Effect of Initiator Type and

Concentration on Polymeri-
zation Rate and Molecular
Weight in the Bimolecular
Nitroxide-Mediated Radical
Polymerization of Styrene
TELMA REGINA NOGUEIRA, MARIA CECÍLIA GONÇALVES,
LILIANE MARIA FERRARESO LONA
School of Chemical Engineering, University of Campinas, Campinas 13083-970, S.P., Brazil

EDUARDO VIVALDO-LIMA
Departamento de Ingenierı́a Quı́mica, Facultad de Quı́mica, Universidad Nacional Autónoma de
México, 04510, México D.F., México

NEIL MCMANUS, ALEXANDER PENLIDIS

Institute for Polymer Research, Department of Chemical Engineering, University of Waterloo,
Waterloo, Ontario, Canada N2L 3G1
Received: February 11, 2009
Accepted: January 4, 2010

Correspondence to: Liliane Maria Ferrareso Lona; e-mail:

liliane@feq.unicamp.br.
Contract grant sponsor: São Paulo Research Foundation
(FAPESP).
Contract grant sponsor: National Council for Scientific and
Technological Development (CNPq) (Brazil).
Contract grant sponsor: Consejo Nacional de Ciencia y Tec-
nologı́a (CONACYT) (Mexico) (Projects CIAM U40259-Y and CB
101682) (Mexico).
Contract grant sponsor: Natural Sciences and Engineering Re-
search Council of Canada (NSERC/CRO).
Contract grant sponsor: Canada Research Chair (CRC)
Program (Canada), for a special Inter-American Materials
Collaboration (IAMC or CIAM) joint project.

Advances in Polymer Technology, Vol. 29, No. 1, 11–19 (2010)


C 2010 Wiley Periodicals, Inc.
BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

ABSTRACT: To increase the polymerization rate in the bimolecular

nitroxide-mediated radical polymerization (NMRP) of styrene, without using
expensive non-commercial reagents, an experimental study using
2,2,6,6-tetramethyl-1-piperidinoxyl as a controller and tert-butylperoxy
2-ethylhexyl carbonate (TBEC) as the initiator was carried out. The basis for
comparison was the bimolecular NMRP of styrene with dibenzoyl peroxide as
initiator. It was found that faster polymerization rates and still relatively low
polydispersities were possible using TBEC.  C 2010 Wiley Periodicals, Inc. Adv

Polym Techn 29: 11–19, 2010; Published online in Wiley InterScience

(www.interscience.wiley.com). DOI 10.1002/adv.20170

KEY WORDS: Kinetics (polym.), Living polymerization, Polystyrene, Radical

polymerization

the chosen temperatures, the decomposition rate of

Introduction the DCP is comparable to the thermal self-initiation
rate of styrene. The addition of the DCP increased

