Synthesis, characterization, and thermal properties of diacrylic/ divinylbenzene copolymers

Article abstract of DOI:10.1007/s10973-009-0574-6

In this article, synthesis, characterization, and thermal properties of diacrylic/divinylbenzene copolymers based on the new aromatic tetrafunctional acrylate monomers are presented. The new monomers were generated by treatment of epoxides derived from various aromatic diols: naphthalene-2,3-diol (NAF), biphenyl-4,4′-diol (BIF), bis(4-hydroxyphenyl)methanone (BEP) or 4,4′-thiodiphenol (BES), and epichlorohydrin with acrylic acid. The addition reaction was carried out by a ratio of 0.5 mol of suitable epoxy derivative and 1 mol of acrylic acid in the presence of 0.7 wt% of triethylbenzylammonia chloride (TEBAC) as a catalyst and 0.045 wt% of hydroquinone as a polymerization inhibitor. The chemical structure of the prepared acrylate monomers was confirmed by ¹³C NMR and GC MS spectra. The emulsion-suspension polymerization of acrylate monomers with divinylbenzene (DVB) in the presence of pore-forming diluents (toluene + decan-1-ol) allowed obtaining microspheres containing pendant functional groups (hydroxyl groups). This process was carried out at constant mol ratio of acrylate monomers: DVB (1:1), and constant volume ratio of pore-forming diluents to monomers (1:1). The different concentrations of toluene in the mixture with decan-1-ol were used for qualifying the effect of the diluents on the microsphere characteristics. The influence of synthesis's parameters on the properties of copolymer beads, e.g., pore size and surface area by BET method, the surface texture by AFM, swelling behavior in polar and non-polar solvents as well as thermal stability by differential scanning calorimetry (DSC), and thermogravimetric analysis (TG) was studied and discussed.

Full text of DOI:10.1007/s10973-009-0574-6

J Therm Anal Calorim (2010) 101:235–241
DOI 10.1007/s10973-009-0574-6
Synthesis, characterization, and thermal properties
of diacrylic/divinylbenzene copolymers
•
Beata Podkoscielna Marta Worzakowska
´
Received: 27 June 2009 / Accepted: 16 October 2009 / Published online: 5 November 2009
´
´
Ó Akademiai Kiado, Budapest, Hungary 2009
Abstract In this article, synthesis, characterization, and
thermal properties of diacrylic/divinylbenzene copolymers
based on the new aromatic tetrafunctional acrylate mono-
mers are presented. The new monomers were generated by
treatment of epoxides derived from various aromatic diols:
naphthalene-2,3-diol (NAF), biphenyl-4,40-diol (BIF),
bis(4-hydroxyphenyl)methanone (BEP) or 4,40-thiodiphe-
nol (BES), and epichlorohydrin with acrylic acid. The
addition reaction was carried out by a ratio of 0.5 mol of
suitable epoxy derivative and 1 mol of acrylic acid in the
presence of 0.7 wt% of triethylbenzylammonia chloride
(TEBAC) as a catalyst and 0.045 wt% of hydroquinone as a
polymerization inhibitor. The chemical structure of the
prepared acrylate monomers was confirmed by 13C NMR
and GC MS spectra. The emulsion–suspension polymeri-
zation of acrylate monomers with divinylbenzene (DVB) in
the presence of pore-forming diluents (toluene ? decan-
1-ol) allowed obtaining microspheres containing pendant
functional groups (hydroxyl groups). This process was
carried out at constant mol ratio of acrylate monomers:
DVB (1:1), and constant volume ratio of pore-forming
diluents to monomers (1:1). The different concentrations of
toluene in the mixture with decan-1-ol were used for
qualifying the effect of the diluents on the microsphere
characteristics. The influence of synthesis’s parameters on
the properties of copolymer beads, e.g., pore size and
surface area by BET method, the surface texture by AFM,
swelling behavior in polar and non-polar solvents as well
as thermal stability by differential scanning calorimetry
(DSC), and thermogravimetric analysis (TG) was studied
and discussed.
