Influence of Camphorsulfonic Acid in Nitroxide-Mediated

Styrene Miniemulsion Polymerization

MICHAEL F. CUNNINGHAM,1 KARINE TORTOSA,1 MARCUS LIN,1 BARKEV KEOSHKERIAN,2

MICHAEL K. GEORGES3
1
Department of Chemical Engineering, Queen’s University, Kingston, Ontario, Canada K7L 3N6

2
Xerox Research Centre of Canada, Mississauga, Ontario, Canada L5K 2L1

3
Department of Chemistry, University of Toronto, Mississauga, Ontario, Canada L5L 1C6

Received 29 January 2002; accepted 29 May 2002

Published online 00 Month 2002 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pola.10377

ABSTRACT: The rate-accelerating effects of camphorsulfonic acid (CSA) on nitroxide-

mediated styrene miniemulsion polymerization were studied. Polymerizations were
initiated with benzoyl peroxide (BPO) as an initiator and mediated with either 2,2,6,6-
tetramethylpiperidinyloxy (TEMPO) or 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy
(OH-TEMPO). Although CSA has been used to accelerate the rate in bulk nitroxide-
mediated polymerizations, it has not been well studied in emulsion/miniemulsion. With
dispersed systems, the effectiveness of CSA is likely to be affected by partitioning
between the aqueous and organic phases. In styrene miniemulsion experiments per-
formed over a range of conditions, the effect of adding CSA varied from negligible to
significantly increasing the final conversion and molecular weight, depending on the
nitroxide:BPO ratio. At a ratio of nitroxide:BPO ⫽ 1.7, the effect of CSA addition is
small, whereas the final conversion and molecular weight are dramatically enhanced by
CSA addition when the nitroxide:BPO ratio is 3.6. CSA is most effective in enhancing
the rate and molecular weight when the initial free-nitroxide concentration is higher.
The magnitude of the rate and molecular weight enhancement was similar for TEMPO
and OH-TEMPO despite their differences in water solubility. © 2002 Wiley Periodicals,
Inc. J Polym Sci Part A: Polym Chem 40: 2828 –2841, 2002
Keywords: living polymerization; radical polymerization; kinetics (polym.)

INTRODUCTION crostructure, but they require rigorous purifica-

The control of macromolecular structure has be-
come increasingly important for academic and in-
dustrial interests, including efforts to achieve bet-
ter control of the molecular weight, chain-end
functionality, and architecture. Anionic and cat-
ionic polymerization are established techniques
for synthesizing polymers with a controlled mi-
Correspondence to: M. F. Cunningham (E-mail: cunning@
chee.queensu.ca)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 40, 2828 –2841 (2002)
© 2002 Wiley Periodicals, Inc.
2828
tion procedures, are often run at low tempera-
tures (⬍⫺50 °C), and tend to be selective toward
monomers. However, nitroxide-mediated living
radical polymerization (NMRP) has been demon-
strated to be reliable in the accurate control of
molecular weight and polydispersity and has been
applied successfully to bulk and solution styrene
polymerization.1–10 This process involves equilib-
rium between dormant and growing polymer
chains (Scheme 1). Homolytic dissociation of the
C–O bond above temperatures of ⬃120 °C yields
an active polymeric radical and nitroxide mole-
cule. The exchange reactions between dormant