T he first patent on the use of nitroxides as stable

radicals for control of radical polymerizations
appeared in 1985.1 In this work, Rizzardo et al.2 stud-
ied the production of polymers with well-defined
molecular weights and controlled molecular weight
distribution by free radical polymerization.
Living free radical polymerization (LFRP) is a col-
lection of radical polymerization processes in which
a “trapping agent” or controller is added to the reac-
tion mixture, and an equilibrium is established be-
tween growing polymeric radicals (living polymer)
from activation and different types of dormant poly-
mer species from deactivation reactions (Eq. (1)).
kda
R• + X• −→
←− R − X (1)
ka
The equilibrium is usually shifted toward dor-
mant polymer (R–X), reducing the overall concen-
tration of free radicals, and therefore, the rate of
bimolecular radical termination. The result is a
living-like behavior of the polymerization system.
However, the low free radical concentration also
leads to relatively low polymerization rates. This re-
duction in the polymerization rate is one of the main
drawbacks of LFRP, and several research groups
have attempted to overcome this issue by using dif-
ferent approaches. More details about living free
radical polymerization can be found in Moad and
Solomon.3
Greszta and Matyjaszewski4 tried to increase
the polymerization rate by using a long half-life
initiator, dicumyl peroxide (DCP), in addition to a
unimolecular initiator, 1-phenyl ethyl-TEMPO. At
the observed polymerization rates from those seen
with 1-phenyl ethyl-TEMPO on its own. They also
observed that the molecular weights increased lin-
early with conversion. However, the use of DCP in-
creased polydispersity (PDI), which became larger
as the concentration of DCP was increased, but the
PDI was still below the limit of 1.5 for standard
free radical polymerization. Their results did show
that the polydispersities observed always decreased
as the reaction progressed. When they examined
the use of DCP as initiator, they noticed a long
induction period at the beginning of the polymer-
ization. Another alternative examined by Greszta
and Matyjaszewski4 consisted of using a mixture
of DCP and azobisisobutyronitrile (AIBN) initiators
in the bimolecular nitroxide-mediated radical poly-
merization (NMRP) process. Faster polymerization
rates were obtained, similar to what happened with
the case of 1-phenyl ethyl-TEMPO, but larger poly-
dispersities were observed for the products (PDI =
1.55), due to this new source of radicals generated
by the DCP decomposition (PDI = 1.3 when no DCP
was used).
Similarly, Goto and Fukuda5 studied the effect
of adding tert-butyl hydroperoxide (BHP) at 114◦ C,
on polymerization rate and molecular weight in the
LFRP of styrene initiated by 2,2,6,6,-tetramethyl-
1-poly(styroxypiperidine) (PS-TEMPO) (unimolec-
ular process). They demonstrated that the use of
BHP increased the polymerization rate by a fac-
tor higher than 3, but polydispersity values were
higher than those obtained for standard unimolecu-
lar NMRP in the initial stages of the reaction. They
showed that polydispersity depends on the initiator

12 Advances in Polymer Technology DOI 10.1002/adv

 BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE
concentration and increases with increasing BHP
concentration, at a given conversion. The authors
concluded that polydispersity is determined by the
number of activation-deactivation cycles and that
the propagation rate has no effect on polydispersity.
Another technique that has been used to in-
crease the polymerization rate in NMRP is the
use of additives, such as camphorsulfonic acid,6−9
2-fluoro-1-methylpyridinium p-toluenesulfonate,10
acetic anhydride,11−14 ascorbic acid15−17 and dode-
cylbenzenesulfonic acid.18 However, the use of addi-
tives in controlled polymerization makes the process
more expensive and/or complicates things further
due to possible side reactions.
Following what Greszta and Matyjaszewski4 and
Goto and Fukuda5 have done for unimolecular
NMRP, in this paper we describe the use of an initia-
tor (tert-butylperoxy 2-ethylhexyl carbonate, TBEC)
with a low decomposition kinetic rate constant (kd )
in combination with TEMPO. This makes use of
slow initiator decomposition and a longer availabil-
ity of free radicals from the added initiator (in ad-
dition to those produced by thermal self-initiation)
throughout the polymerization. Using this tech-
nique, overall faster polymerization rates and rel-
atively low polydispersities were obtained. These
improvements were obtained without using more
complicated operation regimes (e.g., continuous or
semibatch), or additives, and so they may offer yet
another potentially useful alternative for the prepa-
ration of narrow polydispersity polymers.
We decided to consider the bimolecular process
because it is simpler and faster since in the unimolec-
ular process alkoxyamine should be synthesized be-
fore the reaction. Although the unimolecular process
provides a good control of the structure of the poly-
mer, the bimolecular process is cheaper.
Experimental
Styrene (Sigma-Aldrich, St. Louis, MO; 99%)
was washed thrice with a NaOH solution and
a fourth time with deionized water. It was then
dried over calcium chloride and finally distilled
under vacuum. TEMPO (Acros Organics, Geel,
Belgium; 98%) and TBEC (Sigma-Aldrich; 95%) were
used as received. Dibenzoyl peroxide (BPO; Akzo
Nobel, Chicago, IL; 75%) was dried over a sil-
ica gel desiccant. The required amounts of styrene,
initiator, and controller were weighed, mixed, and
Advances in Polymer Technology DOI 10.1002/adv
poured into glass ampoules. The contents of the am-
poules were degassed by three successive freeze–
thaw cycles under vacuum (0.03 mbar). The am-
poules were torch-sealed under vacuum and then
placed in liquid nitrogen until used. The polymer-
izations were carried out in a circulator bath, con-
taining silicone oil, with temperature control, at
the predetermined temperatures (125, 130, or 135 ±
0.1◦ C). The ampoules were weighed and broken, and
the polymer/monomer mixture was dissolved in
methylene chloride and precipitated with ethanol.
After monomer and solvent evaporation, all sam-
ples were placed in an oven to complete drying.
After the evaporation of solvent and monomer, the
conversion was obtained by gravimetric method.
The polymer molecular weight was characterized
by gel permeation chromatography (GPC). The GPC
system was composed of a Viscotek triple detec-
tor, with refractive index, right angle (90◦ ) laser
light scattering, and capillary viscometer. The eluent
used was tetrahydrofuran, and the Viscogel columns
(I-MBHMW-30783—limit of exclusion of 10MK) had
dimensions of 300 mm (length) × 7.8 mm (inside di-
ameter), with particle size of 10 μm.
Results and Discussion
Runs were performed following an experimen-
tal design, in which temperature, initiator concen-
tration, and the ratio between controller and initia-
tor concentrations were the factors, and time (min),
number average molecular weight, and polydisper-
sity were the responses of interest. This way, a 23
factorial design was obtained, where 3 is the number
of studied factors and 2 is the number of the differ-
ent levels (high and low) studied. In Table I, details
are shown of these eight treatments (runs 1–4 and
6–9), two replicates at the center point (runs 10 and
11) plus an additional run using BPO as initiator
(run 5).
For the comparison between BPO and TBEC in the
NMRP process, the decomposition kinetic rate con-
stants kd for both initiators were taken into account.
Their values were calculated by Dhib et al.19
EFFECT OF THE TYPE OF INITIATOR
Figure 1a shows conversion versus time profiles
using TBEC and BPO at 125◦ C (runs 1, 2, and 5).
It is observed that the polymerization rate is faster
13
BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