Keywords Emulsion–suspension polymerization ꢀ
Multifunctional acrylate monomers ꢀ Copolymers ꢀ
Porous microspheres
Introduction
Synthetic polymers play a very important role in everyday
life as well as in different branches of industry. They exist
throughout the world as materials ranging from nylon fibers
to reinforced composites. Functional polymer networks
have gained a great importance in many fields of science
and industrial applications due to the variety of alternative
modifications of their chemical and physical properties
[1–4]. In recent years, polymeric materials with porous
structure are finding ever increasing applications in various
fields. They are applied as precursors for the preparation of
various types of ion exchange resins, inert supports for
chromatographic purposes, supports for classical catalysts,
and membranes. They are usually used in chromatography,
biotechnology, optics, electronics, and chemical technol-
ogy [5–10]. Porous polymer beads have been prepared by
copolymerization of vinyl monomers and cross-linking
agents such as divinylbenzene in the presence of an inert
diluents (porogens) by different methods of polymeriza-
tions: suspension, emulsion, dispersion, emulsion–suspen-
sion, etc. [11, 12]. The various factors, e.g., temperature,
amount of cross-linking monomer and initiator, the type of
vinyl monomers, composition of the porogenic solvents
influence on porous structure, mechanical strength, thermal
stability, and resistance to solvent absorption of beads [13].
´
B. Podkoscielna (&) ꢀ M. Worzakowska
Department of Polymer Chemistry, Faculty of Chemistry,
MCS University, Gliniana 33 Street, 20-614 Lublin, Poland
e-mail: beatapod@poczta.umcs.lublin.pl
M. Worzakowska
e-mail: marta.worzakowska@poczta.umcs.lublin.pl
123

´
B. Podkoscielna, M. Worzakowska
236
The most popular macroporous copolymers based on sty-
rene/divinylbenzene are hydrophobic materials which are
characterized by insufficient exchange rates in aqueous
media [14]. For application in aqueous system, less
hydrophobic polymeric materials are desirable. Hydroxy-
acrylate or meth(acrylate) monomers or resins represent an
important group of less hydrophobic materials. Copoly-
merization of multifunctional (meth)acrylate monomers
with vinyl monomer allows to produce highly cross-linked
polymers with high thermal stability, porous structure,
mechanical strength, and resistance to solvent absorption
due to the presence of hydrophilic groups in the structure of
the obtained materials [15–24]. The meth(acrylate) mono-
mers are frequently produced during the esterification
process of epoxide compounds or resins with acrylic or
methacrylic acid in the presence of a acidic or basic type
catalyst or transition metal complexes [25]. Recently, many
such hydrophilic, porous materials have received a great
amount of attention due to their unique properties suitable
for applications in biomedicine- or polymer-supported
reactions using enzymes.
Germany). DVB was washed with 3% aqueous sodium
hydroxide prior to use. Reagent grade acetone, methanol,
chloroform, toluene, sodium hydroxide, potassium hydrox-
ide, and hydroquinone were from POCh (Gliwice, Poland).
Triethylbenzylammonia chloride (TEBAC) was prepared as
per the procedure described by Ma˛kosza [26].
Preparation of new aromatic tetrafunctional acrylate
monomers
The new aromatic tetrafunctional acrylate monomers were
generated by treatment of epoxides derived from various
aromatic diols:naphthalene-2,3-diol (NAF), biphenyl-4,40-
diol (BIF), bis(4-hydroxyphenyl)methanone (BEP) or 4,40-
thiodiphenol (BES), and epichlorohydrin (I step, Fig. 1)
with acrylic acid (II step, Fig. 1). This process was per-
formed in a three-necked round-bottomed flask (500 cm3)
equipped with a thermometer, a mechanical stirrer, and a
heating jacket in the temperature range of 80–100 °C. The
reaction was carried out with a ratio of 0.5 mol of suitable
epoxy derivative of aromatic diols and 1 mol of acrylic
acid in the presence of 0.7 wt% of TEBAC as a catalyst,
and 0.045 wt% of hydroquinone as a polymerization
inhibitor. The reaction course extent was controlled by
estimating the value of an acid number (defined as a
number of mg KOH required for the titration of 1 g of a
sample) of the reaction mixture. The drop in the value of an
acid number below 3 mg KOH/g marked the indication of
the process completion. In this way, the new, correspond-
ing aromatic tetrafunctional acrylate monomer derivatives
of various diols, such as NAF–DA, BIF–DA, BEP–DA, or
BES–DA were prepared. Their respective chemical struc-
tures were confirmed by 13C NMR and GC MS methods.