Scheme 1. Reversible termination of polystyrene radical by TEMPO (2,2,6,6-tetra-
methyl-1-piperidinyloxy).
chains and growing chains are considerably faster
than propagation (kp/K ⫽ 1.03 ⫾ 0.18 ⫻ 10⫺7 s⫺1
at T ⫽ 125 °C).11 Initiators are selected to give
near-instantaneous decomposition at the poly-
merization temperature, and therefore all chains
are initiated at about the same time, resulting in
narrow polydispersity. Moreover, the deactiva-
tion of the growing chains by a stable nitroxide
radical reduces the likelihood of recombination
between two radicals, giving NMRP its “pseudo-
living” character.
Although nitroxide-mediated polymerizations
in bulk have been well investigated, less effort
has been directed toward heterogeneous reac-
tions. Conducting a nitroxide-mediated polymer-
ization in emulsion (or miniemulsion) would be an
attractive route for commercial production of liv-
ing radical polymers. Miniemulsion is similar to
emulsion polymerization, but in miniemulsion
the monomer droplets are small (⬃0.05– 0.2 ␮m)
as compared with the monomer droplets in emul-
sion (⬃5–50 ␮m) and are the primary loci of nu-
cleation. A costabilizer such as a long-chain al-
kane is required to achieve the small monomer
droplet size in miniemulsion.
Nitroxide-mediated polymerizations in emul-
sion have been problematic and typically have
suffered from poor colloidal stability and loss of
living character during polymerization.12–14
Much better success has been achieved with mini-
emulsion polymerization15–23 because it essen-
tially eliminates the particle nucleation stage and
thereby simplifies the process. Only Prodpran et
al.15,16 have reported results where camphorsul-
fonic acid (CSA) was used in nitroxide-mediated
miniemulsion polymerizations. They polymerized
styrene at 125 °C with benzoyl peroxide (BPO)
and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEM-
PO), with CSA added to some of the runs to ac-
celerate the polymerization. The rate in bulk
(with the same amounts of BPO, TEMPO, and
CAMPHORSULFONIC ACID 2829
CSA) was faster than in miniemulsion, signifying
that CSA was less effective in the miniemulsion
system.
The use of organic acids such as CSA to accel-
erate in bulk NMRP polymerizations is
known.11,24 –27 Veregin and coworkers11,25,27 ob-
served a dramatic increase in the rate of TEMPO-
mediated styrene polymerization in the presence
of CSA. They obtained higher molecular weight in
less time but observed a broadening of the poly-
dispersity if the CSA concentration was too high.
CSA influences different aspects of living radical
polymerizations. The most important effect is
rapid consumption of the nitroxide, as shown by
Veregin et al.11 with in situ electron spin reso-
nance measurements in bulk styrene NMRP. Ni-
troxide disproportionation by the acid was cited
as the most probable route for TEMPO consump-
tion. Reduction of the nitroxide concentration
drives the equilibrium to favor the formation of
active radicals, thereby increasing the polymer-
ization rate. In addition to direct consumption of
the nitroxide, evidence suggests the rate constant
for the deactivation between a growing radical
and nitroxide decreases in the presence of ac-
id.11,26 Veregin et al.11 estimated that the value of
the ratio of the propagation-rate parameter to the
equilibrium constant for deactivation (kp/K) in-
creased ⬃30% in the presence of CSA, which they
attributed to a decrease in the deactivation rate.
There is also evidence that the thermal poly-
merization of styrene is influenced by CSA and
other organic acids. Mayo28 proposed the mecha-
nism outlined in Scheme 2. Thermally initiated
radicals could result in increasing polydispersity
and a loss of living character. However, they pro-
vide a means of mitigating the effects of nitroxide
accumulation resulting from irreversible termi-
nation reactions between polymeric radicals. In
the absence (or near absence) of thermally initi-
ated radicals, nitroxide accumulation can com-
2830 CUNNINGHAM ET AL.
Scheme 2. Mayo’s mechanism of thermal styrene polymerization.
pletely suppress the rate before complete conver-
sion is achieved. Some thermal initiation is thus
beneficial for most nitroxide-mediated polymer-
izations. Buzanowski et al.29 examined the ther-
mal polymerization of styrene in the presence of
five acids covering a large fluid-pressure range.
They demonstrated that in the presence of acid,
dimer 1 is reduced to 4. CSA retarded the poly-
merization dramatically. Georges and cowork-
ers24,30 explored the autopolymerization of sty-
rene in the presence of TEMPO with and without
added acid (benzoic acid and CSA). Less low mo-
lecular polymer was seen in the molecular weight
distribution when acids were used, which was
taken as evidence of reduced thermal initiation.
The number of thermally initiated chains was
reportedly reduced by a factor of 4 with CSA.
Nitroxide partitioning between the aqueous
and organic phases plays a defining role in the
evolution of miniemulsion NMRP. Although
phase-partitioning data for CSA is not available,
CSA can be expected to partition to some extent
into the aqueous phase during polymerization,
thereby reducing the concentration inside the
particles. As described by Prodpran et al.,15,16 this
may result in CSA being less effective in rate
enhancement than in bulk. We have studied the
effectiveness of CSA in heterogeneous styrene
miniemulsion polymerizations, initiated with
BPO, in the presence of two similar nitroxides
with widely differing water solubility [TEMPO
and 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy
(OH-TEMPO)]. Two key experimental parame-
ters in miniemulsion NMRP22 have been exam-
ined at varying CSA concentrations—the nitrox-
ide-to-initiator ratio and the initiator concentra-
tion. The role of the acid concentration in
determining the conversion, molecular weight,
and polydispersity in the miniemulsion polymer-
izations has been considered.
EXPERIMENTAL
Reagents
BPO, sodium dodecylbenzenesulfonate (SDBS),
hexadecane, TEMPO, OH-TEMPO, and CSA (Sig-
ma–Aldrich, Inc.) were used as received. Styrene
(Sigma–Aldrich) was washed three times with a 2
wt % NaOH solution to remove the inhibitor and
then washed three times with distilled water.
Washed styrene was dried on calcium chloride
overnight, distilled under vacuum, and refriger-
ated prior to use.
Polymerization
The aqueous phase consisted of SDBS (0.88 g,
2.52 mmol) and deionized water (120 mL),
whereas the organic phase consisted of styrene
(33 mL), hexadecane (5.4 g), BPO, and nitroxide
(Table 1). CSA was added to the aqueous phase.
The two phases were mixed with a stirring rod
and then passed twice through a Microfluidizer-
110S (Microfluidics International Corp.) operat-
ing at 300 kPa psi inlet pressure. The miniemul-
sion was then poured into a 300-mL autoclave
reactor. The reactor was purged six times with
nitrogen. The polymerization was run at 135 °C
 CAMPHORSULFONIC ACID 2831