TABLE I when TBEC is used (compare run 2 against run 5).

Experimental Conditions for the NMRP Process It is also observed from runs 1 and 5 of Fig. 1a
Initiator Molar Ratio that the polymerization rate remained faster when
Temperature Concentration (R = [TEMPO]/ TBEC was used even if TBEC’s concentration was
Run Initiator (◦ C) (M) [I]) 12 times lower than the concentration of BPO. This
can be explained by the fact that BPO has a far higher
1 TBEC 125 0.0029 1.1 decomposition rate (kd = 0.226 min−1 ), and at these
2 TBEC 125 0.036 1.1 conditions it will be completely decomposed after a
3 TBEC 135 0.0029 1.1 few minutes of reaction time. After this period, the
4 TBEC 135 0.036 1.1
polymerization rate follows standard NMRP kinet-
5 BPO 125 0.036 1.1
6 TBEC 125 0.0029 1.3
ics. More data on NMRP using BPO as initiator can
7 TBEC 125 0.036 1.3 be found in Nabifar et al.,20 who studied the effect of
8 TBEC 135 0.0029 1.3 temperature and molar ratio between TEMPO and
9 TBEC 135 0.036 1.3 BPO on polymerization rate, molecular weight, and
10 TBEC 130 0.0195 1.3 polydispersity and in Roa-Luna et al.,21 who studied
11 TBEC 130 0.0195 1.3 diffusion effects in NMRP of styrene in the presence
of TEMPO and BPO. On the other hand, TBEC has
1 a relatively low decomposition rate at this temper-
ature (kd = 0.017 min−1 ). This results in significant
differences between the courses of reaction with the
0.8 different initiators. First, extrapolation of the conver-
sion versus time profile for the initial stages shows
Co nversio n

