European Polymer Journal 37 (2001) 1499±1505

www.elsevier.nl/locate/europolj

Copolymerization of vinyl acetate with acrylic monomers in

microemulsion
Dan Donescu a,*, Liana Fusulan a, Cristian Petcu a, Adrian-Gelu Boborodea b,
Dan-Sorin Vasilescu b
a
Department of Polymer Syntheses, ICECHIM, Institute for Chemical Research, 202 Splaiul Independentei, P.O. Box 15-159,
Bucharest 77208, Romania
b
Laboratory of Polymer Physics, University ``Politehnica'' of Bucharest, 149 Calea Victoriei, Bucharest 77101, Romania
Received 16 August 1999; received in revised form 15 August 2000; accepted 7 December 2000

Abstract
Composition domains corresponding to ``one phase microemulsions'' have been studied for the monomer mixtures
consisting in vinyl acetate (VAc)±2-ethyl-hexyl acrylate (EHA) and VAc±ethyl acrylate (EtA). Maleic monoester with
nonyl phenol ethoxylated with 25 mol ethylene oxide has been used as surfactant; n-propanol (n-PrOH), t-butanol (t-
BuOH) and 2-ethyl-hexanol have been employed as cosurfactants. The number of microemulsions formed in the frame
of the existing systems (as shown in ternary diagrams) is higher for polar monomers and cosurfactants: EtA > EHA;
n-PrOH > t-BuOH. Refractometric and conductometric studies have proved the reality of three types of microemul-
sions: O=W , bicontinuous and W =O respectively. The homogeneous domains lessen after radical copolymerization.
However, for the zone with a bicontinuous microstructure the conversion for the comonomer mixture reaches a
minimum; a degradative chain transfer of the growing radicals with the cosurfactant might explain this phenomenon. It
has been proved by GPC, that the concentration of unreacted surfactant increases when the concentration of the acrylic
monomer increases as well. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Microemulsion; Vinyl acetate; Acrylic monomers; Monomaleate; n-Propanol; H2 O

1. Introduction toluene [10], SCC produce an increase of their solubility

Polymerization of vinyl and acrylic monomers in
microemulsion, in the presence of short chain cosurf-
actants (SCC) has been the subject of numerous studies
[1±17]. When preparing microemulsions it has been
proved that the presence of cosurfactants increases the
composition domain corresponding to ``single phase
microemulsion'' in the case of methyl methacrylate
(MMA) [1±8] or vinyl acetate (VAc) [11]. Also for more
hydrophobic monomers such as styrene [9] or vinyl-
*
Corresponding author. Tel.: +401-315-3299; fax: +401-312-
3493.
E-mail address: icctrim@sunu.rne.ro (D. Donescu).
in O=W microemulsions.
The fact that microemulsions are obtained only in
``surfactant-free'' systems [2±4,18] represents the evi-
dence that SCC exhibit an amphiphilic nature. Although
the hydrophobic part of SCC (C1 ±C4 ) is quite short, in
aqueous solutions, hydrophobic demixtion may take
place [19]. For instance, nanostructures containing eight
molecules of propanol (PrOH) and 40 molecules of
water (the hydrophobic zone has a diameter of 12.4 A) 
have been put into evidence; alcohol-type SCCs induce
an un-structuration of water, as they are included in its
hexagonal clusters [20]. It has been found for the system
alcohol/water, that for a ratio one-®fth the physical
properties undergo marked changes [21]; nonetheless it
has to be pointed out that this ratio is the same as that
from above-described nanostructures [20].

