Synthesis of Butyl AcrylateStyrene Block Copolymers

in Emulsion by Reversible Addition-Fragmentation

Chain Transfer: Effect of Surfactant Migration upon
Film Formation

MICHAEL J. MONTEIRO,1 MARIE SJOBERG,2 JEROEN VAN DER VLIST,1 CHRISTIANNE M. GOTTGENS1
1
Department of Polymer Chemistry and Coatings Technology, Eindhoven University of Technology, P.O. Box 513,
5600 MB Eindhoven, The Netherlands

2
Ytkemiska InstitutetInstitute for Surface Chemistry, 45 Drottning Kristinas Vag, P.O. Box 5607,
114 86 Stockholm, Sweden

Received 5 May 2000; accepted 31 August 2000

ABSTRACT: The synthesis of block copolymers in an environmentally friendly medium

was carried out in emulsion polymerizations through the reversible addition-fragmen-
tation chain transfer process, using a transfer active xanthate (MADIX) agent, under
batch and starved-feed conditions. First, ab initio experiments were carried out to
prepare a seed of PBA dormant chains (i.e., poly(butyl acrylate) (PBA) polymer attached
with a transfer active xanthate). The M and polydispersity were predicted accurately
n
with numerical simulations and equations derived by Muller from the method of
moments. Those seeds were then used in a second-stage polymerization under starved-
feed and batch conditions to prepare composite polymer colloids of block PBA-co-
poly(styrene). Under starved feed conditions, approximately 90% of total polymer
consisted of blocks, whereas under batch conditions only 70% consisted of blocks, which
is proposed to be due a higher entry efficiency and thus greater termination rate. The
films of these latexes were examined by atomic force microscopy. Surfactant migration
to the surface increased with an increase in the amount of MADIX, resulting from a
combination of a smaller particle size and a lower average molecular weight. 2000 John
Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4206 4217, 2000
Keywords: block copolymers; RAFT; living; emulsion polymerization; MADIX