Table 1. Summary of Nitroxide-Mediated Styrene Miniemulsion Polymerizations with and without CSA (CSA:
Nitroxide⫽1) Run at 135 °C for 6 h. Aqueous Phase: SDBS (0.88 g, 2.52 mmol), Deionized Water (120 mL).
Organic Phase: Styrene (33 mL), Hexadecane (5.4 g), BPO, Nitroxide, and CSA

Nitroxide Nitroxide BPO Nitroxide: CSA Conversion Dv

Experiment Type (mmol) (mmol) BPO (mmol) (%) Mn PDI (nm) fapp

1a TEMPO 0.70 0.41 1.7 0 57.7 42,530 1.20 156 0.49

1b TEMPO 0.70 0.41 1.7 0.70 59.8 53,970 1.27 145 0.40
2a TEMPO 1.47 0.41 3.6 0 24.6 13,360 1.16 162 0.67
2b TEMPO 1.47 0.41 3.6 1.47 60.1 69,000 1.19 139 0.32
3a TEMPO 2.11 1.24 1.7 0 48.5 17,340 1.15 174 0.34
3b TEMPO 2.11 1.24 1.7 2.11 63.8 32,510 1.20 156 0.24
4a TEMPO 4.40 1.24 3.6 0 16.9 2,360 1.07 263 0.87
4b TEMPO 4.40 1.24 3.6 4.40 46.5 36,920 1.25 378 0.15
5a OH-TEMPO 0.70 0.41 1.7 0 48.2 43,360 1.13 163 0.40
5b OH-TEMPO 0.70 0.41 1.7 0.70 55.9 54,300 1.31 133 0.38
6a OH-TEMPO 1.47 0.41 3.6 0 23.7 16,070 1.18 225 0.54
6b OH-TEMPO 1.47 0.41 3.6 1.47 58.5 71,740 1.25 146 0.30
7a OH-TEMPO 2.11 1.24 1.7 0 57.9 16,920 1.26 201 0.41
7b OH-TEMPO 2.11 1.24 1.7 2.11 66.0 35,180 1.17 128 0.23
8a OH-TEMPO 4.40 1.24 3.6 0 19.4 2,990 1.07 266 0.78
8b OH-TEMPO 4.40 1.24 3.6 4.40 41.4 48,970 1.19 172 0.10

for 6 h under approximately 300 kPa pressure.
Samples were withdrawn every 90 min.
Characterization
Conversion was determined gravimetrically. Mo-
lecular weight and polydispersity were deter-
mined by size exclusion chromatography with a
Waters 2690 separations module equipped with a
Waters 410 differential refractometer, Waters
Styragel columns, and an online degasser. Data
analysis was performed with Millennium 2010
software. A calibration curve was constructed
from monodisperse polystyrene standards rang-
ing from 8.7 ⫻ 102 to 2.8 ⫻ 106 amu. The eluent
was tetrahydrofuran flowing at 1 mL/min and at
a temperature of 30 °C. A Malvern Mastersizer
2000 was used to measure the particle size distri-
butions.
RESULTS AND DISCUSSION
We have reported the synthesis of polystyrene by
nitroxide-mediated free-radical polymerization in
miniemulsion.22 The importance of both the initi-
ator concentration and the ratio of nitroxide
(TEMPO) to initiator on conversion, molecular
weight, polydispersity, and initiator efficiency
was elucidated, and it was suggested that there is
an interaction between these two factors in mini-
emulsion NMRP (i.e., the quantitative effects of
changing one of the variables depend strongly on
the value of the other variable). In this article, we
report the results of a study on the role of CSA as
a rate accelerant in the miniemulsion NMRP of
styrene. We used two nitroxides (TEMPO and
OH-TEMPO) having very different partition coef-
ficients between styrene and water (K ⫽ [nitrox-
ide]styrene/[nitroxide]water) at 135 °C; KTEMPO
⫽ 98.8 M/M and KOH-TEMPO ⫽ 2.2 M/M).19 Two
sets of experiments were run in the study. In the
first set, equimolar amounts of CSA and either
TEMPO or OH-TEMPO were used in the poly-
merization. Following the experimental design
used previously,22 the role of CSA was investi-
gated in experiments in which we independently
varied the initiator concentration and the nitrox-
ide-to-initiator ratio. In the second set of experi-
ments, the CSA concentration was varied with
either TEMPO or OH-TEMPO at fixed values of
the initiator concentration and nitroxide-to-initi-
ator ratio.
Table 1 summarizes the experimental condi-
tions used in the first series of experiments. There
are four different experimental conditions that
comprise a two-factor, two-level experimental de-
sign where the factors are the initiator concentra-
tion and nitroxide:initiator ratio. For all runs in
Table 1, the CSA:nitroxide ratio was 1.0.
2832 CUNNINGHAM ET AL.

