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e-Polymers 2005, no. 025.
ISSN 1618-7229

Synthesis and characterization of poly(methyl

methacrylate) obtained by ultrasonic irradiation

Cristina Parra 1, Gema González 1, Carmen Albano 2 *

1
Laboratorio de Materiales, Instituto Venezolano de Investigaciones Científicas,
apdo. 21827, Caracas 1020-A, Venezuela; gemagonz@ivic.ve
2
Laboratorio de Polímeros, Centro de Química, Instituto Venezolano de
Investigaciones Científicas, apdo. 21827, Caracas 1020-A, Venezuela;
Fax +58 212 5041418; calbano@ivic.ve

(Received: November 14, 2004; published: April 10, 2005)

This work has been presented at the 12th Annual POLYCHAR World Forum on
Advanced Materials, January 6-9, 2004, in Guimaraes, Portugal

Abstract: We have studied the influence of surfactant nature and concentration,

and monomer concentration on the synthesis of poly(methyl methacrylate) (PMMA)
using high-frequency ultrasound. Polymerization was carried out via free radicals
from aqueous solutions with several concentrations of an anionic (sodium lauryl
sulfate, SLS) or a cationic surfactant (cetyltrimethylammonium bromide, CTAB)
and different concentrations of the insoluble monomer methyl methacrylate (MMA)
as the dispersed phase. The polymer particles obtained were characterized by
FTIR, differential scanning calorimetry (DSC) and scanning electron microscopy
(SEM). The IR spectra show the presence of the characteristic absorption bands
for PMMA when SLS was used. When CTAB was employed, for all surfactant
concentrations and high monomer concentration (14% v/v), PMMA was obtained.
However, bands of the surfactant were present for lower monomer concentrations.
The glass transition temperature measured by DSC was in the range 106 - 126°C
characteristic of PMMA. Maximum conversion was obtained when the anionic
surfactant was employed. SEM studies show the formation of sub-micrometric
PMMA latex spheres with average particle size from 65 to 100 nm when the
anionic surfactant was used and 65 nm - 0.3 µm for the cationic surfactant.

1. Introduction
Poly(methyl methacrylate) (PMMA) is a very versatile polymer due to its excellent
properties such as resistance to strong alkaline or acid solutions and its stability to
heat and light. The polymer behaves quite satisfactory in the presence of very
aggressive environments. Therefore, its applications have extended to many areas
including medicine [1], e.g., in osseous cements [2], dental applications [3], intra-
ocular lenses [4] and as facial implants and a number of other applications [5].
PMMA can be obtained by conventional methods by polymerization in emulsion
resulting in particles in the range of 1 to 20 µm. Recently, other methods have been
used for the synthesis of this polymer, among them sonochemistry [6] using ultra-
sound waves as the source of energy.
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The last method is based on the fact that when a sound wave travels through a liquid
medium an elevated number of bubbles are formed which grow and collapse in a few
microseconds. This phenomenon is called cavitation [7]. Several theoretical studies
on sonochemistry [8] have shown that ultrasonic cavitation can generate temper-
atures of the order of 5000 K and local pressures of 500 atm, heating and cooling the
system at rates as high as 109 K/s. The environment created by the dramatic
collapse of bubbles has enough energy to produce bond rupture, forming free
radicals (from the monomer, surfactant and solvent), which play the role of initiators
in the polymerization. Furthermore, this is a relatively simple method (beginning only
with a monomer and the aqueous solution of an emulsifier), the product obtained has
a high degree of purity and due to a very efficient dispersion of the medium it has
been possible to synthesize nanometric polymers [9].
The work of Suslick and Price [10] has been a pioneer in the first attempts of ultra-
sound application to the synthesis of materials. For instance, the sonochemical
decomposition of organometallic precursors in low volatile solvents produces nano-
structure materials with high catalytic activities. Also metals, alloys, oxides, carbides,
sulfides and nanometric colloids can be obtained by this new route. Another impor-
tant application has been the preparation of biomaterials based on microspheres of
proteins and polymers.
Many syntheses of various polymers and copolymers have been carried out by ultra-
sonic irradiation [11-13]. Also detailed studies have been reported on the mecha-
nisms of degradation suffered by macromolecules due to the effect of ultrasonic
waves [14]. An important factor considered has been the increase in the medium
viscosity as the polymer is synthesized affecting the cavitation process and, there-
fore, the reaction velocity [15]. PMMA polymerization based on the irradiation of pure
monomer following the effect of a number of parameters on the process has been
reported by Price [16] and Kruus [17]. They obtained polymers with controlled molec-
ular weight, polydispersity and tacticity although low conversions were achieved.
Recently, Yongqin et al. [18] synthesized PMMA through the polymerization in
emulsion of the anionic surfactant sodium dodecyl sulfonate. A high molecular weight
polymer with a conversion of 67% was obtained after 30 min of reaction.
A new scope to the synthesis of polymeric materials by the use of ultrasound energy
has been opened and important contributions are still to come. The object of the
present work is to study the influence of the type and concentration of surfactant and
of monomer concentration in the synthesis of PMMA by sonochemical methods.