INTRODUCTION celles aggregates. Surfactant plays a dual role; it

Emulsion free-radical polymerization has proven
to be an environmentally friendly method for the
production of a wide range of polymers. The meth-
od1,2 uses water as the continuous medium in
which monomer is polymerized in surfactant mi-
Correspondence to: M. Monteiro (E-mail: m.j.monteiro@
tue.nl)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 4206 4217 (2000)
2000 John Wiley & Sons, Inc.
4206
not only provides the locus of polymerization but
also stabilizes the polymer particles. This results
in stabilized latex particles dispersed in an aque-
ous medium. The main advantages of emulsion
over conventional bulk or solution polymeriza-
tions are that polymerizations reach very high
conversions and thus contain low amounts of re-
sidual monomer, the heat produced by the highly
exothermic reactions is dissipated by the water,
and the processing of the high polymer solids
content latex is easy owing to its low viscosity.
 SYNTHESIS OF BLOCK COPOLYMERS USING RAFT
The practical problem is that the virtues of emul-
sion polymerization to produce high solids con-
tent, high molar mass, and hard polymer prod-
ucts can be detrimental to film properties.2 In
addition, the presence of additives in the recipe
such as surfactant, initiator, buffer, and other
components can create inhomogeneous films. For
example, surfactant can migrate to the surface
and concentrate into pockets during film forma-
tion.3 This can affect the gloss of the coating and
hardness of the film, reduce adhesion, and in-
crease water sensitivity.4,5
In recent years there has been a great deal of
industrial interest in composite latex particles,
which uses the virtues of emulsion polymeriza-
tion to tailor-make film properties for specific end
uses. This process has created a new class of
materials and allows one to design a large num-
ber of structures from a wide variety of mono-
mers. Composite particles are usually prepared
by a series of consecutive emulsion polymeriza-
tion steps. In general, ab initio emulsion polymer-
izations are first carried out to form a latex or
seed latex consisting of the chosen polymer. These
seeds are then swollen with the second monomer
and polymerized either under batch or semibatch
conditions. Semibatch processes are usually car-
ried out under starved-feed conditions, such that
the feed rate is equal to or less than the intrinsic
polymerization rate. These two processes can pro-
duce a myriad of latex morphologies depending
upon the experimental conditions,6,7 for example,
core-shell, raspberry, sandwich-like, and occluded
domains. The morphologies are controlled by both
thermodynamic and kinetic factors, and in some
cases kinetics of polymerization can lock an unfa-
vorable thermodynamic morphology into place.
The composite of soft and hard polymer [e.g.,
polybutyl acrylate (PBS) and poly(styrene)
(PSTY)] represents one environmentally friendly
strategy for the production of latex coatings that
compete with solvent-based systems.8 In effect,
the soft polymer forms the continuous phase en-
gulfing the hard particles, allowing good film for-
mation. The hard phase therefore provides the
mechanical strength and block resistance, result-
ing in film properties close to those produced by
solvent-based systems. The appearance of the
film depends on the size of the hard domains, and
can be made transparent if the hard domains are
sufficiently small.
With the advent of controlled radical polymer-
ization,9 synthesizing polymers with tailor-made
molecular weight distributions and polydispersi-
4207
ties is achievable. More importantly, controlled
polymer architectures such as block, triblock,
branched, and even star can now be made.10 13
This extends the making of latex composites and
thus polymer properties to a range of possibilities
far greater than previously envisaged.
The reversible addition-fragmentation chain
transfer (RAFT)10,14 16 offers a promising method
to produce polymer architectures through emul-
sion polymerization. The technique relies on a
sequence of addition-fragmentation events, as
shown in Scheme 1. The first step involves the
chain transfer of active species, P i , to the RAFT
agent (1), which then undergoes fragmentation to
reinitiate polymerization. The active moiety from
the RAFT agent is now attached to the polymeric
chain end, making it a dormant species (2). Once
the RAFT agent is consumed, equilibrium is es-
tablished between active (P i ) and dormant spe-
cies (2), and continues until all monomer is con-
sumed, resulting in a living growth of chains. The
technique can be used for a wide range of mono-
mers and reaction conditions, and offers a versa-
tile controlled free-radical route. MADIX agents
(e.g., Scheme 1) are a small category of RAFT-
type compounds, and have been reported to have
chain transfer constants, C tr , close to 1.
This work presents the preparation of block
copolymers of butyl acrylate and styrene in emul-
sion using the MADIX agent, [1-(O-ethylxanthyl)-
ethyl]benzene.17 The methodology was first to po-
lymerize BA with MADIX by conventional ab in-
itio emulsion polymerization, and then through a
second-stage polymerize styrene to prepare block
copolymers either under batch or starved-feed
conditions. The polymer was characterized by
double detection [i.e., ultraviolet (UV) and differ-
ential refractive index detector (DRI)] size exclu-
sion chromatography. Atomic force microscopy
(AFM) was then used to study the migration of
surfactant after film formation of these latexes.
EXPERIMENTAL
Ab Initio BA Emulsion Polymerizations