higher for the low nitroxide:BPO runs than the

high nitroxide:BPO runs in the absence of CSA,
the final conversions for high and low nitroxide:
BPO ratios are similar when CSA is added, sug-
gesting most of the excess nitroxide initially
present is consumed by CSA.
The ⫺ln(1 ⫺ X) versus time trends are approx-
imately linear for most experimental conditions.
For the high ratio of TEMPO:BPO ⫽ 3.6 in the
presence of CSA, the ⫺ln(1 ⫺ X) versus time plot
[Fig. 1(a)] shows a sharp upward curvature be-
yond 4.5 h, which may reflect a loss of livingness
caused by insufficient TEMPO to deactivate all
of the living chains. For the high ratio of OH-
TEMPO:BPO with CSA, however, the ⫺ln(1 ⫺ X)
versus time plot is fairly linear and does not ex-

Figure 1. ⫺ln(1 ⫺ X) versus time of miniemulsion

styrene polymerizations with and without CSA for dif-
ferent nitroxide:BPO ratios with (a) TEMPO or (b) OH-
TEMPO (0.41 mmol BPO, CSA:nitroxide ⫽ 1.0).

Figures 1 and 2 compare the conversion versus

time behavior and number-average molecular
weight (Mn) versus conversion, resepctively, with
and without added CSA (CSA: nitroxide ⫽ 1), at
both low (1.7) and high (3.6) ratios of nitroxide:
BPO for runs using 0.41 mmol BPO. CSA addition
moderately increases conversion at nitroxide:
BPO ⫽ 1.7 but has a much more pronounced
effect at nitroxide:BPO ⫽ 3.6. As CSA plays a role
in consuming free nitroxide,11 a greater effect
should be observed when the nitroxide concentra-
tion is initially high. The induction period usually Figure 2. Mn versus conversion in the presence of
observed without acid is not seen when CSA is CSA:nitroxide ⫽ 1.0 with (a) TEMPO or (b) OH-
added. Although the final conversions are much TEMPO (0.41 mmol BPO, CSA:nitroxide ⫽ 1.0).