In this article, synthesis, characterization, and thermalpro-
perties of porous diacrylic/divinylbenzene copolymers are
presented. They were produced during emulsion–suspension
polymerization of new aromatic tetrafunctional acrylate
monomers derivatives of various diols: naphthalene-2,3-diol
(NAF), biphenyl-4,40-diol (BIF), bis(4-hydroxyphenyl)
methanone (BEP), or 4,40-thiodiphenol (BES) with divinyl-
benzene (DVB) in the presence of pore-forming diluents
(toluene ? decan-1-ol). This preparation method allowed
obtaining more hydrophilic porous microspheres containing
ester groups and pendant functional groups (hydroxyl
groups). The influence of synthesis’s parameters on surface
area, surface texture, swelling behavior in polar, and non-
polar diluents as well as thermal stability was discussed.
Preparation of diacrylic/divinylbenzene copolymers
The copolymers in the form of microspheres were pro-
duced during the emulsion–suspension polymerization of
new aromatic tetrafunctional acrylate monomers and DVB.
First, 150 mL of redistilled water and 1.4 g of bis(2-eth-
ylhexyl)sulfosuccinate sodium salt (surfactant) were placed
in a three-necked flask equipped with a stirrer, a water
condenser, and a thermometer and stirred for 1 h at 80 °C
to obtain the aqueous medium. Then, 1.5 wt% of a,a0-
azoisobisbutyronitrile (initiator), the mixture of pore-
forming diluents (toluene and decan-1-ol), suitable acrylate
monomer, and DVB were added to the aqueous medium
forming a solution with stirring. The emulsion–suspension
polymerization was performed at the constant mol ratio of
acrylate monomer:DVB (1:1) at 80 °C for 18 h. The
obtained microspheres (NAF.A–DVB, BIF.A–DVB,
BEP.A–DVB, or BES.A–DVB) were thoroughly washed
Experimental
Materials
Epoxides derived from various aromatic diols: naphtha-
lene-2,3-diol (NAF), biphenyl-4,40-diol (BIF), bis(4-
hydroxyphenyl)methanone (BEP) or 4,40-thiodiphenol
(BES), and epichlorohydrin (I step, Fig. 1) were used as
basic reagents in the synthesis of the new acrylate mono-
mers. Their preparation and properties were precisely
described in our previous articles [23, 24].
Bis(2-ethylhexyl)-sulfosuccinate sodium salt (DAC,BP),
decan-1-ol, tetrahydrofuran (THF), and acrylic acid (A) were
purchased from Fluka AG (Buchs Switzerland). Bis(4-
hydroxyphenyl)sulfide, a,a0-azoisobisbutyronitrile, and divi-
nylbenzene (DVB) were obtained from Merck (Darmstadt,
123

Synthesis, characterization, and thermal properties
237
Fig. 1 Structure of acrylate
monomers and their
copolymerization with DVB
with distilled water, filtered out, dried, and extracted in a
Soxhlet apparatus with boiling acetone and methanol.
atmosphere (30 mL min-1). The mass of the sample was
*10 mg. As a reference, an empty aluminum crucible was
used. The glass transition temperature (Tg), decomposition
temperature (Td), and enthalpy of decomposition (DHd)
were evaluated.
Characterization
GC MS was made on a Thermo-Finnigan DSQ spectrom-
eter (Finnigan, USA) connected to a gas chromatograph
Trace GC-Ultra equipped with a fused-silica RTX-5 cap-
illary column (20 m 9 0.18 mm I.D., film thickness
0.20 lm). The conditions were as follows: injector PTV-
split 1:20, program temperature 35–320 °C at the rate of
20 °C min-1, MS electron ionization at 70 eV, and tem-
perature of ion volume 220 °C.
Thermogravimetric analysis (TG) was carried out on a
Paulik and Erdey derivatograph (Budapest, Hungary) at a
heating rate of 10 °C min-1 in air, in the temperature range
of 20–1000 °C with the sample weight of 100 mg. As a
reference, a-Al2O3 was used. The initial decomposition
temperature (IDT), T20%, and T50% of weight loss, final
decomposition temperature (Tend), and temperature of the
maximum rate of weight loss (Tmax) were determined.
13C NMR spectra were recorded on a Brucker 300 MSL
instrument (Brucker, Germany). Chemical shifts were
referred to chloroform serving as an internal standard.
The specific surface areas were calculated by the BET
method, assuming that the area of a single nitrogen mole-
Results and discussion
Characterization of new aromatic tetrafunctional
acrylate monomers
2
˚
cule is 16.2 A . These determinations were made with the
use of an adsorption analyzer ASAP 2405 (Micrometrics
Inc., USA). The measurements of the surface properties of
the copolymers were preceded by activation of the samples
at 200 °C for 2 h.