Water (700 g), sodium dodecyl sulfate (SDS; 4.3 g)
and NaHCO3 (0.095 g) were added in a glass-
reactor vessel and stirred (100 rpm) at 70 C
while argon was bubbled through the mixture.
After 1 h, BA (300 g) and MADIX agent (0.5 or
1.5 g) were added and the stirring rate increased
to 250 rpm. When the temperature reached 70 C
4208 MONTEIRO ET AL.
Scheme 1. Mechanism for RAFT.
again, sodium persulfate (SPS; 0.248 g in water)
was added. In the first hour samples were taken
every 5 min, and after that every half hour. The
reaction was stopped after 5 h and the final solids
content was 30%.
STY Emulsion Polymerizations Using PBA Seeds
Batch
Water (353 g), SDS (0.21 g), and PBA seed latexes
(500 g at 15% solids) prepared above were added
in a glass reactor vessel and stirred (100 rpm).
Styrene (150 g) was added dropwise and the mix-
ture was stirred overnight to swell. The temper-
ature was then increased to 70 C, argon was
bubbled through the mixture and the stirring rate
was increased to 250 rpm. After 1 h SPS (0.22 g in
water) was added. In the first hour samples were
taken every 5 min, and after that every half hour.
The reaction was stopped after 5 h and the final
solids content was 30%.
Starved Feed
Water (353 g), PBA seed latexes (500 g at 15%
solids) prepared above, and SDS (0.21 g) were
added in a glass reactor vessel and stirred at 100
rpm. Then, 85 g of styrene was added such that
the majority of monomer was swollen into the
particles of the seed latex. The mixture was
stirred overnight. The temperature was then in-
creased to 70 C, argon was bubbled through the
mixture and the stirring rate was increased to
250 rpm. After 1 h SPS (0.22 g in water) was
added. The remaining styrene was then added
with a dosimate at a rate of 0.2 mL/min. In the
 SYNTHESIS OF BLOCK COPOLYMERS USING RAFT
first hour samples were taken every 5 min, and
after that every half hour. The reaction was
stopped after 5 h and final solids were 30%.
AFM Methods
Atomic force microscopy is a powerful technique
for determining the morphology and topography
of polymer films. The latex samples were applied
on thin sheets of mica with an applicator 60 m
thick. AFM was thereafter performed on these
latex films under three different conditions: (1)
after drying at room temperature under ambient
conditions for 24 h; (2) after treatment of (1),
heating at 60 C in 50% relative humidity for
19 h; and (3) after treatment of (2), washing with
water, and drying to remove the remaining water.
The AFM instrument used was Nanoscope IIIa
Multimode from Digital Instruments, and both
topographic imaging (tapping mode) and phase
imaging were used for all samples.
Gel Permeation Chromatography (GPC) Analysis
We carried out GPC analysis using a Waters Cor-
poration Model 510 pump, Waters Model WISP
712 autoinjector, Model 410 refractive index de-
tector, and Model 486 UV detector (at 254 nm).
The columns used were a PLgel guard 5-m 50
7.5-mm precolumn, followed by two PLgel
mixed-C 10-m 300 7.5-mm columns (40 C) in
series. Tetrahydrofuran (THF) was used as eluent
(flow rate 1.0 mL/min) and calibration was done
using polystyrene standards (M 580 to 7.1
106). Data acquisition was performed using
Waters Millennium 32 (v. 3.05) software.
Light Scattering
Dynamic light-scattering measurements of PBA
latex particle sizes were carried out using a
Malvern 4700 multiangle light scatterer with
PCS for Windows.
RESULTS AND DISCUSSION
Ab Initio Emulsion Polymerization of BA
with MADIX
Ab initio experiments of BA and MADIX were
carried out at 70 C in the presence of SPS initi-
ator, SDS as surfactant, and deionized water. The
MADIX agent used was [1-(O-ethylxanthyl)ethyl]-
4209
Figure 1. Conversion-time plots of ab initio emulsion
polymerizations of BA at 70 C with (a) no MADIX ();
(b) 2 mM of MADIX (F); and (c) 6 mM of MADIX ().
The concentrations of MADIX are with respect to total
reaction volume.
benzene, and has a water saturation concentra-
tion of 0.4 mmol dm3, which is an order of mag-
nitude less than styrene. The effect of increased
MADIX concentration led to a decrease in the rate
of polymerization (Fig. 1), with an inhibition time
for all reactions between 2 and 5 min. Bulk and
solution experiments did not show retardation.
Therefore, it is believed that exit, through trans-
fer to the MADIX agent and fragmentation to
produce R (Scheme 1), resulted in retardation
through termination of R either with radicals in
the aqueous phase or reentry into a particle al-
ready containing a growing chain. C tr for this
MADIX agent is close to 1.5 for BA,18 which
means that MADIX agent will be consumed at a
slightly faster rate than monomer. The implica-
tion of this is that exit due to transfer to MADIX
will retard polymerization over most of the con-
version range. Further support for this argument
is from the decrease in average particle size with
increasing MADIX concentration (Table I). The
decrease corresponds to a greater number of mi-
celles being nucleated in interval I owing to exit
and reentry into another micelle.
The molecular weight distribution (MWD) is
important when considering the amount of con-
trol or living behavior a system obeys. Figure 2
shows the number-average molecular weight
) and polydispersity (PD) of PBA prepared at
(M n
two concentrations of MADIX agent. The M de-
n
creased from 1.6 105 to 5 104 when the
MADIX agent concentration was tripled. The PD
at low conversions started at approximately 2 and
decreased to 1.9 and 1.6 for MADIX concentra-
tions of 2 and 6 mM, respectively. Growth of dor-
mant chains (that is, living behavior) was seen by
4210 MONTEIRO ET AL.