Table 2. Effect of the Presence of CSA on Final Sample Properties (t⫽6 h) for TEMPO-Mediated
Polymerizations (CSA:TEMPO⫽1.0).
Without CSA
Conversion
BPO (mmol) TEMPO:BPO (%)
0.41 1.7 57.7
0.41 3.6 24.6
1.24 1.7 48.5
1.24 3.6 16.9
hibit upward curvature [Fig. 1(b)]. This suggests
that OH-TEMPO is consumed more slowly than
TEMPO by CSA as the reaction proceeds. Al-
though we know the partition coefficients of
TEMPO and OH-TEMPO, we do not know the
CSA partition coefficient, but it is appreciably
soluble in both water and styrene. The overall
nitroxide-consumption rate will be the sum of the
rates in the aqueous and particle phases. Under
the conditions in our experiments, greater parti-
tioning of OH-TEMPO into the aqueous phase
likely results in a slower overall nitroxide-con-
sumption rate by CSA.
Figures 2(a,b) depict the relationship between
molecular weight and conversion with TEMPO
and OH-TEMPO, respectively, for runs initiated
with 0.41 mmol BPO. Linear plots are expected
for living polymerizations. The approximate lin-
earity of these plots indicates nitroxide-mediated
styrene polymerizations in the presence of CSA
exhibiting the same living character as styrene
polymerizations without acid. Moreover, the poly-
dispersities (PDI ⫽ Mw/Mn) remain quite reason-
able even when CSA is used, usually less than 1.3
in the final sample for all experimental conditions
(Table 1).
To better appreciate the role of CSA, we inde-
pendently varied the nitroxide-to-BPO molar ra-
tio and the BPO concentration for both TEMPO-
and OH-TEMPO-mediated polymerizations. Ta-
ble 1 gives an overview of the final conversion,
molecular weight, and polydispersity obtained af-
ter 6 h of reaction. The apparent initiator effi-
ciency, fapp, was calculated according to the fol-
lowing equation (for the sample taken at 6 h):
# chains
f app ⫽
2 ⫻ nI
where nI is the number of moles of initiator
CAMPHORSULFONIC ACID 2833
With CSA
Mn Conversion Mn
(g/mol) PDI (%) (g/mol) PDI
42,530 1.20 59.8 53,970 1.27
13,360 1.16 60.1 69,000 1.19
17,340 1.15 63.8 32,510 1.20
2,360 1.07 46.5 36,920 1.25
(mstyrene)t ⫽ 0 ⫻ conversion
# chains ⫽ ;
Mn
(mstyrene)t⫽0 is initial number of moles of styrene.
Effect of Variation of the Nitroxide:BPO Ratio
CSA was added to polymerizations at nitroxide-
to-BPO ratios of 1.7 and 3.6. Polymerization was
performed in the presence of one molar equivalent
of CSA with respect to the nitroxide. At a nitrox-
ide:BPO ratio of 1.7, there is a slight deficiency of
nitroxide with respect to the number of primary
radicals that could be formed by BPO decomposi-
tion, whereas at a ratio of 3.6, a significant excess
of nitroxide exists. Figures 1(a,b) suggest that
higher conversion is achieved at any time when
CSA is added, although the enhancement is more
pronounced at a TEMPO:BPO ratio of 3.6. The
effect is similar when either TEMPO or OH-
TEMPO is used. At a nitroxide:BPO ratio of 1.7,
there is only a minor increase in the molecular
weight upon addition of CSA [Figs. 2(a,b)]. When
the nitroxide:BPO ratio is 3.6, the increase in
molecular weight is more pronounced than at a
ratio of 1.7, with TEMPO-mediated systems
showing a larger effect. These results indicate a
reduction in the number of chains upon CSA ad-
dition. Although lower molecular weights are ex-
pected at higher nitroxide:BPO ratios (because of
more chains being nucleated), which is true in the
absence of CSA, when CSA is added the molecular
weights are higher at a nitroxide:BPO ratio of 3.6,
reflecting fewer chains being nucleated despite
the presence of more nitroxide initially. This re-
duction in chain number upon addition of CSA
can be attributed to CSA consumption of the ni-
troxide in the early stages of reaction. This trend
is also reflected in a decrease of fapp (Table 1).
Tables 2 and 3 compare the final sample proper-
2834 CUNNINGHAM ET AL.
Table 3. Effect of the Presence of CSA on Final Sample Properties (t⫽6 h) for OH-TEMPO-Mediated
Polymerizations (CSA:TEMPO⫽1.0)
Without CSA
Conversion
BPO (mmol) OH-TEMPO:BPO (%)
0.41 1.7 48.2
0.41 3.6 23.7
1.24 1.7 57.9
1.24 3.6 19.4
ties with and without CSA with either TEMPO
(Table 2) or OH-TEMPO (Table 3).
Effect of the Variation of BPO Concentration
In this series of experiments, the added BPO was
varied from 0.1 (0.41) to 0.3 g (1.24 mmol) while
keeping the nitroxide-to-BPO ratio constant (ei-
ther 1.7 or 3.6). The significance of increasing the
BPO concentration is that the initial number of
chains is higher at higher BPO levels.
The amount of CSA was equal to one molar
equivalent with respect to the nitroxide. Tables 2
and 3 indicate that for either nitroxide, the aver-
age molecular weight decreases with an increase
in the initiator amount for the reactions per-
formed without acid. The effects of CSA addition
on the conversion, molecular weight, and polydis-
persity are similar at either BPO concentration
and for either TEMPO or OH-TEMPO.
Effect of the Variation of the CSA Concentration
We were also interested in studying the effect of
the CSA concentration on conversion and molec-
ular weight distribution. Figures 3(a,b) illustrate
the effects of increasing the CSA concentration on
conversion and molecular weight, respectively,
for TEMPO-mediated polymerizations. Figures
4(a,b) show these effects when OH-TEMPO is
used to mediate the polymerizations. The runs
shown in Figures 3 and 4 all used a nitroxide:BPO
ratio of 1.7 for which rate and enhancement ef-
fects are less pronounced and resemble conditions
when alkoxyamines are used. For both TEMPO
and OH-TEMPO, conversions at low times in-
crease with increasing [CSA]. However, as the
polymerization progresses, the differences in con-
version become less pronounced, and in fact the
relative order changes such that the runs with the
With CSA
Mn Conversion Mn
(g/mol) PDI (%) (g/mol) PDI
43,360 1.13 59.8 54,300 1.31
16,070 1.18 60.1 71,140 1.25
16,920 1.26 63.8 35,180 1.17
19,600 1.08 46.5 48,970 1.19
highest [CSA] do not have the highest conversion
at 6 h. At a given conversion, the effects of CSA on
molecular weight for either nitroxide are minimal
for CSA:nitroxide ratios of 0.5 or 1.0 but become
more significant at ratios of 1.5 and 5.0 [Figs. 3(b)
and 4(b)]. Conversion and molecular weight are
both enhanced without any significant broaden-
ing of the molecular weight distribution except at
the highest concentration of CSA (Table 4), al-
though more-pronounced broadening has usually
been seen at lower CSA levels in bulk systems
with comparable degrees of rate enhancement.
Partitioning of CSA into the aqueous phase may
be responsible for this apparent benefit, because
its concentration in the particle phase is initially
lower (as compared with bulk systems), thereby
causing less nitroxide consumption early in the
reaction. Later in the reaction, it can continue to
act as a nitroxide “sink” capable of consuming
excess nitroxide accumulating within the parti-
cles. However, as shown previously, the overall
consumption rate of nitroxide during polymeriza-
tion by CSA will be influenced by the partitioning
of both the nitroxide and CSA between the aque-
ous and particle phases.
Polymerization was also performed with a
TEMPO:BPO ratio of 2.7, whereas the CSA-to-
TEMPO ratio was varied from 0.5 to 1.5. Figures
5(a,b) describe the evolution of conversion and
molecular weight, respectively. With a TEMPO:
BPO ratio of 2.7, more excess TEMPO is initially
present than for the experiments shown in Fig-
ures 3 and 4, and consequently greater effects of
adding CSA are expected. Significant differences
are observed at all conversions with upward cur-
vature seen at CSA:TEMPO ratios of 1.0 and 1.5,
suggesting the loss of “livingness.” Molecular
weight profiles for CSA:TEMPO ratios of 1.0 and
1.5 also show downward curvature, consistent
with a loss of livingness at higher conversions
 CAMPHORSULFONIC ACID 2835