2. Experimental part
Methyl methacrylate (MMA) analytical grade 99.8% (density: 0.943 g/cm3) was
employed. This monomer was thoroughly washed in 10% NaOH solution to remove
the inhibitor agent and several times in distilled water, dried with anhydrous Na2SO4
and finally distilled in vacuum. The surfactants used were sodium lauryl sulfate (SLS)
and cetyltrimethylammonium bromide, both analytical grade, without any additional
treatment.
An ultrasonic generator (Fisher PG100 MSE, Mod. 150W) operating at a frequency of
20 kHz was employed. Fig. 1 shows a schematic diagram of the equipment used -
similar to the schematic diagram presented in ref. [11]. This is formed by a double
jacket glass vessel and a 13 mm Ti sonic wave emission probe controlled by a
standard power source.

2
 N2 inlet

Ultrasonic
Horn

N2 outlet

Water out Titanium Probe

Reaction Vessel

Water in

Fig. 1. Schematic diagram of our high-frequency equipment

The preparation of the dispersion for the reaction was the following: 3 - 7 ml of MMA
were introduced in the reaction vessel and an appropriate volume of surfactant to
complete a total volume to 50 ml. Tab. 1 shows a summary of the experimental
variables.

Tab. 1. Experimental variables

MMA concentration Surfactant concentration Surfactant
in % (v/v) in % (w/v)
14 0.5; 1.0; 1.5; 2.0 SLS, CTAB
10 0.5; 1.0; 1.5; 2.0 SLS, CTAB
8 0.5; 1.0; 1.5; 2.0 SLS, CTAB
6 0.5; 1.0; 1.5; 2.0 SLS, CTAB

Once both phases were introduced in the reaction vessel, a constant flow of oxygen-
free N2 was bubbled through the solution until the end of the process. Ultrasonic irra-
diation was carried out for 1 h for all the different conditions of reaction. Cool water
was circulated to maintain the temperature at 28°C. For polymer precipitation the
emulsion produced was poured into semi-frozen water-methanol (1:1) mixture. The
precipitated solid was separated from the mother liquor by centrifugation at 30 000
rpm, and three consecutive washes of 20 min each with cold water. Finally, the
weight of the polymer obtained was determined and the conversion calculated.
The morphology of the synthesized polymer was determined in a scanning electron
microscope (SEM) Hitachi Field Emission S-4500 operating at 8 kV. The particle size
was determined from SEM micrographs. The samples to be observed in the SEM
were prepared by suspension in an ethanol-water mixture (75/25) and Pt-C coated in
a Balzers BAE 300 evaporator.

3
All synthesized polymers were analyzed in a Nicolet FTIR spectrophotometer Mod.
500. Thermal analysis was also carried out for all the samples in a Mettler Toledo
differential scanning calorimeter, Mod. DSC821e, from 25 to 230°C at a heating rate
of 20°C/min.
The efficiency of the reaction towards the formation of polymer was determined by
the conversion:
Conversion in % = Mp/Mm · 100
where Mp is mass of polymer obtained from the reaction, and Mm the mass of mono-
mer employed in the reaction.

a
b
c
d

3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Fig. 2. FTIR spectra of PMMA synthesized with: (a) 0.5% SLS - 14% MMA; (b) 1.0%
SLS - 10% MMA; (c) 1.5% SLS - 8% MMA; (d) 2.0% SLS - 6% MMA