Table I. Average Particle Size and Nc for Ab Initio

BA Polymerizations at 70 C in the Presence of
MADIX Agent

[MADIX]a Particle Sizeb

(mol dm3) (nm) Ncc

0 98 1.5 1017
2 103 58 7.3 1017
6 103 38 2.6 1018
a
MADIX concentration is calculated from the total reac-
tion volume.
b
Particle size are based on number average as determined
by dynamic light scattering.
c
Nc number of particles per unit volume of water, here Figure 3. Conversion-time plots of second-stage po-
calculated for the second-stage recipes with styrene at 15% lymerization of STY at 70 C using as the PBA seed
solids using the particle sizes above. latexes. (a) PBA prepared with no MADIX (); (b) PBA-
MADIX (2 mM) (F); (c) PBA-MADIX (6 mM) ().

the linear increase in M over the whole conver-

n
sion range, where the rate of increase was greater PD also remained constant at the starting values
for the higher MADIX concentration. These re- of eqs 1 and 2. The fractional conversion for the
sults are consistent with predictions using the changeover from interval II to III was approxi-
experimentally found C tr ( 1.5).18 The equations mately 0.3, after which eqs 1 and 2 became valid.
used to predict the M and PD were derived from
n
the method of moments. Equations 1 and 2 take x
into account the effect of residual MADIX agent n
M M (1)
1 1 1 x 0
due to its low C tr 19 and were only valid during

interval III, in which droplets were no longer
present. During interval II the ratio of monomer
1 1 1
PD 2 2 x
to MADIX being transported was equal to the x x
initial ratio, , which is in accord with the two- 2 1
films theory.23 Therefore, was constant in the 1 1 x 1/ (2)
2 2x 2
particles until all MADIX agent had been con-
sumed in the droplets. During this time, M and
n
where [M] 0 /[RAFT]0 , M 0 is molar mass of
monomer, x is fractional conversion, [P n ]/
[RAFT], and C tr .

Second-Stage Emulsion Polymerization of Styrene

in BA/MADIX Seed
The latexes produced from the previous experi-
ments were used as the seeds, in which styrene
was further batch or starved-fed in a second-stage
polymerization to give a final polymer ratio of BA
to STY 1. The PBA seed prepared with MADIX
at the 2-mM and 6-mM concentrations (denoted
here as PBA-MAD and PBA-MAD3, respectively)
consisted of poly(butyl acrylate)-(thiocarbonyl)
sulfanyl compounds. These dormant chains can
Figure 2. Ab initio emulsions of BA polymerized at
70 C in the presence of MADIX. (a) M at MADIX undergo further RAFT reactions with polystyryl
n
concentrations of 2 mM (}) and 6 mM (); and (b) PD at radicals to produce block copolymers. Figure 3
MADIX concentrations of 2 mM () and 6 mM (F). shows that the rate of polymerization (beyond
and
Lines are theoretical prediction using eq 1 for M experimental error) for styrene in PBA-MAD and
n
eq 2 for PD. PBA-MAD3 under batch conditions was not
 SYNTHESIS OF BLOCK COPOLYMERS USING RAFT 4211