The microspheres were also tested by an atomic force
microscope (AFM), AFM Nanoscope III (Digital Instru-
ments, USA), operating in the contact mode. The presented
images contained 512 9 512 data points obtained within a
few seconds. The typical force applied to obtain these
images ranged from 1.0 to 100 nN.
The theoretical chemical structure of prepared new aromatic
tetrafunctional acrylate monomers: NAF–DA, BIF–DA,
BEP–DA, or BES–DA is presented in Fig. 1. Their structure
is confirmed by 13C NMR, Table 1, Fig. 2; and GC MS
analyses, Fig. 3. The characteristic signals for carbon ter-
minal of the double bond and more highly substituted ones as
well as signals for the carbonyl groups, methylene groups,
and secondary hydroxylic groups were found. It confirmed
that the addition reaction of epoxide groups to the carboxylic
ones was successful. No side reactions of the formed sec-
ondary hydroxyl groups with epoxy groups (etherification)
or with acid groups (esterification) were observed. In addi-
tion, GC MS analysis of prepared monomers clearly showed
the presence of molecular ions corresponding to the calcu-
lated molecular weights of NAF–DA (416 g mol-1), BIF–
DA (442 g mol-1), BEP–DA (470 g mol-1), and BES–DA
The calorimetric measurements were carried out in the
Netzsch DSC 204 calorimeter (Selb, Germany) operating
in a dynamic mode. The dynamic scans were performed at
a heating rate of 10 K min-1 at two temperature scans.
First scan was performed from 20 °C to a maximum of
110 °C to remove any adsorb moisture. The second one
was conducted between 20 and 500 °C under nitrogen
123

´
B. Podkoscielna, M. Worzakowska
238
Table 1 13C-NMR data for acrylate monomers
monomers:DVB (1:1) and a constant volume ratio of pore-
forming diluents to monomers (1:1). Different concentra-
tions of toluene in the mixture with decan-1-ol were used,
Table 2 to study the influence of organic solvents on the
microsphere characteristic, their porous structure, and pore
size distribution. The preparation of microspheres based on
NAF–DA and BES–DA monomers for all the used con-
centrations of toluene with the mixture of decan-1-ol was
observed, Table 2. However, probably owing to the poor
dissolubility of solid BIF–DA and BEP–DA monomers in
toluene, the formation of microspheres in decan-1-ol were
only observed (synthesis no. 6, Table 2). The results pre-
sented in Tables 3 and 4, suggested that the surface char-
acteristic and the pore structure of acrylic copolymers
significantly depended on the chemical structure of
monomers and the nature of the used solvents. The swel-
lability coefficients (B) varied from 12 to 28% for all the
polar solvents. The significantly higher values of B in polar
solvents compared to those values in non-polar hexane
were observed. Such behavior was probably due to the
presence of polar pendant functional groups (hydroxyl
groups) in copolymers. Moreover, the highest swelling and
surface area but lower average pore diameter for BES.A–
DVB copolymer compared with NAF.A–DVB was
observed, Table 4. It was probably connected with the
presence of macro- and micropores in the structure of
BES.A–DVB copolymer. Higher elasticity of monomer
Monomer
ppm
=CH2
–CH=CH2
–CH2–
OH
CH
O
C
NAF–DA
128.0
68.4
132.0
166.3
65.4
70.5
65.6
70.0
65.4
69.7
65.4
68.9
BIF–DA
BEP–DA
BES–DA
128.0
125.3
127.9
68.9
69.0
68.3
132.0
132.3
132.6
166.4
166.3
194.5
166.2
(474 g mol-1). The exemplary mass spectrum of BES–DA
monomer is presented in Fig. 3.
