall conversion (%) Physical appearance MZc [g/mol] ud [Å] ae Df [cm2/s]

18-p. 0.1 0.069 24 24.1 Powder 9500 346 0.511 1.05  108
18-r. 0.1 0.0114 24 71.5 Resin 7300 303 0.119 1.20  108
19-r. 1 0.335 72 86.2 Resin 21300 529 0.370 6.88  109
20-r. 0.5 0.231 72 80.2 Resin 4100 225 0.077 1.62  108
21-p. 0.1 0.0066 72 35.3 Powder 1400 127 0.112 2.87  108
21-r. 0.1 0.044 72 43.6 Resin 10700 369 0.875 9.86  109
22-r. 0.05 0.474 72 23.2 Resin 14000 426 0.178 8.54  109

a–f, the meaning of the footnotes is the same as indicated in Table 1.

Table 3
Experimental results for Ziegler–Natta copolymerisation of 1 with styrene: hexane, cat. TiCl4/AlEt3, 40 °C.
½sug0 a ½sugb
Sample ½alk0 ½alk
Reaction time [h] Overall conversion (%) Physical appearance MZc [g/mol] ud [Å] ae Df [cm2/s]

23-r. 0.1 0.023 24 42.2 Resin 2800 183 0.155 1.99  108
24-r. 1 0.016 72 63.7 Resin 61300 922 1.066 3.95  109
25-r. 0.5 0.024 72 70.3 Resin 76800 1016 0.740 3.52  109
26-r. 0.1 0.026 72 47.8 Resin 137000 1398 0.737 2.60  109
27-r. 0.05 0.023 72 36.6 Resin 296500 2091 0.831 1.74  109

a–f, the meaning of the footnotes is the same as indicated in Table 1.

Fig. 3. Copolymerisation of 2 with methyl methacrylate: dependence of Fig. 4. Copolymerisation of 2 with methyl methacrylate: dependence of
the incorporation of sugar in the copolymers obtained on the initial the molecular masses on the sugar mole ratio in the copolymers.
monomer ratio.