verted to blocks, the UV will be identical to and

overlap the DRI signal (that is, f PBA-co-PSTY 1).
Under batch conditions [Fig. 4(a)], the DRI and
UV signals do not overlap. The f PBA-co-PSTY used
to obtain the DRI chromatogram was 0.7, which
means that approximately 70% of PBA-MAD was
converted to blocks. Under starved-feed condi-
tions the overlap between the two signals was
much better, where f PBA-co-PSTY used was 0.9. A
small percentage (10%) of dead PBA will be
formed through termination when making the
PBA-MAD seed.
Similar results were also found when PBA-
MAD3 was used as the seed. Figure 5(a) shows
the GPC chromatograms for batch conditions, and
Figure 5(b) for starved-feed conditions. Again,
starved-feed conditions produced the best results
to obtain block copolymers ( f PBA-co-PSTY used was
0.9) compared with f PBA-co-PSTY of 0.7 for batch
conditions.
The difference in the amount of blocks between
batch and starved feed could be due to secondary

Figure 4. GPC w (Log M w )] curves with UV and DRI

detection of second-stage emulsion polymerization of
STY using PBA-MADIX (2 mM): (a) under batch con-
ditions; (b) under starved-feed conditions. The DRI
chromatograms were normalized with respect to the
UV chromatogram, with a fitting parameter for the
fraction of block formation ( f PBA-co-PSTY).

greatly affected by the concentration of the poly-

meric RAFT agent in the seed. It should be noted
that considerable polymerization occurred before
the addition of the initiator when heating (over 30
min) from room temperature to the reaction tem-
perature of 70 C, a consequence presumably due
to the presence of residual initiator unreacted in
the preparation of the seed.
The GPC traces of STY polymerized in a second
stage using PBA-MAD as the seed under batch
and starved-feed conditions are shown in Figure
4(a,b), respectively. A double-detection GPC was
used to determine the amounts of blocks formed.
The differential refractive index (DRI) detector
showed the combined MWD of all polymers,
Figure 5. GPC w(Log M w )] curves with UV and DRI
whereas the UV detector (at 254 nm) showed only
detection of second-stage emulsion polymerization of
chains containing PSTY, either as homo- or block STY using PBA-MADIX (6 mM): (a) under batch con-
copolymers. All DRI chromatograms were nor- ditions; (b) under starved-feed conditions. The DRI
malized with respect to the UV chromatogram, chromatograms were normalized with respect to the
with a fitting parameter for the fraction of block UV chromatogram, with a fitting parameter for the
formation ( f PBA-co-PSTY). 20 If all PBA-MAD is con- fraction of block formation ( f PBA-co-PSTY).
4212 MONTEIRO ET AL.
Figure 6. AFM images of PBA dried at room temperature under ambient conditions
for 24 h: (a) topographic image, size 15 15 m; (b) phase image, size 15 15 m.
particle formation and/or excess radicals, produc-
ing homopolymer of polystyrene. Secondary par-
ticle formation is highly unlikely in our systems
because the number of particles per unit volume
was far greater (Table I) than the catastrophic
region of 1 1014 found for seeded STY poly-
merizations.21 The most probable difference be-
tween batch and starved feed is the lower entry
efficiency of radicals into the particles22 for
starved-feed conditions, which lowers the amount
of termination and consequently the amount of
STY homopolymer.
AFM of Films
Polybutyl Acrylate Latexes
The topographic image and phase image of PBA
(prepared without MADIX) after drying for 1 day
at room temperature are shown in Figure 6. From
the phase image we acquired information about
regions of different viscoelastic properties at the
surface: dark contrast regions correspond to soft
domains, whereas regions with light contrast cor-
respond to hard domains. In Figure 6(b) we de-
tected flakes of a phase with light contrast on top
of a darker phase. The darker phase probably
consisted of the soft PBA polymer, and the light
phase was probably a second phase that migrated
to the surface during drying.
After heating the sample at 60 C (Fig. 7), we
observed that the amount of the light second
phase at the surface increased. This indicated
that there was more and faster migration of the
second phase at elevated temperatures, owing to
increased mobility of the polymer chains in the
PBA phase at higher temperatures. After the
sample was washed with water (Fig. 8) the second
white phase was removed almost completely from
the surface and there were holes left in the film.
This behavior was previously found for other
types of latex films,3,4 and it has been explained
as migration of the surfactant used in the emul-
sion polymerization process to the surface. It is
probable that also in this case we had migration
of the surfactant (SDS) to the surface of the film,
as this was the only low-molecular-weight sub-
stance present in the formulation in relatively
large amounts (ca. 1.4 wt % of the monomer con-
tent). However, it is possible that short oligomers
of the polymers also can migrate to the surface.
PBA-PSTY Latexes
The topographic images of the PBA-PSTY latexes
displayed high surface roughness of the films and
no additional information about the morphology
of the films could be obtained from these images;
therefore, only phase images of these latexes will
be shown here. PBA-PSTY composite latexes
were studied with AFM. All samples gave two
 SYNTHESIS OF BLOCK COPOLYMERS USING RAFT 4213

