Iron(III)-Mediated AGET ATRP of Styrene Using

Tris(3,6-Dioxaheptyl)amine as a Ligand
LIANGJIU BAI, LIFEN ZHANG, JIAN ZHU, ZHENPING CHENG, XIULIN ZHU

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,

Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

Received 1 December 2008; accepted 14 January 2009

DOI: 10.1002/pola.23300
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: A commercially available tris(3,6-dioxaheptyl)amine (TDA-1) was used as

a novel ligand for activator generated by electron transfer atom transfer radical poly-
merization (AGET ATRP) of styrene in bulk or solution mediated by iron(III) catalyst
in the presence of a limited amount of air. FeCl3
6H2O and (1-bromoethyl)benzene
(PEBr) were used as the catalyst and initiator, respectively; and environmentally
benign ascorbic acid (VC) was used as the reducing agent. The polymerizations show
the features of living/controlled free-radical polymerizations and well-dened poly-
styrenes with molecular weight Mn 240036,500 g/mol and narrow polydispersity
(Mw/Mn 1.111.29) were obtained. The living feature of the obtained polymer was
further conrmed by a chain-extension experiment. V C 2009 Wiley Periodicals, Inc.

J Polym Sci Part A: Polym Chem 47: 20022008, 2009

Keywords: atom transfer radical polymerization (ATRP); AGET ATRP; living
polymerization; tris(3,6-dioxaheptyl)amine (TDA-1); polystyrene

INTRODUCTION To control over the polymerization with liv-

Atom transfer radical polymerization (ATRP), as
a metal-mediated living/controlled radical poly-
merization (LRP), provides a simple way to syn-
thesize well-dened polymers with predetermined
molecular weights and narrow molecular weight
distributions.1 In ATRP, the polymeric chain
growth is mediated by a transition-metal complex,
and the mechanism is outlined in Scheme 1. A
low radical concentration, which facilitates to
minimize the termination reaction, can be main-
tained by a dynamic equilibrium between the rad-
ical species (Rn) and the dormant species (Rn-X)
due to the redox reaction of the metal catalyst
between the lower oxidation state (Mnt -X/L) and
higher oxidation state (X-Mtn1 -X/L).1(e)
Correspondence to: Z. Cheng (E-mail: chengzhenping@
suda.edu.cn)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 20022008 (2009)
V
C 2009 Wiley Periodicals, Inc.
2002
ing fashion, a high-catalyst concentration
(5000 ppm of catalyst) has been often used in
a normal ATRP. Thus, the catalyst must be
removed from the product by laborious and
costly purication methods.2 Several different
techniques including activators generated by
electron transfer ATRP (AGET ATRP),3 activa-
tors regenerated by electron transfer ATRP
(ARGET ATRP),4 and initiators for continuous
activator regeneration ATRP (ICAR ATRP)5
have been successfully developed to decrease
the amounts of catalyst. Recently, Percec et al.6
have successfully developed a single electron-
transfer living radical polymerization (SET-
LRP) technique for activated and nonactivated
vinyl monomers containing electron-withdraw-
ing groups such as acrylates, methacrylates,
and vinyl chloride. All these techniques are
based on the metal-mediated LRP, whereby
the ligand provides appropriate solubility and
adjustable redox potential for transition-metal
 IRON(III)-MEDIATED AGET ATRP OF STYRENE 2003

Scheme 1. Typical ATRP mechanism.