0014-3057/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 4 - 3 0 5 7 ( 0 0 ) 0 0 2 6 0 - 3
1500 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505
The initial ratio between the organic O† and aqueous
W † phases is paramount in forming O=W , bicontinuous
or W =O microemulsions [2±8].
In previous studies [22], we have presented the
copolymerization of VAc with 2-ethyl-hexyl-acrylate
(EHA) in the presence of PrOH and of an ethoxylated
surfactant. It has been shown that the probability to
form initial microemulsions and homogeneous systems
after polymerization, for this comonomer mixture, de-
creases when EHA concentration increases [22].
In the present paper, we depict the in¯uence of co-
surfactant, and of acrylic comonomer, for copolymer-
ization of VAc in the presence of a reactive surfactant.
2. Experimental
2.1. Materials
VAc, EHA and ethyl acrylate (EtA), as commercial
products have been puri®ed by conventional distillation.
PrOH, t-butanol (t-BuOH) (Loba) and 2-ethyl-hexanol
(EHOH) (Solventul) have been used as such. Benzoyl
peroxide (Bz2 O2 ) (Chimopar) has been used without
further puri®cations.
The surfactant, monomaleate of nonyl-phenol eth-
oxylated with 25 mol of ethylene oxide (MEMNPEO25 )
has been synthesized from maleic anhydride and nonyl-
phenol ethoxylated with 25 mol of MEMNPEO25 at
65°C, according to a previously reported procedure [23].
2.2. Procedures
Microemulsions have been obtained by carrying out
the same procedure as previously reported [15±17].
Fig. 1. Modi®cation of the number of (a±c) homogeneous samples and (d±f) homogeneous systems after polymerization for the
mixtures: VAc=EHA ˆ 80=20 (a,b,d,e), 50/50 (c,f), Bz2 O2 ˆ 2%† (d,e), 0.5% (f); polymerization time 24 h, 65°C.
Monomer mixtures consisting in VAc/acrylic monomers
have been prepared in the ratios 80/20 and 50/50 (w/w).
As organic phase O† we have prepared ®ve mixtures
monomers=alcohol ˆ 10=90; 30/70; 50/50; 70/30; 90/10
(weight ratios); each solution was in turn, mixed with the
aqueous phase W †. In all the circumstances, the aque-
ous phase W † consisted in a solution 33% (w/w) of
MEMNPEO25 in water.
After vigorous stirring, the systems have been kept
for 24 h at room temperature, to reach equilibrium; in
this way, 45 distinct mixtures have been achieved.
The homogeneous samples (visually identi®ed as
such) have been presented in Figs. 1 and 4; those, where
three phases are in copresence have been mentioned in
Fig. 2. All systems separated in two phases have not
been represented.
Homogeneous samples containing initiator (Bz2 O2 ±
2% with respect to monomers) have been introduced in
glass ampoules which, subsequently, have been sealed
o€. Polymerizations were carried out at 65°C during
24 h.
2.3. Analyses
Monomer conversion has been gravimetrically ob-
tained. Refractive indexes were measured with an Abbe
refractometer, while the conductivities have been ob-
tained with a Radelkis OK 102/1 instrument; all mea-
surements have been carried out at 25°C.
Molecular weight distribution, as well as the con-
sumption of the reactive surfactant has been found out
by gel permeation chromatography with an Waters
Model 510 apparatus endowed with a RI Model 410
detector. The set of columns used has covered the do-
 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505
Fig. 2. Domains where there are three phases (o) for the sys-
tems: VAc=EHA ˆ 80=20, EHOH, MEMNPEO25 , 33%.
main between 100 and 4  106 ; all calculations were
made based on polystyrene standards.
3. Results and discussion
The domains found for ``one-phase microemulsion''
for the mixtures VAc/EHA are presented in Fig. 1.
In good agreement with previously reported data
[12,22], the presence of a comonomer (or SCC) with a
higher hydrophoby, would reduce the number of mi-
croemulsions formed; indeed, a comonomer (or SCC)
with a long hydrocarbon chain (EHA or tBuOH) would
induce a powerful ``hydrophobic demixtion'', which, in
turn, would generate phase separation and, accordingly,
reducing of the number of homogeneous systems.
The same result has been reported for MMA, when
using methacrylic acid as SCC [3]. When EHOH (an
alcohol not soluble in water) has been used as cosurf-
Fig. 3. Dependence of refractive indexes, derivatives curves and conductivity for the microemulsions as a function of the X value;