the molecules, it was unclear. Nevertheless, the 1H NMR
spectra had provided us with information about the nature
of the structural groups presenting in the copolymers, and
from the integration their relative content or incorporation
ratio had been calculated. For polymers in which pseudo-
asymmetric carbon atoms are formed in the polymerisa-
tion process, such as substituted vinyls, the incorporation
of successive monomer units can take place with the same
configuration (isotactic), or with a regularly alternating
configuration (syndiotactic), or with random changes of
configuration (atactic) [38]. In the case of copolymers,
due to the differences in chemical shifts originating from
different comonomer units surrounding, we observed that
the peaks became more complex and poorly resolved.
Observing the multiplicity of the signals, for example for
the –CH2– and a-CH3 groups of the methyl methacrylate
units, there was splitting of the signals, which suggested
heterogeneity of the chain configuration and could be con-
cluded that the monomer units were connected in atactic
and random manner.
13
C NMR was employed, because the detection of very
small changes in chemical shift is necessary to identify
the microstructure sequences [38,39]. The C-1 aromatic
carbon from the aromatic in styrene units is an asymmetric
carbon and is sensitive to the monomer insertion along the
macromolecular chains, and resonance of this carbon
shows different chemical shifts due to the microstructure.
The normal 13C solution NMR spectrum of polystyrene
copolymers in deuterated chloroform did not show a good
spectral resolution and the complete assignment of the
tacticity-originated sequences could not be done. This dif-
ficulty could be overdone at later stage by different physi-
 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301
Fig. 5. Copolymerisation of 1 with styrene: dependence of the molecular
masses of the copolymers obtained on the initial monomer ratio.
cal pretreatment, like solution casting, preparing pressed
films or quenching [40] or increase of temperature might
sharpen some of the signals to a certain extent due to im-
proved mobility of the polymer backbone.
It has been shown [41], that Ziegler–Natta catalysts,
based on TiCl4/AlEt3, are providing highly isotactic polysty-
rene with elevated molecular weight, but with broad
molecular weight distribution, as it is the result in our case.
Based on the literature data [42], and closely following the
polymerisation procedures described, we assumed that our
experiments were following the coordination mechanism
as well, without having direct evidence on it. We also note
that there is a close identity between catalysts which cause
Ziegler–Natta polymerisation and those which give rise to
olefin metathesis. There are many systems where metath-
esis is accompanied by oligomerisation of the olefin [43],
and often the same catalyst or virtually identical catalysts,
effect both ring-opening polymerisation of cycloalkenes
and alkenes [44]. Necessary precautions to avoid possibil-
ities for cationic polymerisation by degassing the reaction
mixtures and working in inert atmosphere had been taken.
The polystyrene copolymers obtained were insoluble in
acetone, which is a feature of isotactic polystyrene versus
atactic. Also, the melting point was elevated in comparison
to the commercial atactic polystyrene – 205 versus 100 °C,
which is another feature of structured polymers.
The mechanism of catalytic polymerisation, composi-
tion of active centers of Ziegler–Natta catalysts and the
mechanism of propagation and chain transfer reactions
can be studied by known methods [45,46] and it will be
an objective of future work.
3. Conclusions
In summary, a, b-unsaturated esters of sucrose were
obtained regioselectively in high yields and purity by four
steps starting from unprotected sucrose. These units have
been copolymerised with olephine monomers, namely sty-
rene and methyl methacrylate using Ziegler–Natta cata-
lysts, yielding unbranched linear polymer materials with
pending sucrose moieties. The characterisation of the poly-
299
mer samples – the average molecular mass, as well as
some physical properties of the resulting polymeric mate-
rials – permits an assessment of structural, thermal,
mechanical and rheological information. Under the condi-
tions chosen, we achieved good overall conversions, com-
pared to the reported in the literature [4], lower
incorporation of sugar and higher average molecular mass.
Further optimisation of the physical properties with a view
to possible applications, as well as deprotection and biode-
gradability of copolymers, containing sucrose moieties side
groups, is under investigation. The resulting copolymers
were formed using sucrose – easy accessible natural prod-
uct, and continue our program of research on the synthesis
of polymeric materials from renewable starting materials
with possible biomedical applications.
4. Experimental
4.1. General methods
The sucrose monomers 10 ,2,3,30 ,4,40 ,6-hepta-O-benzyl-
60 -O-crotonyl-sucrose 1 and 10 ,2,3,30 ,4,40 ,6-hepta-O-
benzyl-60 -O-methacryloyl-sucrose 2 were synthesised as