Figure 3. (a) Conversion versus time in the presence of varying CSA:nitroxide ratios
for TEMPO-mediated polymerizations (0.41 mmol BPO, TEMPO:BPO ⫽ 1.7). (b) Mn
versus conversion in the presence of varying CSA:nitroxide ratios for TEMPO-mediated
polymerizations (0.41 mmol BPO, TEMPO:BPO ⫽ 1.7).

caused by dead chains resulting from higher ter- sion, signifying a reduction in the number of
mination rates. CSA does, however, significantly chains. These results underscore the necessity of
increase the molecular weight at a given conver- understanding the interaction of the CSA:
2836 CUNNINGHAM ET AL.

Figure 4. (a) Conversion versus time in the presence of varying CSA:nitroxide ratios
for OH-TEMPO-mediated polymerizations (0.41 mmol BPO, OH-TEMPO:BPO ⫽ 1.7).
(b) Mn versus conversion in the presence of varying CSA:nitroxide ratios for OH-
TEMPO-mediated polymerizations (0.41 mmol BPO, OH-TEMPO:BPO ⫽ 1.7).

Table 4. Effect of CSA:Nitroxide Ratio on Final Polydispersities (t⫽6 h) (0.41 mmol
BPO, Nitroxide:BPO⫽1.7)
Nitroxide CSA:Nitroxide
TEMPO 0 1.20
TEMPO 0.5
TEMPO 1.0
TEMPO 1.5
TEMPO 5.0
OH-TEMPO 0 1.13
OH-TEMPO 0.5
OH-TEMPO 1.0
OH-TEMPO 1.5
OH-TEMPO 5.0
TEMPO ratio with the TEMPO:initiator ratio
used in the experiment.
CSA Effects in Presence of TEMPO versus
OH-TEMPO
The observed effects of CSA addition on conver-
sion and molecular weight did not generally
show significant differences between TEMPO-
and OH-TEMPO-mediated polymerizations de-
spite the vastly greater tendency of OH-TEMPO
to partition into the aqueous phase. The predom-
inant role played by thermal initiation in deter-
mining the radical concentration and therefore
the polymerization rate is probably also the rea-
son why few differences are observed between the
two nitroxides when CSA is added.
Effect of CSA on Final Mean Particle Size
With the exception of runs 4a and 4b, the addition
of CSA always resulted in a decrease in the mean
particle diameter, signifying more particles were
nucleated in the presence of CSA. The reason for
this trend is unclear but may be attributable to
CSA lowering nitroxide concentrations within un-
nucleated droplets to low enough levels that ther-
mal initiation proceeds more readily, thereby nu-
cleating more droplets earlier in the polymeriza-
tion. Runs 4a and 8a, which had the highest
amount of nitroxide added, both displayed unusu-
ally large particle sizes. We previously observed
anomalously large particle sizes at the same lev-
els of TEMPO used in runs 4a and 8a with potas-
sium persulfate as the initiator.22 This may be
related to the long induction periods under these
conditions, potentially leading to more droplet co-
CAMPHORSULFONIC ACID 2837
Polydispersity Final Conversion (%)
52.0
1.19 49.2
1.27 60.0
1.22 57.1
1.39 55.2
50.6
1.22 49.5
1.31 56.0
1.27 58.7
1.67 49.5
alescence. It is interesting that in the run medi-
ated with OH-TEMPO, addition of CSA reduces
the particle size, whereas when TEMPO is used to
mediate the polymerization, CSA addition results
in a larger diameter. A possible explanation is
that the OH-TEMPO concentration in the drop-
lets is lower than the TEMPO concentration
(⬃60% of OH-TEMPO is initially in the aqueous
phase as compared with ⬃2% of TEMPO being in
the aqueous phase). Consequently CSA addition
results in lower OH-TEMPO than TEMPO con-
centrations, allowing droplets to nucleate faster
when OH-TEMPO is used, therefore yielding a
smaller particle size.
CSA Effects in Miniemulsion versus Bulk
The CSA:nitroxide ratios used in this study
ranged from 0.5 to 5.0. Although other studies in
bulk systems witnessed significant rate enhance-
ments with CSA:nitroxide ratios of 0.5–1.0, the
effects observed in miniemulsion are not as dra-
matic. For example, Veregin et al.11 observed a
substantial rate enhancement in bulk using CSA:
TEMPO ⫽ 0.34 (TEMPO:BPO ⫽ 1.3), with the 6-h
conversion increasing from 50 to 80%. Although
we used higher CSA:TEMPO ratios, this is much
greater than we observed with a TEMPO:BPO
ratio of 1.7 that should give a larger effect than a
TEMPO:BPO ratio of 1.3. As noted previously,
Prodpran et al.15,16 observed a lower polymeriza-
tion rate in miniemulsion as compared with bulk
with CSA in their recipe. However, bulk and
miniemulsion rates are usually nearly the same
in the absence of CSA.22 Their results are consis-
tent with lower CSA concentrations in the parti-
cles because of phase partitioning, indicating
2838 CUNNINGHAM ET AL.