0.6 that there must be an induction period for the re-

T = 125°C actions using TBEC as the initiator. The induction
0.4 Molar ratio = 1.1 period has already been described by Bonilla et al.22
and Butté et al.23 This occurs because the rate of
[TBEC] = 0.036 M/ run 2 initiator decomposition is slow compared to that
0.2 [TBEC] = 0.0029 M/ run 1
[BPO] = 0.036 M/ run 5 when BPO is the added initiator. After this period,
there still will be a significant concentration of TBEC
0 present and so extra radical production will con-
0 100 200 300 400 500 tinue, because the half life of TBEC is much higher
Time (min) (t1/2 = 40.6 min at T = 125◦ C) than the one of BPO
(a) (t1/2 = 3.1 min at T = 125◦ C). The polymerization
rate is then dictated by both thermal self-initiation of
120,000 2
Mn / [TBEC] = 0.0029 M/ run 1 T = 125°C styrene plus initiator decomposition, so that a higher
Mn / [TBEC] = 0.036 M/ run 2 Molar ratio = 1.1 polymerization rate is possible because the radi-
100,000 Mn / [BPO] = 0.036 M/ run 5
PDI/ [TBEC] = 0.0029 M/ run 1 1.8 cal concentration is higher than in standard NMRP.
PDI/ [TBEC] = 0.036 M/ run 2
80,000 PDI/ [BPO] = 0.036 M/ run 5 This also leads to a low free TEMPO concentra-
Po lyd isp ersity

1.6 tion because of the necessity to maintain equilibrium

Mn (g/mol)

60,000 conditions.
1.4
The number average molecular weight, Mn , and
40,000 polidispersity for runs 1, 2, and 5 are shown
in Fig. 1b. The measurements obtained by GPC
1.2
20,000 (Mn and polydispersity) can present errors below
10%. Figure 1b shows that molecular weight in-
0 1 creases linearly with conversion and that poly-
0 0.2 0.4 0.6 0.8 1 dispersity is always lower than 1.5. These results
Conversion indicate that with TBEC the polymerization was
(b) not well controlled in the initial stages of reac-
tion as the PDI is quite high, but as reaction pro-
FIGURE 1. Effect of initiator type (TBEC or BPO) on (a) gresses the PDI drops. The poor control in the
conversion versus time, (b) M n versus conversion, and initial stages of the polymerization has already
polydispersity versus conversion. been shown through theoretical description,24,25

14 Advances in Polymer Technology DOI 10.1002/adv

 BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

experimentally,26 and both kinetic modeling and ex- 1

perimental studies.27
0.8

Conversion
EFFECT OF THE MOLAR RATIO 0.6
[TEMPO]/[TBEC] Molar ratio = 1.1/ run 2
Molar ratio = 1.3/ run 7
A monofunctional initiator can produce two ini- 0.4
tial free radicals if its efficiency is 100%. In the case
of bimolecular NMRP, a controller to initiator ratio 0.2
of 2 would be needed to achieve the same equimolar
conditions (assuming 100% efficiency). If the initia- 0
tor efficiency is 50%, the controller to initiator molar 0 100 200 300 400 500 600
ratio should be equal to 1. Since the efficiency of BPO
Time (min)
and AIBN at 115–135◦ C is around 0.55, the most ad-
equate controller/initiator ratio is 1.1, to obtain the (a)
correct balance of initiating radicals to TEMPO. A
20,000 1.5
similar efficiency value was assumed for TBEC, and
so TEMPO/initiator ratios were kept at this level for
our study. 16,000 1.4
Roa-Luna et al.21 simulated a NMRP system con-