Figure 7. AFM images of PBA heated at 60 C in 50% relative humidity for 19 h:

(a) topographic image, size 15 15 m; (b) phase image, size 15 15 m.

glass-transition temperatures (T g s), of 51.4 C
and 96.9 C, which correspond to the T g s of PBA
and PSTY, respectively. The latexes were synthe-
sized under both starved-feed and batch condi-
tions. However, there were no large differences in
the AFM images comparing the starved and the
batch types of latexes.
The AFM images of the latexes with and with-
out MADIX differed in some respects; however,
this will be explained in detail later, and we will
start with the general AFM appearance of the
PBA-PSTY latexes under different conditions.
As an example, we have chosen to show the
AFM images of PBA-PSTY (batch) without

Figure 8. AFM images of PBA heated at 60 C in 50% relative humidity for 19 h and
thereafter washed with water and dried: (a) topographic image, size 15 15 m;
(b) phase image, size 15 15 m.
4214 MONTEIRO ET AL.

Figure 9. AFM images of PBA-PSTY (batch) dried at room temperature under am-
bient conditions for 24 h: (a) phase image, size 2 2 m; (b) phase image, size 15
15 m.

MADIX. Phase images of this sample after drying
at room temperature for 24 h are displayed in
Figure 9. In the 2 2-m image more or less
spherical domains of light contrast embedded in a
darker phase can be observed. These spherical
domains probably consisted of the hard PSTY
phase and the dark continuous phase was proba-
bly the soft PBA phase. The diameter of the PSTY
domains was approximately 100 nm; however, it

Figure 11. AFM phase image of PBA-PSTY (batch)

Figure 10. AFM phase image of PBA-PSTY (batch) heated at 60 C in 50% relative humidity for 19 h and
heated at 60 C in 50% relative humidity for 19 h, size thereafter washed with water and dried, size 15
15 15 m. 15 m.
 SYNTHESIS OF BLOCK COPOLYMERS USING RAFT 4215

Figure 12. AFM phase images of PBA-PSTY (batch) and PBA-PSTY-MADIX (batch),
size 2 2 m: (a) PBA-PSTY (batch) dried at room temperature under ambient
conditions for 24 h; (b) PBA-PSTY-MADIX (batch) dried at room temperature under
ambient conditions for 24 h; (c) PBA-PSTY (batch) heated at 60 C in 50% relative
humidity for 19 h and thereafter washed with water and dried; (d) PBA-PSTY-MADIX
(batch) heated at 60 C in 50% relative humidity for 19 h and thereafter washed with
water and dried.