Characterization of diacrylic/divinylbenzene
copolymers
The copolymers were produced during the emulsion–sus-
pension polymerization of new aromatic tetrafunctional
acrylate monomers with DVB in the presence of pore-
forming diluents (toluene ? decan-1-ol). This process
was performed at a constant mol ratio of acrylate
O
3
2
C
1
4
O
O
C
5
10
C
9
HC
CH
O
C
O
O
C
O
CH
8
6
7
H
CH
H
CH
CH
2
11
10
3
2
2
2
2
2
CH
OH
CH
HO
O
3
OH
CH
6
CH
8
CH 11
2
CH
7
O
C
9
CH
10
2
2
2
4
3
1
5
O
O
1
4
OH
O
3
CH
CH CH
O
C
CH CH
2
2
2
11
5
3
9
78
10
4
9
2
11
5
6
2
7
1
6
1
8
ppm
ppm
200 190 180 170 160 150 140 130 120110 100 90 80 70 60 50 40 30 20 10
170 160 150 140 130 120 110 100 90
80
70
60
50
10
O
O
9
2
CH
C
CH
C
S
1
9
2
8
3
3
O
C
O
C
3
H
C
O
O
CH
2
10
5
CH
7
CH
2
8
1
4
4
CH
CH
6
CH
9
CH
H
C
O
O
2
CH
2
O
2
2
O
CH
7
2
2
CH
CH
O
O
CH
HC
6
10
0
CH
CH
5
2
2
10
CH
2
OH
OH
2
HO
OH
2
4
6
7
8
2
5
9
5
8
7,6
1
4
4
2
1
Fig. 2 13C-NMR spectra of acrylate monomers: 1 NAF–DA, 2 BIF–DA, 3 BEP–DA, 4 BES–DA
123

Synthesis, characterization, and thermal properties
239
Fig. 3 Mass spectrum of BES–
DA monomer
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
50
100
150
200
250
m/z
300
350
400
450
Table 2 Volume ratio of diluents used for emulsion–suspension polymerization process and product characterization
Synthesis no.
Diluent/mL
T
Product
D
NAF.A–DVB
BIF.A–DVB
BEP.A–DVB
BES.A–DVB
1
2
3
4
5
6
16
14
8
0
m
m
m
m
m
m
k
k
k
k
k
m
k
k
k
k
k
m
m
m
m
m
m
m
2
8
4
12
14
16
2
0
T toluene, D dekan-1-ol, m microspheres, k coagulated
Table 3 Swelling studies for diacrylic/divinylbenzene copolymers
Table 4 Porous structure of diacrylic/divinylbenzene copolymers
Copolymer
Swellability coefficient, B/%
Copolymer
Specific surface Pore volume/ Average pore
mL g-1
area/m2 g-1
˚
diameter/A
Acetone Methanol THF Acetonitryle Hexane
NAF.A–DVB—
synthesis No. 5
72
0.42
231
NAF.A–DVB 12
12
10
5
14
12
8
10
8
5
5
BIF.A–DVB
BEP.A–DVB
15
6
BES.A–DVB—
synthesis No. 3
103
0.43
162
6
0
BES.A–DVB 16
24
28
20
12
Thermal properties of NAF.A–DVB, BIF.A–DVB,
BEP.A–DVB and BES.A–DVB copolymers were studied
by means of DSC and TG analyses. The DSC was per-
formed in a nitrogen atmosphere with temperatures ranging
from 20 to 500 °C. The TG was conducted in air from 20 to
1000 °C. The DSC curves of diacrylic/divinylbenzene
copolymers are presented in Fig. 5. In addition, the char-
acteristic temperatures: Tg, Td, and the enthalpy of
decomposition (DHd) are given in Table 5. DSC analysis
showed similarity in thermal behavior for all the prepared
copolymers. The characteristic, well-shaped calorimetric
containing sulfur caused larger penetration of porogens
diluents during polymerization process resulting in the
formation of more developed porous structure with a rel-
atively broad pore size. The surface texture studies by
AFM performed in addition confirmed that NAF.A–DVB
and BES.A–DVB copolymers were characterized by a
porous structure, Fig. 4. On the contrary, BIF.A–DVB and
BEP.A–DVB copolymers were characterized by the lowest
swelling properties. This characterization is connected with
non-porous, faintly developed surface area which is clearly
observed from AFM images.
123

´
B. Podkoscielna, M. Worzakowska
240
1
Exo
Digital Instruments Nanoscope
Scan size
1.000 µm
Scan rate
0.2999 Hz
256
Height
Number of samples
Image data
Data scale
1
2
1.000 µm
3
4
0.2
0.4
0.6
0.6
0.6
X
Z
0.200 µm/div
0.8
0.8
0.8
1000.000 nm/div
µm
naf–akr.002
20
80
380
200
260
440
320
140
500
Digital Instruments Nanoscope
Scan size
Scan rate
Number of samples
Image data
Data scale
2
Temperature/°C
1.000 µm
0.5003 Hz
256
Height
300.0 nm
Fig. 5 DSC curves of diacrylic/divinylbenzene copolymers:
1 NAF.A–DVB, 2 BIF.A–DVB, 3 BEP.A–DVB, 4 BES.A–DVB
Table 5 DSC data for diacrylic/divinylbenzene copolymers
0.2
Copolymer
Tg/°C
T
max1/°C
Td/°C
DHd/J g-1
0.4
X
Z
0.200 µm/div
300.000 nm/div
NAF.A–DVB
BIF.A–DVB
BEP.A–DVB
BES.A–DVB
101.5
100.6
102.4
100.6
390
404
408
396
421.5
434.4
433.4
422.3
91.3
100.6
58.8
bif–a.000
µm
Digital Instruments Nanoscope
Scan size
Scan rate
Number of samples
Image data
Data scale
1.000 µm
0.4002 Hz
256
Height
300.0 nm
3
73.5
characterized by rather high thermal stability, and no
endothermic decomposition peak until 250–300 °C was
observed. The TG analysis confirmed those observations.