P o ly d is p e rs it y
sidering a decrease in the effective TEMPO concen- Mn (g/mol) 12,000 1.3
tration, to consider potential reactions that can occur
between initiator and controller. They found a higher 8,000 1.2
polymerization rate at the beginning of the reaction, Mn / molar ratio 1.3/run 7
but no significant change was observed in the over- Mn / molar ratio 1.1/run 2
4,000 1.1
all profile. They also observed that a better agree- PDI/ molar ratio 1.3/run 7
ment between the experimental data and simulation PDI/ molar ratio 1.1/run 2
results is obtained if the decrease in the effective 0 1
controller concentration is considered, to take into 0 0.2 0.4 0.6 0.8 1
account chemical (side) reactions between TEMPO Conversion
and initiator. The reaction between controller and
initiator is not the focus of this work, but in this (b)
present paper a higher ratio between TEMPO and
TBEC is also considered (ratio = 1.3). FIGURE 2. Effect of [TEMPO]/[TBEC] ratio on (a)
Figure 2 shows profiles of conversion versus time conversion versus time, (b) M n versus conversion, and
(Fig. 2a) and number average molecular weight and polydispersity versus conversion. T = 125◦ C and
PDI versus conversion (Fig. 2b), for two different [TBEC] = 0.036 M.
molar ratios of TEMPO and TBEC (runs 2 and 7).
It is observed in Fig. 2a that an increase in the
[TEMPO]/[TBEC] ratio from 1.1 to 1.3 (maintain-
is the activation-deactivation equilibrium constant,
ing the initiator concentration constant and vary-
and [M] is monomer concentration. A longer time to
ing the TEMPO concentration) decreases the rate of
a given conversion also relates to a longer induction
polymerization, which was expected, according to
period that stems from the higher concentration of
Eq. (2).
TEMPO in the system.
It is also seen from Fig. 2b that the profiles con-
d[M] k p [R − T][M] sidering different molar ratios of TEMPO and TBEC
= − (2)
dt K L [T• ] are very similar. Nabifar et al.20 also related that
the effect of this factor on molecular weights was
k p in Eq. (2) is the propagation kinetic rate con- not pronounced for some experimental conditions.
stant, [R – T] is the concentration of dormant poly- Figure 2b also shows that the molecular weights
mer chain using (TEMPO) as controller, [T• ] is the increase linearly with conversion, which is ex-
concentration of TEMPO stable free radicals, K L pected for a controlled polymerization process. In a

Advances in Polymer Technology DOI 10.1002/adv 15

BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

bimolecular initiated system, it has been shown by 1

Roa-Luna et al.21 that the true concentration of con-
troller is difficult to assess because peroxide reacts 0.8 T = 125°C
with nitroxide and reduces the concentration of ac- [TBEC] = 0.029 M

tive TEMPO in the polymerization reaction. This is

Conversion
0.6
well evidenced for BPO, and it is likely that TBEC
would lead to a similar outcome. In Fig. 2b, it is ob-
0.4
served that polydispersity decreases when the ra- Molar ratio = 1.1/ run 1
tio TEMPO/TBEC is increased, which can be ex- Molar ratio = 1.3/ run 6
0.2
plained by the fact that the higher TEMPO levels
better maintain the equilibrium condition required
for controlled radical polymerization. Furthermore, 0
0 100 200 300 400 500
lower polydispersities (below 1.5) were obtained Tim e (m in)
and they followed the trend expected for NMRP,
that is, the decrease of PDI with the increase of (a)
conversion. 120,000 1.5
The effect of the ratio [TEMPO]/[TBEC] was fur-
ther analyzed by looking at the effect of reducing 100,000
1.4
by about an order of magnitude both the concentra-

Polydispersity
80,000
tions of TEMPO and TBEC, but keeping their ratios

Mn [g/mol]
1.3
equal to 1.1 and 1.3 (see Fig. 3). It was observed 60,000
(Fig. 3a) that increasing the TEMPO/TBEC ratio 1.2
from 1.1 to 1.3 did not result in a pronounced 40,000 Mn / Molar ratio = 1.3/ run 6
Mn / Molar ratio = 1.1/ run 1
difference between the profiles. Figure 3b shows 20,000
T = 125°C 1.1
[TBEC] = 0.029 M PDI/ Molar ratio = 1.3/ run 6
similar behavior in molecular weight trends (com- PDI/ Molar ratio = 1.1/ run 1
pare with Fig. 2b). Also, the effect of increasing the 0 1
TEMPO/TBEC ratio has a negligible effect on poly- 0 0.2 0.4 0.6 0.8 1
dispersity. However, molecular weight values seen Conversion
in this case would indicate a significant level of un- (b)
controlled polymerization overlaid with some con-
trolled polymerization. This is clear from the fact FIGURE 3. Effect of [TEMPO]/[TBEC] ratio on (a)
that an extrapolation of the Mn versus conversion conversion versus time, (b) M n versus conversion, and
trendline would not intercept the molecular weight polydispersity versus conversion. T = 125◦ C and
axis close to 0, the implication being that in the early [TBEC] = 0.0029 M.
stages, the polymerization is not controlled and only
becomes so when the levels of produced radicals
drop sufficiently for the NMRP equilibrium to con- tures of 120 and 130◦ C. The trends in the polydis-
trol the system. persity versus conversion profile (Fig. 4b) are rather
different at the two temperatures. The large differ-
ences in polydispersity at high conversions, shown
in Fig. 4b, are likely to stem from the higher rate of
EFFECT OF TEMPERATURE USING
radical production at 135◦ C. This reduces the con-
TBEC AS INITIATOR
centration of free TEMPO in the reaction mixture
The results presented in Fig. 4 show the effect of and thus reduces the rate of deactivation relative to
temperature on the polymerization rate (expressed propagation and so leads to broadening of the molec-
as conversion vs. time, Fig. 4a), molecular weight ular weight distribution (MWD). It will also lead to
(Mn vs. conversion), and polydispersity versus con- a greater proportion of standard termination, since
version (Fig. 4b). An increase in temperature from the radical concentration and the termination kinetic
125 to 135◦ C results in a higher polymerization rate rate constant are higher. The same behavior on PDI
(Fig. 4a) and no significant change in Mn profiles profiles with the temperature is observed when the
(Fig. 4b). Nabifar et al.20 reported similar results for molar ratio between TEMPO and TBEC is 1.3, keep-
the living free radical polymerization of styrene us- ing the concentration of TEMPO equal to 0.0029 M
ing BPO as the initiator and considering tempera- (not shown).