Figure 5. (a) Conversion versus time in the presence of varying CSA:nitroxide ratios
for TEMPO-mediated polymerizations (TEMPO:BPO ⫽ 2.7). (b) Mn versus conversion
in the presence of varying CSA:nitroxide ratios for TEMPO-mediated polymerizations
(TEMPO:BPO ⫽ 2.7).

higher CSA:TEMPO ratio concentrations are re-
quired to achieve the same degree of rate en-
hancement seen in bulk. Furthermore, as previ-
ously discussed, partitioning of CSA into the
aqueous phase may enable the CSA-containing
aqueous phase to act as a nitroxide “sink”
throughout polymerization, capable of consuming
excess nitroxide accumulating within the parti-
cles.
Control of Molecular Weight
An important consideration in designing living
radical polymerization processes is the predict-
ability of the molecular weight. With unimolecu-
lar initiators, there is generally close agreement
between the experimental and theoretical molec-
ular weight. However, with two-component initi-
ator systems, molecular weight prediction is
much less reliable and depends on several factors
including the nature of the initiator-derived rad-
icals and the ratio of nitroxide to initiator. Table
1 lists the “apparent” initiator efficiencies for
these experiments varying over a wide range de-
pending on the reaction conditions. CSA con-
sumes nitroxide, thereby reducing the number of
chains and thus the initiator efficiency. Although
the experimental molecular weights are repro-
 CAMPHORSULFONIC ACID 2839

ducible for a given set of conditions, a priori mo-

lecular weight prediction requires knowledge of
the initiator efficiency that is not readily avail-
able except from previous experiments.