is not possible to say whether the whole PSTY
domain was visible at the surface or whether only
the top of the domains was visible. Furthermore,
while islands 0.51 m in size were observed in
the 15 15-m phase image of the same sample
[Fig. 9(b)]. These islands were consequently much
larger than the PSTY domains and probably con-
sisted of a second phase.
When the sample was heated to 60 C, the
white second phase covered more than 50% of the
surface; however, in the areas of the surface that
were not covered with the second phase the STY
domains were still visible (Fig. 10). Finally, when
the surface was washed with water after heating,
the second phase was removed completely and the
STY domains were again exposed over the whole
4216 MONTEIRO ET AL.
surface (Fig. 11). As for the PBA samples, we
believe that the second white phase observed on
top of the film was surfactant that migrated to the
surface. This is plausible because the surfactant
was the only low-molecular-weight component
that was soluble in water and present in the for-
mulation in relatively large amounts.
When comparing the samples with and without
MADIX, differences in both the size of the PSTY
domains and the amount of surfactant that mi-
grated at 60 C were detected. As mentioned pre-
viously, the size of the PSTY domains was 100 nm
for PBA-PSTY without MADIX after drying in
room temperature [Fig. 12(a)]. The corresponding
samples with MADIX had PSTY domains with a
size only half this value (40 50 nm) [Fig. 12(b)].
However, when these samples were heated and
washed, we observed that the PSTY domains of
the latex with MADIX became larger, more mono-
disperse, and more close-packed at the surface
[Fig. 12(d)], whereas the size and shape of the
PSTY domains in the sample without MADIX
were almost unchanged [Fig. 12(c)]. It is not prob-
able that the PSTY domains grew in size upon
heating; it is more likely that the PSTY domains
rose to the surface and therefore became more
visible in the AFM images when the sample was
heated. This could be because the soft PBA phase
moved down into the bulk of the film, filling out
cavities and voids left in the film after film forma-
tion of the latex particles. This process was accel-
erated when the temperature increased, and thus
the mobility of the PBA phase increased. More-
over, the PBA-MADIX seed had a lower average
molecular weight than the PBA seed without
MADIX (1 105 compared with 7 106), and the
PBA-MADIX chains were therefore expected to be
more mobile than the PBA chains. Consequently,
movement of PSTY domains to the surface of the
film would be facilitated when MADIX was
present.
We also observed that more surfactant mi-
grated to the surface for PBA-PSTY with MADIX
than without, after heating the samples to 60 C.
Again, the difference in molecular weight (and
thus mobility) of the PBA polymer probably
caused this difference in migrated surfactant.
However, in this study we investigated the sam-
ples at only a relatively short time scale (12
days). After longer times (weeks to months) the
amount of migrated surfactant might become the
same for the two samples.
CONCLUSION
Block copolymers were prepared in emulsion
through the RAFT process using the MADIX
agent under batch and starved-feed conditions.
First, ab initio experiments were carried out to
prepare a seed of PBA dormant chains (i.e., PBA
polymer attached with a transfer-active xan-
thate). Those seeds were then used in a second-
stage polymerization under starved-feed and
batch conditions to prepare composite polymer
colloids of block PBA-co-PSTY. Under starved-
feed conditions approximately 90% of total poly-
mer consisted of blocks, whereas under batch con-
ditions only 70% consisted of blocks, which is
proposed to be due a higher entry efficiency and
thus greater termination rate. The films of those
latexes were examined by AFM. Surfactant mi-
gration to the surface increased with an increased
amount of MADIX, resulting from a combination
of smaller particle size and lower molecular
weight.
The authors gratefully acknowledge the support of the
European Community within the Brite-EuRam pro-
gram (Contract no. BRPR-CT-0510).
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Schoonbrood, H. A. S.; Unzue, M. J.; Asua, J. M.;
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