complexes. In addition, unlike ATRP, the role of EXPERIMENTAL

the ligand is also to mediate disproportion of
Cu(I) into active Cu(0) and Cu(II) in a SET-LRP Materials
process. Therefore, ligand design is extremely
Styrene (St) ([99%), was purchased from Shang-
important to achieve high activity and to pro-
hai Chemical Reagents Co. (Shanghai, China). It
vide polymer with narrow molecular weight
was washed with an aqueous solution of sodium
distribution.7
hydroxide (5 wt %) three times, followed by deion-
Building on the known use of ligands, nitrogen-
ized water until neutralization, and then dried
based ligands and phosphorus-based ligands are
over anhydrous magnesium sulfate, distilled
the most frequently used ones. A large number
under reduced pressure, and stored at 18  C.
of nitrogen-based neutral ligands have been used
Tris(3,6-dioxaheptyl)amine (TDA-1) (97%) was
for different metal-mediated LRPs,1(e),6(a) such
purchased from Linhai Xinghua Chemical Fac-
as 2,20 -bipyridine (bpy),8 N,N,N0 ,N00 ,N00 -pentame-
tory (Zhejiang, China) and used as received.
thyldiethylenetriamine (PMDETA),9 tris(2-pyri-
Iron(III) chloride hexahydrate (FeCl3
6H2O)
dyl)methyl)amine (TPMA),3(e),10 tris(2-(dimethyl-
([99%) and ascorbic acid (VC) ([99.7%) were pur-
amino) ethyl)amine (Me6TREN),6(a,i),11 and oth-
chased from Shanghai Chemical Reagents Co.
ers.2(b),12 A cheap and commercially available
(Shanghai, China) and used as received. (1-Bro-
amine, tris(3,6-dioxaheptyl) amine (TDA-1), can
moethyl)benzene (PEBr) (97%) was purchased
complex with many cations such as Cu(II),
from Acros and used as received. N,N-dimethyl-
Ni(II), Fe(II), and Fe(III) and is a highly active
formamide (DMF) (analytical reagent), tetrahy-
ligand.13 Unfortunately, to the best of our knowl-
drofuran (THF) (analytical reagent), and all other
edge, few documents have reported the TDA-1
chemicals were obtained from Shanghai Chemi-
ligand in the metal-mediated LRPs. Zhu et al.
cal Reagents Co. and used as received unless
rst reported a normal ATRP of styrene (St) using
mentioned.
FeX2(X Cl, Br)/TDA-1 complex catalyst sys-
tem in 2006, and the results showed that the
FeX2(X Cl, Br)/TDA-1 complex is a highly active
General Procedure for AGET ATRP of St
iron-based catalyst system for the normal ATRP
of St.14 In view of the intrinsic toxicity of the cop- A typical bulk polymerization procedure for the
per compound, the environmentally benign iron molar ratio of [St]0/[PEBr]0/[FeCl3
6H2O]0/[TDA-
complexes using iminodiacetic acid3(g) or triphe- 1]0/[VC]0 500/1/1/2/1 is as follows: a mixture
nylphosphine3(h) as a ligand have been success- was obtained by adding FeCl3
6H2O (14 mg, 0.052
fully to mediate AGET ATRP of methyl methacry- mmol), TDA-1 (33.1 lL, 0.101 mmol), St (3.0 mL,
late. However, the catalyst systems mentioned 26.2 mmol), PEBr initiator (7.3 lL, 0.052 mmol),
above are not highly active catalyst systems due and VC (9.1 mg, 0.052 mmol) to a dried ampoule.
to their relatively lower initiator efciencies. For the deoxygenated system, the mixture was
Thus, considering of the higher activity of the thoroughly bubbled with argon for 20 min to elim-
FeX2(X Cl, Br)/TDA-1 complex in a normal inate the dissolved oxygen, and then ame-sealed.
ATRP process, the aim of this work is to report For the oxygenated system, the ampoule was
the results of the iron(III)-mediated AGET ATRP ame-sealed directly (no bubbling with argon)
of styrene using FeCl3
6H2O as the catalyst, (1- and then transferred into an oil bath held by a
bromoethyl)benzene (PEBr) as the initiator, ascor- thermostat at the desired temperature (110  C) to
bic acid (VC) as the reducing agent, and TDA-1 polymerize under stirring. The oxygen concentra-
as the ligand in the presence of a limited amount tion from air ([O2] 1.7  102 mol/L, based on
of air. the reaction solution (3 mL)) was calculated from
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
2004 BAI ET AL.

the residual volume (air volume, 5.3 mL) of

ampoule after adding the reaction mixture.3(g,h),15
After the desired polymerization time, the
ampoule was cooled by immersing it into iced
water. Afterwards, it was opened and the contents
were dissolved in THF (2 mL), and precipitated
into a large amount of methanol (200 mL). The
polymer obtained by ltration was dried under
vacuum until constant weight at 50  C. The mono-
mer conversion was determined gravimetrically.

Chain Extension of PS
A predetermined quantity of PS (obtained by bulk
AGET ATRP of St in the presence of a limited
amount of air) was added to a dried ampoule, and
then the predetermined quantity of St, FeCl3

6H2O, TDA-1, and VC was added. The rest of the
procedure was the same as the deoxygenated sys-
tem described above. The chain-extension poly-
merization was carried out in bulk under stirring
at 110  C.