VAc=EHA ˆ 80=20 (a,a0 ,c), 50/50 (b,b0 ); monomers=PrOH ˆ 50=50, 30/70, 10/90; X ˆ W = W ‡ O†.
1501
actant in the presence of a mixture VAc=EHA ˆ 80=20,
then ``one-phase microemulsions'' cannot be obtained.
In this case, two or even three di€erent phases are pro-
duced; the domains where there are three phases are il-
lustrated in the ternary diagram presented in Fig. 2.
Also, it has been noticed that microemulsions are
formed in the intermediate layer between the already
separated organic and aqueous phases, respectively.
Both, for Figs. 1 and 2, the systems separated in two
phases are not speci®cally marked; the composition
zones for these systems are very di€erent.
It is known that alcohols, even in dilute solutions,
reveal a tendency towards association (hydrophobic
demixtion) [24]. EHOH forms mixed aggregates where
some monomers are included; the volume of the inter-
mediate phase (having a gel-like appearance), which
contains these aggregates, reaches a maximum for a
molar ratio monomer=EHOH ˆ 10=90 and in the do-
main characterized by a large amount of aqueous phase
(and accordingly for high concentrations of both surf-
actant and cosurfactant).
The very existence of nanostructures in SCC-con-
taining microemulsions has been con®rmed by the
nonlinear variation of refractive indexes as a function of
the X W = O ‡ W †† (see Fig. 3); the organic phase
consisted in mixtures monomer=PrOH ˆ 50=50; 30/70;
10/90.
Refractive indexes of the organic phase are higher
than those of the aqueous phase; introduction of the
organic phase leads to an association of SCC. In the
formed nanostructures, hydrocarbon zones (containing
1502 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505
Fig. 4. Changes in the number of initially homogeneous sam-
ples (a) after polymerization (b) for the system VAc=EtA ˆ
80=20 (Bz2 O2 ˆ 2%; polymerization time 24 h, 65°C).
SCC, monomers and surfactant ± at local concentrations
higher than the average concentrations) are produced.
For this reason, a positive alteration from linearity
arises; this behavior was not noticed at systems con-
taining monomers/PrOH, where there are no such
nanostructures [22].
To put into evidence the changes for the refractive
indexes, we have also presented the di€erentials of the
0 0
curves n25D ˆ f X †, as shown in Fig. 3a and b . The
system corresponding to ®gures a, a0 for the ratio
monomer=PrOH ˆ 30=70 has been already reported
[22]; it suggests the resemblance of the reactive surfac-
tant MEMNPEO25 with the nonionic surfactant from
which the former has been prepared.
By studying the conductivity of microemulsions (see
Fig. 3c) we have noticed the very good agreement with
the already published results [3±8,12,15,17]. Three zones
may be noticed: (A) a rapid decrease of the conductivity
Fig. 5. Variation of refractive indexes and conductivity and their derivatives respectively, for the microemulsions with the X value;
VAc=EtA ˆ 80=20, monomers=PrOH ˆ 10=90 (a,a0 ), 30/70 (b,b0 ), 50/50 (c,c0 ); X ˆ W = W ‡ O†.
when the concentration of the aqueous phase decreases
as well; (B) characterized by a moderate decrease of
conductivity; (C) a very small reduction in conductivity.
These three zones correspond to di€erent structures of
the formed microemulsions: O=W (A); bicontinuous (B);
W =O (C). The di€erential curve has been previously re-
ported [22].
Comparing conductometric results (see Fig. 3c) with
the refractometric ones (Fig. 3a and a0 ) it may be seen
that the speci®c changes for refractive indexes corre-
spond to di€erent structures as de®ned by conductivity
modi®cations. The three regions are mentioned in the
ternary diagrams (Figs. 1 and 3a, a0 , b, b0 ).
To put into evidence the in¯uence of comonomer
polarity, we have studied the system containing the
mixture VAc=EtA ˆ 80=20 (see Fig. 4). Di€erent from
the data given in Fig. 1a, in Fig. 4a the increase in the
number of homogeneous samples has taken place in the
zone rich in the aqueous phase; more polar monomers
may be easily dissolved by their interaction with the
polyethoxylated section of the surfactant [16].
Simultaneous measurements of refractive indexes and
of conductivity, o€er useful information to elucidate the
structure of microemulsions (see Fig. 5); the three zones,
namely O=W (A), bicontinuous (B) and W =O (C) are
obvious ones. The di€erential curves representing