reported [24]. Reagents and solvents were purified before
use [47]. NMR spectra were recorded at 400 MHz in CDCl3
with chemical shift values (d) in ppm downfield from TMS.
Average molecular weights were determined using a dy-
namic light-scattering apparatus with operational angle
90°, red light 675 nm, calculated from the diffusion coeffi-
cients of polymer solutions suspended in ethanol, at 20 °C,
using the MHS-equation [48,49]. All solvents used for dilu-
tion were filtered through a 0.2 lm membrane filter. Two
thousand five hundred cycles of experiment duration were
used for each run, and the dust cut-off, above 21, had no
effect on the measurement, indicating a reasonably
dust-free sample. The calibration and determining the
MHS-coefficients were performed with commercial mono-
disperse polystyrene standards. Gel permeation chromato-
graph (GPC) results were obtained using light-scattering,
refractive index, ultraviolet and viscometer detectors in a
temperature controlled oven (set at 35 °C) coupled to a
integrated solvent and sample delivery module (degasser,
pump and auto sampler), at a flow rate 1 mL/min, using
dichloromethane as eluent, and with an injection volume
of 150 ll. The detectors alignment and instrument sensi-
tivity parameters were previously calibrated using a low
molecular weight narrow polystyrene standard.
4.2. General procedures for Ziegler–Natta copolymerisation of
monomers (1) and (2) with styrene and methyl methacrylate
To the solutions of 0.0628 g (0.060 mmol) of 1 or
0.0721 g (0.069 mmol) of 2 in 1 mL hexane were added un-
der Ar the corresponding amount of styrene or methyl
methacrylate in sugar/alkene mole ratio 1, 0.5, 0.1 and
0.05, and 0.04 mL solution of TiCl4/AlEt3 (8 mg) in hexane
in molar rate Ti/Al = 8:1 under flow of Ar. The vials were
kept at 40 °C in an oil bath at normal pressure and conven-
tional heating for the estimated time (see Supplementary
data), then were cooled to r.t. and the product precipitated
300 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301
by dropping it into a 10-fold amount of cold EtOH. The
white solid (powder fraction) was filtered and washed sev-
eral times with cold EtOH. When possible (if the product
was easily soluble), the powder polymers were purified
by repeated dissolution in toluene and reprecipitation in
cold EtOH and dried under vacuum. In the cases where
no solid polymer was obtained, the unreacted alkene
monomers were distilled-off under vacuum to obtain a re-
sin-like polymer (resin fraction).
Acknowledgements
This work has been supported by Fundação para a Ciên-
cia e a Tecnologia (SFRH/BPD/9474/2002 and PTDC/QUI/
72120/2006).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.eurpolymj.
2008.10.013.
References
[1] Haworth WN, Gregory H, Wiggins KF. Some derivatives of simple
carbohydrates containing unsaturated substituents. J Chem Soc
1946:488–91.
[2] Patil DR, Dordick JS, Rentwisch D. Chemoenzymatic synthesis of
novel sucrose-containing polymers. Macromolecules
1991;24:3462–3.
[3] Chen X, Martin BD, Neubauer TK, Linhardt RJ, Dordick JS, Rethwisch
DG. Enzymatic and chemoenzymatic approaches to synthesis of
sugar-based polymer and hydrogels. Carbohydr Polym
1995;28(1):15–21.
[4] Jhurry D, Deffieux A, Fontanille M. Sucrose based polymers. Linear
polymers with sucrose side-chains. Macromol Chem
1992;193:2997–3007.
[5] Fanton E, Fayet C, Gelas J, Jhurry D, Deffieux A, Fontanille M.
Ethylenic acetals of sucrose and their copolymerization with vinyl
monomers. Carbohydr Res 1992;226:337–43.
[6] Akashi M, Sakamoto N. Synthesis and functionality of polysaccharide
vinyl analogue. Kagaku Kogyo 1994;45(6):507–15.
[7] Narain R, Jhurry D, Wulff G. Synthesis and characterization of
polymers containing linear sugar moieties as side groups. Eur Polym
J 2002;38:273–80.
[8] Ferreira L, Vidal MM, Geraldes CF, Gil MH. Preparation and
characterisation of gels based on sucrose modified with glycidyl
methacrylate. Carbohydr Polym 2000;41:15–24.
[9] Chen J, Park K. Synthesis of fast-swelling, superporous sucrose
hydrogels. Carbohydr Polym 2000;41:259–68.
[10] Carneiro MJ, Fernandes A, Figueiredo CM, Fortes AG, Freitas AM.
Synthesis of carbohydrate based polymers. Carbohydr Polym
2001;45:135–8.
[11] Park K, Waleed S, Shalaby W. Biodegradable hydrogels for drug
delivery. New York: CRC Press; 1993.
[12] Pachence JM, Kohn J. Principles of tissue engineering. New
York: Academic Press; 2000.
[13] Satomi M, Sogawa S. Hard coating layer for coated products useful in
pharmaceuticals and foodstuffs, contains sugar, and reduced
amylolysis product containing sugar composition of hydrogenated
saccharides with varying polymerization degree. Japan Patent
2007,053,952-A; 2007.
[14] Popplewell LM, Henson L. Method useful to deliver active ingredient
to cleaning composition involves preparing structured material of
hydrophilic particle, hydrophobic active ingredient and polyhydric
material; and providing the structured material into composition US
Patent 2007,048,339-A1; 2007.
[15] Singh RP, Pandey JK, Rutot D, Degee P, Dubois P. Biodegradation of
poly(E-caprolactone)/starch blends and composites in composting