3. Results and discussion

Polymerization using SLS surfactant always resulted in PMMA as the synthesis
product for all different concentrations of surfactant and monomer. Fig. 2 shows
some of the FTIR spectra obtained for different conditions.
The presence of the characteristic bands of PMMA is observed at exactly the same
vibration frequencies for all samples. All the bands correspond to those of PMMA
without any other contribution present. This is indicative of the purity of the polymer
obtained. The bands at 3000 and 2900 cm-1 correspond to the C-H stretching of the
methyl group (CH3). The intense band located at 1730 cm-1 corresponds to the C=O
bond of the carbonyl group. Also the 1300 and 1450 cm-1 bands are observed asso-
ciated to C-H symmetric and asymmetric stretching, respectively. The 1240 cm-1
band is assigned to torsion of the methylene group (CH2) and the 1150 cm-1 band
corresponds to vibrations of the ester group C-O. The 1000 and 800 cm-1 bands are
assigned to C-C stretching. In the synthesis with CTAB, for all different surfactant
concentrations but only for high monomer concentrations, PMMA was obtained with

4
only a very small amount of surfactant remaining. For the other monomer concen-
trations either a mixture of surfactant and polymer or other products were obtained.
Fig. 3 shows the IR spectra for different samples obtained with CTAB at different
surfactant and monomer concentrations, as an example of the products obtained with
this surfactant.

Fig. 3. FTIR spectra of PMMA synthesized with: CTAB 1.5% - MMA 8%; (b) CTAB
0.5% - MMA 14%; (c) CTAB 1.5% - 14%MMA

Fig. 3a corresponds to 1.5% CTAB - 8% MMA; the presence of all the characteristic
PMMA bands can be observed except the band at 2849 cm-1, which corresponds to
the surfactant indicating that some is remaining in the structure. Fig. 3b corresponds
to 0.5% CTAB - 14% MMA; the bands in this spectrum correspond very nearly to
PMMA, indicating that only a very small amount of surfactant is present, and Fig. 3c
corresponds to 1% CTAB - 14% MMA, in which the formation of a different product is
observed. This is an evidence of the strong influence of surfactant and monomer
concentration on the product obtained.
5
 Solvent (water)
H2O H• + OH•

Surfactant (SLS)
C12H25OSO 3Na C 12H25 • + NaSO 3O•

O .
• CH3 + CH 2 = C− CH = CH 2
CH2 C C O CH3
CH2 = C − CH 3 + • CH = CH 2
CH3
.
Fig. 4. Free radicals formed by ultrasonic irradiation during MMA polymerization

The vibration bands observed in the range 3600 - 3300 cm-1 correspond to OH-
groups, which could be indicative of the H• and OH• radicals formed from the decom-
position of water under ultrasonic radiation (see Fig. 4). Some radicals will react to
form H2O, H2, H2O2 and O2 [20-21].
Tabs. 2 and 3 show a summary of the glass transition temperatures, Tg, obtained
from the DSC analysis of a representative group of the synthesized polymers. The Tg
values correspond to that expected for PMMA. NMR experiments (not shown here)
confirm the presence of atactic PMMA (Tg = 106 - 114°C) or syndiotactic PMMA (Tg =
120 - 126°C) observed for different synthesis conditions, which are in agreement with
the reported temperatures for these configurations [19]. The general tendency ob-
served seems to show that high monomer concentrations (14%) using different
concentrations of SLS result in the formation of atactic PMMA and low monomer
(8%) concentrations for the same surfactant seem to produce syndiotactic PMMA.
However, when the surfactant is changed to CTAB, for high monomer concentrations
PMMA was obtained with the presence of some remaining surfactant. For low mono-
mer concentration no formation of PMMA was observed in some cases; in other
cases a mixture of surfactant and polymer was obtained. These results indicate that
the stereochemistry of the polymer obtained by ultrasonic irradiation varies depend-
ing on the reaction conditions. It seems that the principal factors affecting the PMMA
configuration are the nature of the surfactant and the surfactant concentration. This
could be explained considering that ester substituents are oriented in alternate order
(indicating syndiotacticity) or in a completely random way (indicating atacticity).
Given the complexity of the synthesis environment, it can be understood that the
growth of the polymer chains depends on the size of the radical species, what will
increase or decrease the steric effect and, therefore, will limit the space region where
the bonding to a new monomer molecule will take place and, thus, will contribute to
form one of the polymer configurations.
Fig. 5 shows the apparent conversion vs. surfactant concentration for four different
monomer concentrations. In general, as the SLS surfactant concentration increases,
the conversion increases. Maximum conversion is obtained with 1.5% surfactant
concentration, except for the highest monomer concentration (14%) where con-
version increases monotonically with surfactant concentration.