changes of the conductivity or refractive indexes with X
(Fig. 5a0 , b0 , c0 ) are more suggestive in order to indicate
the domains where the properties change in a signi®cant
way.
After polymer formation, new phase separations may
arise [2±8] due to the increase in interfacial tension;
consequently, the initial homogeneity reduces its prob-
ability [25,26].
 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505
The same phenomenon takes place for the systems
presented in this paper (see Fig. 1d, e and f); the higher
the polymer concentration, the smaller become the ho-
mogeneity domain of samples, after polymerization. By
comparing diagrams 1a and d, it may be noticed that
from an initial number of 29 homogeneous systems, only
seven would remain homogeneous in the end; when
initiator concentration was relatively small (i.e. Bz2 O2 ±
0.5%), after 24 h of reaction time, a number of 22
samples remain homogeneous.
Increasing the concentration of EHA the number of
homogeneous samples decreases from 25 to 15 (see Fig.
1c and f); this fact may be explained taking into account
that the copolymers rich in the acrylic comonomer
(initially formed) are not soluble in the mixture PrOH/
H2 O [27]. Such results are in good agreement with pre-
viously published ones [1], which show that the homo-
geneity of monomer microemulsions is kept, provided
that SCC represents a solvent for the polymer [1,13,14].
When replacing EHA with EtA, the number of ho-
mogeneous systems after polymerization increases (Fig.
4b); this is due to an increased solubility of formed
co-polymers in cosurfactant [28]. During the copoly-
merization of the pair VAc/EHA the number of homo-
geneous systems after polymerization is restrained to
seven (see Fig. 1d), while for the pair VAc/EtA, this
number becomes 18 (Fig. 4b).
Under the conditions imposed by a low initiator
concentration (Bz2 O2 ± 0.5%), it has been noticed that
conversions decrease when the X value increases, both
for monomer=PrOH ˆ 10=90 and for 30/70 (see Fig. 6).
By increasing four times initiator concentration (see
Figs. 7 and 8), the decrease of conversion may be,
however, noticed only for a ratio monomers=SCC ˆ
10=90; for high monomer concentrations, the conver-
sions show a minim for a certain X value. For the con-
ditions described in Fig. 7, it has been proved
(conductometric measurements) that in the range
X ˆ 0:2 up to 0.8, monomers=SCC ˆ 30=70† the initial
microemulsions adopt a bicontinuous structure (see Fig.
Fig. 6. Dependence of monomer conversion versus the X value;
conditions are the same as those from Fig. 1f (Bz2 O2 ˆ 0:5%;
VAc=EHA ˆ 50=50, monomers=PrOH ˆ 10=90 (a) and 30/70
(b)).
1503
Fig. 7. Monomer conversions as a function of the X value;
conditions are the same as those from Fig. 1d (Bz2 O2 ˆ 2:0%;
VAc=EHA ˆ 80=20, monomers=PrOH ˆ 10=90 (a) 30/70 (b)
and 50/50 (c)).
3c) [22]; similar results have been reported in the copo-
lymerization of VAc with di-2-ethyl-hexyl maleate [23].
The manifest tendency towards a decrease of the
conversion even at the highest concentration of PrOH
monomers=PrOH ˆ 10=90† might be explained by a
degradative radical transfer with alcohol. A high con-
version may be reached for a high X value [16] as the
concentration of transfer agent (alcohol) is now reduced.
Obviously, high initiator concentrations would favor the
increase of radical number and accordingly, the proba-
bility of initiation; this represents the apparent reason
for which conversions increase, after the zone corre-
sponding to the bicontinuous structure. As it may be
seen from Fig. 7, important conversions are reached in
the case of initial W =O microemulsions (C) with a high
monomer concentration.
The same way for the evolution of conversion has
been noticed for the pair VAc/EHA in the presence of t-
BuOH (see Fig. 8); this result suggests a similar behav-
ior, namely a structuration of the mixture.
Unlike the previous examples, in the system VAc/EtA
(see Fig. 9) the ®nal conversions are less modi®ed. In the
range of O=W structures (A), one cannot obtain high
Fig. 8. Dependence of monomer conversion versus the X value;
conditions are the same as those from Fig. 1e (Bz2 O2 ˆ 2:0%;
VAc=EHA ˆ 80=20, monomers=t-BuOH ˆ 10=90 (a) and 30/70
(b)).
1504 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505