Characterization
The number-average molecular weight (Mn,GPC)
values and molecular weight distribution (Mw/Mn)
values of the polymers were determined using
Waters 1515 gel permeation chromatograph
(GPC) equipped with a refractive index detector
(Waters 2414), using HR 1, HR 2, and HR 4 (7.8 
300 mm, 5 lm beads size) columns with molecu-
lar weights in the range 1025  105 g/mol. THF
was used as an eluent at a ow rate of 1.0 mL/min
and 30  C. The GPC samples were injected using
a Waters 717 plus autosampler and calibrated
with polystyrene standards from Waters. 1H NMR
spectrum was recorded on an Inova 400 MHz
nuclear magnetic resonance (NMR) instrument
using CDCl3 as the solvent and tetramethylsi-
lane (TMS) as the internal standard at ambient
temperature.
RESULTS AND DISCUSSION
Polymerization of St in the Absence of Oxygen
(Deoxygenated System)
The bulk polymerizations of St in the absence of
oxygen were rst investigated using TDA-1 as the
ligand. FeCl3
6H2O was used as the catalyst, and
PEBr was used as the initiator. Figure 1(a) shows
the kinetic plot of ln([M]0/[M]) versus time for the
bulk AGET ATRP of St with a molar ratio of [St]0/
Figure 1. ln([M]0/[M]) and conversion as a function
of time (a) and number-average molecular weight
(Mn,GPC) and molecular weight distribution (Mw/Mn)
versus theoretical molecular weight (Mn,th) (b) for
bulk AGET ATRP of St in the absence of oxygen. Poly-
merization conditions: [St]0/[PEBr]0/[FeCl3
6H2O]0/
[TDA-1]0/[VC]0 500/1/1/2/1; [St]0 3 mL; tempera-
ture 110  C.
[PEBr]0/[FeCl3
6H2O]0/[TDA-1]0/[VC]0 500/1/1/
2/1 at 110  C. The linearity of the plot through
zero point indicates that the polymerization is
approximately rst order with respect to the
monomer concentration and that the number of
active species remains constant during the poly-
merization process. The monomer conversion can
reach up to 76% after 16 h. Figure 1(b) shows the
evolution of the number-average molecular
weight (Mn,GPC) of PS and polydispersity (Mw/Mn)
on the Mn,th (Mn,th [St]0/[PEBr]0  MSt  con-
version%) for the bulk AGET ATRP of St using
TDA-1 as the ligand in the absence of oxygen at
110  C. From Figure 1(b), it can be seen that the
Mn;GPC values of the polymers increase linearly
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
 IRON(III)-MEDIATED AGET ATRP OF STYRENE 2005

manipulation. Thus, the polymerizations in the

presence of a limited amount of air were inten-
sively investigated in this work. In addition, to
obtain a homogeneous reaction solution, a polar
solvent such as DMF was used to improve the sol-
ubility of FeCl3/TDA-1 complexes in the reaction
system. Actually, a homogeneous reaction solution
was obtained under the experimental conditions.
Figure 2(a) shows the kinetic plots of AGET ATRP
of St in bulk and in DMF with the same molar ra-
tio of [St]0/[PEBr]0/[FeCl3
6H2O]0/[TDA]0/[VC]0
500/1/1/2/1 at 110  C. The rst-order reactions in
[St]0 are still observed under both polymerization
conditions, indicating that the propagating radi-
cal concentrations remain constant in the pres-
ence of a limited amount of oxygen. However, an

Figure 2. ln([M]0/[M]) and conversion as a function

of time (a) and number-average molecular weight
(Mn,GPC) and molecular weight distribution (Mw/Mn)
versus theoretical molecular weight (Mn,th) (b) for
bulk and solution AGET ATRP of St with molar ratio
of [St]0/[PEBr]0/[FeCl3
6H2O]0/[TDA-1]0/[VC]0 500/
1/1/2/1 in the presence of a limited amount of air at
110  C. Bulk polymerization conditions: [St]0 3 mL;
[O2] 1.7  102 mol/L. Solution polymerization con-
ditions: [St]0 3 mL; [O2] 1.0  102 mol/L; sol-
vent DMF; DMF/St 1/3 (v/v).

with monomer conversion and are close to their

corresponding theoretical ones; in the meanwhile,
the Mw/Mn values of the obtained polymers are
narrow (less than 1.3), indicating a well-controlled
polymerization process.

Figure 3. ln([M]0/[M]) and conversion as a function

Polymerization of St in the Presence of Limited of time (a) and number-average molecular weight
Amount of Air (Mn,GPC) and molecular weight distribution (Mw/Mn)
versus theoretical molecular weight (Mn,th) (b) for
For a living/controlled free-radical polymeriza- bulk AGET ATRP of St with different molar ratios of
tion process, what the polymerization can be car- [St]0/[PEBr]0/[FeCl3
6H2O]0/[TDA-1]0/[VC]0 in the pres-
ried out in the presence of oxygen is always ence of a limited amount of air at 110  C. Polymeriza-
appreciated due to its simple and economical tion conditions: [St]0 3 mL; [O2] 1.7  102 mol/L.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
2006 BAI ET AL.