16 Advances in Polymer Technology DOI 10.1002/adv

 BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

1 1

0.8 0.8
Conversion

0.6

Conversion
0.6 T = 135°C/ run 4
T = 125°C/ run 1 T = 125°C/ run 2
0.4
T = 135°C/ run 3 0.4

0.2 [TBEC] = 0.036 M

[TBEC] = 0.0029 M
0.2 Molar ratio = 1.1
Molar ratio = 1.1
0
0 100 200 300 400 500 0
Tim e (m in) 0 100 200 300 400 500 600
Time (m in)
(a)
(a)
120,000 1.60
20,000 1.6
100,000 1.50
Polydispersity 16,000 1.5
80,000 1.40

Polydispersity
Mn (g/mol)

[TBEC] = 0.0029 M 1.4

Mn (g/mol)
Molar ratio = 1.1 12,000
60,000 1.30
1.3
40,000 1.20 8,000
Mn / T = 125°C/ run 1 Mn / T = 125°C/ run 2 1.2
Mn / T = 135°C/ run 3 Mn / T = 135°C/ run 4
20,000 PDI/ T = 125°C/ run 1 1.10 4,000 1.1
PDI/ T = 125°C/ run 2
PDI/ T = 135°C/ run 3
PDI/ T = 135°C/ run 4
0 1.00 0 1.0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Conversion Conversion
(b) (b)
FIGURE 4. Effect of temperature on (a) conversion FIGURE 5. Effect of temperature on (a) conversion
versus time, (b) M n versus conversion, and polydispersity versus time, (b) M n versus conversion, and polydispersity
versus conversion. [TEMPO]/[TBEC] = 1.1 and [TBEC] = versus conversion. [TEMPO]/[TBEC] = 1.1 and [TBEC] =
0.0029 M. 0.036 M.

Figure 5 shows the results for the reactions equiv-

alent to those shown in Fig. 4, but using higher con- the temperature on polydispersity. Only when the
centrations of both TEMPO and TBEC. As expected, concentrations of TEMPO and TBEC are low, an in-
the polymerization rate is faster (Fig. 5a) when tem- crease in temperature results in a deviation from
perature is increased, Mn is slightly lower, and there living behavior (an increase in polydispersity). It is
is no change in polydispersity (the profiles practi- probable that the concentration of free radicals pro-
cally overlap). The only differences in behavior be- duced by thermal self-initiation is high enough to
tween Figs. 4 and 5 are observed in the polydisper- alter (reduce) the controller/free radicals ratio, thus
sity versus conversion profiles. In Fig. 4b there is a promoting less of a living behavior.
large difference in the profiles at different temper-
atures, whereas in Fig. 5b the profiles overlap. It is
EFFECT OF A SIMULTANEOUS INCREASE
likely that the very low TEMPO concentration in
IN THE INITIATOR AND TEMPO
Fig. 4b is not high enough to provide controlled be-
CONCENTRATION
havior, even if the TEMPO/TBEC ratio is adequate.4
Results from experiments where the TEMPO/ Figure 6 shows the effect of a simultaneous in-
TBEC ratio was 1.3 and the TBEC concentration was crease in the concentrations of TEMPO and TBEC,
0.036 M showed similar behavior compared to the keeping the TEMPO/TBEC ratio as 1.1, at 125◦ C
one observed in Fig. 5, with no noticeable effect of (similar trend is observed when T = 135◦ C and