Table 1
Molar weight and the content of MEMNPEO25 for the obtained polymers (O ˆ mon=PrOH ˆ 30=70; W ˆ MEMNPEO25 33%;
O=W ˆ 80=20; Bz2 O2 ˆ 2%; 24 h; 63°C)
Monomer Solid content MEMNPEO25 MEMNPEO25 Mn Mw Mn =Mw
(wt.%) (wt.%) in copolymers
(wt.%)
A VAc 20.4 54 20.7 15 800 25 600 1.62
B VAc/EHA 80/20 22.29 54 18.7 24 000 45 900 1.91
C VAc/EHA 50/50 22.46 56 17.35 26 300 63 300 2.41
D VAc/EtA 80/20 21.69 48 11.7 22 500 40 400 1.80
Ea VAc 22.7 ± ± 8000 24 300 3.04
Fa VAc/EHA 80/20 22.0 ± ± 10 500 32 200 3.07
Ga VAc/EHA 50/50 20.51 ± ± 9300 43 500 4.68
Ha VAc/EtA 80/20 20.87 ± ± 11 900 36 100 3.02
a
Without MEMNPEO25 .

In previous studies we have reported that MEMN-

Fig. 9. Monomer conversions as a function of the X value;
conditions are the same as those from Fig. 4b; (VAc=EtA ˆ
80=20, Bz2 O2 ˆ 2:0% (a±c), 6% (d), monomers=PrOH ˆ 50=50
(a), 30/70 (b) and 10/90 (c,d)).
conversions anymore, as the comonomers are quite
soluble in water. In the bicontinuous domain (B) the
conversions increase, reaching maximum values only in
the zone of W =O structures (C).
The further increase of initiator concentration from
2% to 6% (see Fig. 9d), for a ratio monomers=PrOH ˆ
10=90, does not change notably the value of ®nal con-
version. A pertinent phenomenon is that of low con-
versions for systems without aqueous phase, but
containing a high concentration of alcohol; taking into
account the interactions of OH groups [21], a possible
explanation may be given in terms of degradative chain
transfer with SCC. The low conversion obtained in the
absence of water, for all systems characterized by the
ratio monomers=SCC ˆ 10=90 represents a validation
of the above assumptions (see Figs. 6±8).
The presence of a minimal conversion in the absence
of water, recorded for copolymerizations carried out in
t-BuOH (see Fig. 8b) is obviously due to a very intense
chain transfer, taking place in the presence of a SCC
with branched hydrocarbon chain; the same aspect was
noticed for the polymerization of VAc in microemul-
sions without surfactant [29].
PEO25 is not entirely consumed [23]. The resulted co-
polymers in admixture with the unreacted surfactant
have been analyzed by GPC; this way we were able to
obtain both, the molecular weights of copolymers and
the content of free surfactant. By processing the results
we have obtained the content of, MEMNPEO25 in the
®nal products as well as the polydispersity index (see
Table 1).
A useful comparison may be made with the data
presented in Table 1, describing polymerizations carried
out in the absence of surfactant (samples E±H). The
results corresponding to samples A, B and C show that
when the content in EHA increases, the reactivity of the
system augments as well, namely the total conversions as
well as the consumption of MEMNPEO25 ; on the other
hand the molecular weights and the polydispersity in-
dexes increase for high concentrations of EHA. The
same kind of conclusions may be reached for the
copolymerization of the pair VAc±EHA carried out in
the absence of surfactant (samples E,F and G ± Table 1).
In the presence of MEMNPEO25 the molecular
weights increase (may be due to the high volume intro-
duced by the substituent in surfactant), while the poly-
dispersity indexes decrease; this last fact might be
explained by the fact that the propagation step is more
controlled by the maleic radical introduced by copo-
lymerization with MEMNPEO25 . As known, maleic
radical cannot homopropagate by may undergo cross-
propagation with VAc or EHA [28]. The same sort of
behavior described for the copolymers with EHA, has
been noticed for copolymers with EtA (samples D,H ±
Table 1).
4. Conclusions
Microemulsions containing VAc, EHA (EtA), PrOH
(t-BuOH), water and MEMNPEO25 may constitute
 D. Donescu et al. / European Polymer Journal 37 (2001) 1499±1505
O=W , bicontinuous or W =O structures, respectively, as a
function of the ratio between aqueous and organic
phases.
Refractometric measurements, con®rmed by con-
ductometric determinations can put into evidence the
compositional domains corresponding to these three
structures.
Final conversions of the copolymers obtained depend
upon the structure of the initial microemulsions.
The content of the reactive surfactant in copolymer
increases when the concentration of acrylic monomer
decreases.
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