and culture environments; the effect of compatibilization on the
inherent biodegradability of the host polymer. Carbohydr Res
2003;338:1759–69.
[16] Galgali P, Varma AJ, Puntambekar US, Gokhale DV. Towards
biodegradable polyolefines: strategy of anchoring minute
quantities of monosaccharides and disaccharides onto
functionalized polystyrene, and their effect on facilitating polymer
biodegradation. Chem Commun 2002:2884–5.
[17] Tokiwa Y, Fan H, Hiraguri Y, Kurane R. Biodegradation of a sugar
branched polymer consisting of sugar, fatty acid, and poly(vinyl
alcohol). Macromolecules 2000;33:1636–9.
[18] Khan R. Chemistry and new uses of sucrose: how important? Pure
Appl Chem 1984;56(7):833–44.
[19] Zoete MS, Kneepkens MF, Waard P, Osterom MW, Gotlieb KF,
Slagnek TM. Enzymatic synthesis and NMR studies of acylated
sucrose acetates. Green Chem 1999;1(3):153–6.
[20] Breuil VD, Pinel C, Gallezot P. Green approach to substituted
carbohydrates: telomerisation of butadiene with sucrose. Green
Chem 2001;3(4):175–7.
[21] Barros MT, Maycock CD, Rodrigues P, Thomassigny C. Improved
anomeric selectivity for the aroylation of sugars. Carbohydr Res
2004;339:1373–6.
[22] Andrade MM, Barros MT. Facile conversion of O-sylil protected
sugars into their corresponding formates using POCl3.DMF complex.
Tetrahedron 2004;60:9235–43.
[23] Barros MT, Maycock CD, Sineriz F, Thomassigny C. Fast galloylation
of a sugar moiety: preparation of three monogalloylsucroses as
references for antioxidant activity. A method for the selective
deprotection of tert-butyldiphenylsilyl ethers. Tetrahedron
2000;56:6511–6.
[24] Barros MT, Petrova K, Ramos AM. Regioselective copolymerization of
acryl sucrose monomers. J Org Chem 2004;69:7772–5.
[25] Barros MT, Petrova KT, Ramos AM. Biodegradable Polymers based on
a- or b-pinene and sugar derivatives or styrene, obtained under
normal conditions and microwave irradiation. Eur J Org Chem
2007:1357–63.
[26] Barros MT, Sineriz F. Synthesis of optically active monomers and
copolymers derived from protected 60 -O-acryloyl sucroses. Synthesis
2002;10:1407–11.
[27] Andrade MM, Barros MT, Rodrigues P. Selective synthesis under
microwave irradiation of carbohydrate derivatives containing
unsaturated systems. Eur J Org Chem 2007:3655–68.
[28] Fanton E, Fayet C, Gelas J, Deffieux A, Fontanille M, Jhurry D.
Synthesis of 4-O- and 6-O-monoacryloyl derivatives of sucrose by
selective hydrolysis of 4,6-O-(1-ethoxy-2-propenylidene)sucrose.
Polymerisation and copolymerisation with styrene. Carbohydr Res
1993;240:143–52.
[29] Potier P, Bouchou A, Descotes G, Queneau Y. Proteinase N-catalysed
transesterifications in DMSO-water and DMF-water: preparation of
sucrose monomethacrylate. Tetrahedron 2000;41:3597–600.
[30] Queneau Y, Fitremann J, Trombotto S. The chemistry of unprotected
sucrose: the selectivity issue. CR Chimie 2004;7:177–88.
[31] Jarosz S, Mach M. Regio- and stereoselective transformations of
sucrose at the terminal positions. Eur J Org Chem 2002:769–80.
[32] Crucho CC, Petrova KT, Pinto RC, Barros MT. Novel unsaturated
sucrose ethers and their application as monomers. Molecules
2008;13:762–70.
[33] Nobel e-Museum. Available from: <http://wwwnobelse/chemistry/
laureates/1963> [accessed 20.03.04].
[34] Natta G, Mazzanti G. Organometallic complexes as catalysts in ionic
polymerizations. Tetrahedron 1960;8:86–100.
[35] Ziegler K, Holzkamp E, Breil H, Martin H. Das Mülheimer
Normaldruck-Polyäthylen-Verfahren. Angew Chem 1955;67:
541–7.
[36] Elias H-G. Macromolecules I: structure and properties. New
York: Plenum Press; 1979.
[37] Lampe A. Contemporary polymer chemistry. Prentice-Hall; 1981. p.
384–9.
[38] Tonelli AE. NMR spectroscopy and polymer microstructure. New
York: VCH; 1989.
[39] Phan Q, Petiaud R, Waton H, Darricades MFL. Proton and carbon
NMR spectra of polymers. London: Penton Press; 1991.
[40] Pedroza OJO, Tavares MIB. The influence of physical treatment in the
polystyrene pentads microstructure determination by NMR. Polym
Test 2005;24:604–6.
[41] Price GJ, Patel AM. Ziegler–Natta polymerization under high
intensity ultrasound. Polymer 1992;33(20):4423–33.
[42] Hiorns RC, Khoukh A, Ghigo P, Prim S, Francois J. A convenient route
to high molecular weight highly isotactic polystyrene using Ziegler–
Natta catalysts and ultrasound. Polymer 2002;43:3365–9.
[43] Rooney JJ, Stewart A. Catalysis, (specialist periodical
reports). London: The Chemical Society; 1977.
 M.T. Barros, K.T. Petrova / European Polymer Journal 45 (2009) 295–301 301

[44] Hein PR. Ring-opening polymerizations of cyclic olefins. J Polym Sci [47] Perrin DD, Armagedo WLF, Perrin DR. Purification of laboratory
1973;11:163–73. chemicals. New York: Pergamon Press Ltd.; 1980.
[45] Zakharov VA, Bukatov GD, Yermakov YI. On the mechanism of olefin [48] Available from: <http://wwwbiccom/90PDPhtml>.
polymerization by Ziegler–Natta catalysts. Berlin/ [49] Weast RC, editor. Handbook of chemistry and physics. 89th ed. West
Heidelberg: Springer; 1983. Palm Beach, Florida: CRC Press, Inc.; 2008.
[46] Marques MM, Costa C, Lemos F, Ribeiro FR, Dias AR. A kinetic
approach to homogeneous Ziegler type polymerization. Steady state.
React Kinet Catal Lett 1997;62(1):9–15.