Advances in Polymer Technology DOI 10.1002/adv 17

BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE

1
Conclusions
0.8

A comprehensive experimental study on the use

Conversion

0.6
of TBEC in the bimolecular NMRP of styrene was
0.4 [TBEC] = 0.0029 M/ run 1 carried out. It was found that TBEC is more effec-
[TBEC] = 0.036 M/ run 2 tive than BPO, because lower concentrations (about
0.2 T = 125°C an order of magnitude lower than BPO for similar
Molar ratio = 1.1 results) are needed, and faster polymerization rates
0 are possible, thus making TBEC an adequate choice
0 100 200 300 400 500 600 for bimolecular NMRP of styrene.
Time (min) The effects of temperature, concentrations of
(a) TEMPO and TBEC, and their ratios were ana-
lyzed. Typical controlled/“living” features were ob-
120,000 1.50 served, and a reliable experimental database was
generated.
100,000
1.40
T = 125°C
80,000 Molar ratio = 1.1 Polydispersity
Mn (g/mol)

1.30
60,000
1.20
Nomenclature
40,000 Mn / [TBEC] = 0.0029 M/ run 1
Mn / [TBEC] = 0.036 M/ run 2
PDI/ [TBEC] = 0.0029 M/ run 1 [BPO] Dibenzoyl peroxide (BPO)
PDI/ [TBEC] = 0.036 M/ run 2 1.10
20,000
concentration
0 1.00 [I] Initiator concentration
0 0.2 0.4 0.6 0.8 1 ka Activation kinetic rate constant
Conversion kd Initiator decomposition kinetic rate
(b) constant
kda Deactivation kinetic rate constant
FIGURE 6. Effect of a simultaneous increase in the K L = kda /ka Activation/deactivation equilibrium
concentrations of TEMPO and TBEC on (a) conversion constant
versus time, (b) M n versus conversion, and polydispersity kp Propagation kinetic rate constant
versus conversion. [TEMPO]/[TBEC] = 1.1 and [M] Monomer concentration
T = 125◦ C. Mn Number average molecular weight
PS-TEMPO 2,2,6,6,-tetramethyl-1-
poly(styroxypiperidine)
TEMPO/TBEC ratio is 1.3, so only results for T = R• Growing polymer chains
125◦ C and ratio equal to 1.1 will be shown). It is ob- [R–T] Concentration of dormant polymer
served that there is a significant increase in the poly- chains using (TEMPO) as
merization rate when the concentrations of TEMPO controller
and TBEC are simultaneously increased (see Fig. 6a). [R–X] Concentration of dormant polymer
Although the proportion of capping molecules is the chains
same in both cases (at the two concentration levels), T Temperature
in the case of higher concentrations, there are more [T• ] Concentration of TEMPO stable free
growing chains (i.e., faster polymerization rate) in radicals
between capping/decapping cycles. Distribution of t1/2 Half-life of initiator
the added monomer units amongst a higher number [TBEC] Concentration of tert-butylperoxy
of polymer chains also explains the lower molecular 2-ethylhexyl carbonate (TBEC)
weights when the concentrations are higher (Fig. 6b). [TEMPO] Concentration of 2,2,6,6-
It is observed in Fig. 6b that polydispersity does not tetramethyl-1-piperidinoxyl
change much when the concentrations of TEMPO (TEMPO)
and TBEC are increased by almost an order of X Capping molecules (stable free
magnitude. radicals)

18 Advances in Polymer Technology DOI 10.1002/adv

 BIMOLECULAR NITROXIDE-MEDIATED RADICAL POLYMERIZATION OF STYRENE
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