Control Experiments: Nonliving Thermal

Polymerizations
Three nonliving control experiments were run to
isolate the effects of BPO and CSA on thermal
polymerization. Control experiment (CE) #1 had
neither BPO nor CSA, control experiment #2 had
only BPO, and control experiment #3 had only
CSA (Fig. 6, Table 5). The conversion in all runs
leveled off before complete conversion was
achieved, with CE #1 ceasing ⬃65% conversion,
whereas CE #2 and #3 reached ⬃80%. CE #2 and
#3 exhibit the same rate, which is moderately
faster than CE #1. Because these control mini-
emulsion polymerizations are nonliving, the rates
will be proportional to the particle number. How-
ever, the particle sizes for all runs are very simi-
lar, indicating runs CE #2 and CE #3 have inher-
ently higher rates as compared with CE #1.
There are also pronounced differences in the
molecular weight and number of chains among
the three runs. The number of chains decreases
in the order CE #2 ⬎ CE #3 ⬎ CE #1. CE #2 has
initiator and is therefore expected to have the
highest chain number. By the time the reactor
contents reach 135 °C, BPO will have essen-
tially completely decomposed. It could therefore
contribute to polymerization only in the early
stages of reaction. Assuming an initiator effi-
ciency of 50%, ⬃2.5e20 chains could in principle
be initiated by BPO decomposition, in addition
to the number of thermally generated chains.
The final chain number for CE #2 is close (with-
in 10%) to the sum of this value, and the num-
ber of thermally generated chains for CE #1,
explaining the lower molecular weight in CE #2,
and the higher rate. The chain number of CE #3
(only CSA added) lies in between that of CE #1
and CE #2. It is understandable that fewer
chains were produced in CE #3 than CE #2
(which contained BPO), but it is less clear why
CE #3 contains about three times more chains
than CE #1. CSA has been shown to suppress
thermal polymerization and reduce the chain
number (increase molecular weight) in bulk sty-
rene polymerization;29 however, in miniemul-
sion there is little effect on rate and an increase
in the number of chains when CSA is added. In
Figure 6. Conversion and Mn data from nonliving
control experiments.
nonliving miniemulsion, a decrease in molecu-
lar weight (increase in the number of chains)
implies a longer growing period for chains be-
tween termination events. The shorter growing
periods seen in CE #3 could be due to an in-
crease in transfer reactions or shorter periods
between chain initiation and either entry of an
aqueous radical or generation of a thermal rad-
ical within the particle. However, Buzanowski
et al.29 did not see evidence of transfer to CSA,
and reduced thermal initiation would lengthen,
not shorten, the growing period of a chain. A
more plausible explanation that accounts for
both the lower molecular weight and increased
rate is the sulfonic acid moiety of CSA (a strong
acid29) may increase the flux of radicals, a
known phenomenon in styrene emulsion poly-
merizations using sulfonic acid salts.31,32 A pro-
posed mechanism for the increase in radical
generation is found in the literature.32 If CSA
increases the radical flux in miniemulsion poly-
merizations, its role as a rate-enhancing addi-
tive in NMRP needs to be re-examined. In bulk
NMRP, CSA consumes nitroxide and sup-
presses thermal polymerization, thereby reduc-
ing the overall chain number. In miniemulsion
NMRP, CSA still consumes nitroxide but will
also increase the number of chains initiated. If
this postulated additional radical flux is true,
this effect would further reduce excess nitroxide
levels and therefore provide additional rate en-
hancement.
2840 CUNNINGHAM ET AL.

Table 5. Summary of Control Experiments Run at 135 °C for 6 h. Aqueous Phase: SDBS (0.88 g, 2.52 mmol),
Deionized Water (120 mL). Organic Phase: Styrene (33 mL), Hexadecane (5.4 g), BPO, Nitroxide, and CSA

Nitroxide BPO CSA Conversion Dv

Experiment (mmol) (mmol) (mmol) (%) Mn PDI (nm) Number of Chains

CE #1 0 0 0 64.7 261,970 2.47 129 4.42e19

CE #2 0 0.41 0 76.8 51,560 2.78 126 2.70e20
CE #3 0 0 0.48 81.0 106,640 2.67 125 1.37e20

CONCLUSIONS
CSA was added to nitroxide-mediated styrene
miniemulsion polymerizations to analyze its po-
tential role in enhancing the rate and increasing
the molecular weight. Two nitroxides with widely
differing water solubilities, TEMPO and OH-
TEMPO, were used to mediate the polymeriza-
tions. For all conditions, molecular weights are
higher in the presence of the acid, although the
degree of enhancement due to CSA addition var-
ies considerably. At a nitroxide:BPO ratio of 1.7,
moderate increases in conversion and molecular
weight were observed at CSA:nitroxide ratios of
1.0 with only slight increases in polydispersity. At
a nitroxide:BPO ratio of 3.6, conversions and mo-
lecular weights were increased significantly,
again with only slight increases in the polydisper-
sity. The use of CSA in the presence of a large
excess of nitroxide (nitroxide:BPO ⫽ 3.6) can ac-
tually reduce the number of chains to fewer than
observed when a lower nitroxide:BPO ratio of 1.7
is used. Despite the differences in their water
solubility, no significant differences of CSA addi-
tion were observed between TEMPO and OH-
TEMPO.
The rate enhancement obtained with CSA in
miniemulsion is not as dramatic as previously
seen in bulk. The acid may partition between
styrene and the aqueous phases, thereby reduc-
ing the concentration in the particles but also
enabling the CSA-containing aqueous phase to
act as a nitroxide “sink” during polymerization.
CSA may also increase the radical flux in mini-
emulsion (and emulsion) polymerizations, al-
though this effect does not occur in bulk polymer-
izations.
The Région Rhône-Alpes (France) is gratefully acknowl-
edged for K. Tortosa’s salary (contract N°99818999). The
authors also thank the Natural Sciences and Engineering
Research Council of Canada, Materials and Manufactur-
ing Ontario, and the Xerox Research Centre of Canada for
their financial support.
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