6
Tab. 2. Tg values obtained for MMA 14% (v/v)
Surfactant Surfactant conc. in % (w/v) Tg ±2°C
SLS 0.5 117
SLS 1.0 120
SLS 1.5 116
SLS 2.0 106
CTAB 0.5 111
CTAB 1.0 120
CTAB 1.5 117
CTAB 2.0 123

Tab. 3. Tg values obtained for MMA 8% (v/v)

Surfactant Surfactant conc. in % (w/v) Tg ±2°C
SLS 0.5 126
SLS 1.0 115
SLS 1.5 126
SLS 2.0 120
CTAB 0.5 120
CTAB 1.0 110
CTAB 1.5 110
CTAB 2.0 111

60
MMA (6% V/V) MMA (8% V/V)
MMA (10% V/V) MMA (14% V/V)
50
% Conversion

40

30

20

10

0
0 0,5 1 1,5 2 2,5
Surfactant Concentration (%P/V)

Fig. 5. Apparent conversion vs. SLS concentration

7
 25
MMA (14% V/V) MMA (10% V/V)
MMA (8% V/V) MMA (6% V/V)

% Conversion 20

15

10

0
0 0,5 1 1,5 2 2,5
Surfactant Concentration (%P/V)

Fig. 6. Apparent conversion vs. CTAB concentration

For CTAB (Fig. 6) conversion increases with monomer concentration. However, as

was established above for these syntheses, there is always some surfactant
remaining. Comparing both graphs it can be observed that the highest conversions
were obtained in the presence of SLS and in both cases a strong dependence
between yield, concentration and surfactant nature was found. These results suggest
that the increase in the conversion is due to the surfactants acting as a strong source
of free radicals, which are initiators of the polymerization. The fact that CTAB is a
much larger and bulky molecule than SLS could explain the lower conversions
observed for it. It is clear that in the presence of a surfactant of larger size (more
carbon atoms and larger hydrophobic part) an increment in the medium viscosity is
produced, which will cause a decrease in the reaction velocity due to the negative
effect in the cavitation phenomena [22]. This effect was also observed on experi-
ments of styrene polymerization [23]. For SLS the contribution to the viscosity of the
medium is lower due to its smaller molecular size and since its principal role is not
only that of an emulsifier; it can be easily degraded to form free radicals and, there-
fore, its presence increases the velocity of the reaction in a significant way resulting
in an increasing conversion.
The average particle size of PMMA was determined by scanning electron micro-
scopy. Figs. 7 to 14 correspond to electron micrographs of a representative group of
polymer samples prepared under different reaction conditions. In all the samples the
formation of small spherical PMMA particles formed in the polymerization process is
observed. Figs. 7 to 10 show the formation of latex particles from 10% (v/v) MMA and
four different SLS concentrations (0.5, 1.0, 1.5 and 2.0% w/v). The average particle
size is in the range of 65 - 100 nm.
Figs. 11 to 14 show micrographs corresponding to polymers obtained from the
synthesis carried out with CTAB. It is clear that the surfactant and monomer concen-
tration have a strong influence on the polymer formation. As the surfactant concen-
tration increases, the particle size increases. The average particle size is 65 nm for
low surfactant concentration and 0.3 µm for high surfactant concentration.
8
Fig. 7. (left) PMMA synthesized with 0.5% SLS and 10% MMA
Fig. 8. (right) PMMA synthesized with 1.0% SLS and 10% MMA

Fig. 9. (left) PMMA synthesized with 1.5% SLS and 10% MMA
Fig. 10. (right) PMMA synthesized with 2.0% SLS and 10% MMA

Fig. 11. (left) PMMA synthesized with 0.5% CTAB and 10% MMA
Fig. 12. (right) PMMA synthesized with 1.0% CTAB and 10% MMA

9
Fig. 13. (left) PMMA synthesized with 1.5% CTAB and 10% MMA
Fig. 14. (right) PMMA synthesized with 2.0% CTAB and 10% de MMA

It is also observed that the PMMA particles are embedded in a matrix that can be
associated to the surfactant structure. Most probably during the polymerization
process some molecules of CTAB and SLS have remained occluded between the
polymer chains. The polymer particle size is influenced directly by the concentration
and the type of surfactant; smaller particles were obtained for the anionic surfactant.
From the results obtained in the present work it is concluded that ultrasonic irradi-
ation is a very effective and simple method for the synthesis of PMMA. The surfactant
nature and concentration and the monomer concentration strongly influence the syn-
thesis of PMMA. Its yield is affected by the surfactant’s nature and concentration,
SLS being the surfactant that showed the highest conversion. Also particle size is
affected by surfactant nature and concentration; smaller particle sizes were obtained
with SLS.

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