The initial decomposition temperatures (IDTs) for all
copolymers were from 250 to 310 °C. The final decom-
position temperatures (Tend) were in the range of 780–
940 °C. The DTG curves contained two separated degra-
dation steps. The first decomposition peak was observed in
the range of 250–390 °C with the maximum weight loss
(Tmax1) at 360–375 °C. The second decomposition stage
took place between 480 and 940 °C with Tmax2 at 565–
575 °C, Table 6. The first decomposition peak could be
associated with the ester bonds breakdown in copolymers,
whereas the second one could be attributed to the total
degradation of copolymers [27, 28].
0.2
0.4
X
Z
0.200 µm/div
300.000 nm/div
co–a.001
µm
Digital Instruments Nanoscope
Scan size
Scan rate
Number of samples
Image data
Data scale
1.000 µm
0.5003 Hz
256
Height
500.0 nm
4
0.2
0.4
0.6
X
Z
0.200 µm/div
500.000 nm/div
0.8
aes–dvb.013
µm
Fig. 4 Contact-mode AFM imagines of diacrylic/divinylbenzene
copolymers: 1 NAF.A–DVB, 2 BIF.A–DVB, 3 BEP.A–DVB, 4
BES.A–DVB
Conclusions
The synthesis, characterization, and thermal properties of
diacrylic/divinylbenzene copolymers based on the new
aromatic tetrafunctional acrylate monomers were pre-
sented. The acrylate monomers were obtained by treatment
of epoxides derived from various aromatic diols: naph-
thalene-2,3-diol (NAF), biphenyl-4,40-diol (BIF), bis(4-
hydroxyphenyl)methanone (BEP) or 4,40-thiodiphenol
(BES), and epichlorohydrin with acrylic acid. Their
emulsion–suspension polymerization with DVB in the
profile, revealing two non-distributed asymmetrical peaks
was observed. The first, exothermic peak (Tmax1) starting at
about 300 °C can be attributed to the additional double
bond copolymerization process. The endothermic peaks at
421.5–434.4 °C with DHd values from 58.8 to 100.6 J g-1
corresponded with the thermal degradation of cross-
linked microspheres. Moreover, the copolymers were
123

Synthesis, characterization, and thermal properties
241
Table 6 TG and DTG data for diacrylic/divinylbenzene copolymers
Copolymer
IDT/°C
T
20%/°C
T50%/°C
T
end/°C
T
max1/°C
Tmax2/°C
NAF.A–DVB
BIF.A–DVB
BEP.A–DVB
BES.A–DVB
280
310
250
280
380
390
360
380
480
520
500
500
860
940
780
880
375
375
370
360
570
570
575
565
cosolvents by different techniques. J Therm Anal Calorim. 2008;
94:109–18.
13. Bisjak CP, Lubbad SH, Trojer L, Bonn GK. Novel monolithic
poly(phenyl acrylate-co-1,4-phenylene diacrylate) capillary col-
umns for biopolymer chromatography. J Chromatogr A. 2007;
1147:46–52.
14. Rohr T, Knaus S, Sherrigton DC, Gruber H. Synthesis of sugar-
containing hydrophilic porous polymer supports via suspension
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presence of pore-forming diluents (toluene ? decan-1-ol)
allowed obtaining more hydrophilic microspheres due to
the presence of ester and hydroxyl groups in their structure.
Based on the performed analyses, it was found that the
parameters of the synthesis as well as the structure of initial
acrylate monomers had a significant influence on the
properties of final product. DSC and TG analyses indicated
on high thermal stability of diacrylic/divinylbenzene
copolymers up to 250–300 °C which was directly con-
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´
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