Table 1. Effect of the Amount of Catalyst on Bulk AGET ATRP of St in the

Presence of Limited Amount of Air at 110  C
a
[St]0/[PEBr]0/[Fe(III)]0/ Time Conversion Mn.th Mn.GPC
[TDA-1]0/[VC]0 (h) (%) (g/mol) (g/mol) Mw/Mn

300:1:0.5:1:0.75 10.3 22.8 7120 9340 1.22

300:1:0.25:0.5:0.75 20 20.1 6320 7560 1.15
300:1:0.1:0.2:0.75 18 22.5 7020 7170 1.20
300:1:0.05:0.1:0.75 18 52.7 16440 18200 1.21
a
Mn,th ([St]0/[PEBr]0)  MSt  conversion%. Polymerization conditions: [St]0 3 mL; [O2]
1.7  102mol/L.

induction period is observed under both polymer- a 5 mol % catalyst was used. The catalyst concen-
ization conditions. This is due to that there needs tration used here is signicantly lower than those
some time to establish a dynamic equilibrium used in the reported iron(III)-mediated AGET
between the concentration of Fe(II) and Fe(III) ATRPs,3(gi) which indicates that the catalyst sys-
species as the reaction proceeded in the presence tem has a higher activity.
of oxygen.3(h) By comparison of the data in Figure To further investigate the effect of Fe(III) con-
2(a), it can be seen, as expected, that the polymer- centration on the AGET ATRP of St, the poly-
ization rate in DMF is slower than that in the merization kinetic experiments of AGET ATRP of
bulk polymerization. For example, a 61% of con- styrene with different molar ratios of [St]0/
version was obtained in the solution polymeriza- [PEBr]0/[FeCl3
6H2O]0/[TDA]0/[VC]0 were further
tion after 35.3 h polymerization time; while reach- studied. Figure 3(a) shows the kinetic plots with
ing such a conversion just needed about 16.5 h for molar ratios of [St]0/[PEBr]0/[FeCl3
6H2O]0/
the bulk polymerization. Figure 2(b) shows that [TDA]0/[VC]0 300/1/0.5/1/0.75 and 300/1/0.25/
both Mn,GPC values increase linearly with the 0.5/0.75, respectively. Both of the kinetic plots are
monomer conversion and are close to their corre- rst-order with respect to the monomer
sponding theoretical ones. It can also be seen that
the Mw/Mn values (Mw/Mn 1.201.26) of the
obtained polymers for the bulk polymerization are
narrow than these (Mw/Mn 1.311.42) obtained
in DMF solution. This maybe results from some
side reactions such as chain transfer reaction to
the solvent in solution polymerization conditions.
From the results mentioned above, it can be con-
cluded that the iron(III)-mediated AGET ATRP of
styrene using TDA-1 as the ligand not only can be
conducted in the presence of oxygen but also does
not damage the controlled/living radical poly-
merization characteristics of ATRP.

Effect of Concentration of Catalyst on

Polymerization of St
As an efcient catalyst system, lower amount of
catalyst used is necessary. In this work, the bulk
polymerizations of St in the presence of a limited
amount of air were investigated using 550 mol %
catalyst relative to the initiator with a molar ratio
of [St]0/[PEBr]0 300/1. The results are listed in
Table 1. From Table 1, it can be seen that all the
molecular weights are close to theoretical values
and the Mw/Mn values also are low (1.2) even if
Journal of Polymer Science: Part A: Polymer Chemistry
Figure 4. 1H NMR spectrum of PS (Mn,GPC 4300
g/mol, Mw/Mn 1.29) obtained in the presence of air
with CDCl3 as solvent and tetramethylsilane (TMS)
as internal standard. Polymerization conditions: [St]0/
[PEBr]0/[FeCl3
6H2O]0/[TDA-1]0/[VC]0 300/1/0.5/1/
0.75; [St]0 3 mL; [O2] 1.7  102 mol/L; time
6.2 h; conversion 8.6%; temperature 110  C.
DOI 10.1002/pola

concentration, indicating that constant propagat-
ing radical species are also remained during both
the polymerization processes. From Figure 3(b), it
can be seen that both the Mn,GPC values of the
obtained polymers increase linearly with mono-
mer conversion and that the corresponding Mw/
Mn values are low (less than 1.3).
Analysis of Chain End and Chain Extension
The chain end of the PS (Mn,GPC 4300 g/mol,
Mw/Mn 1.29) prepared in the presence of a lim-
ited amount of air was analyzed by 1H NMR spec-
troscopy, as shown in Figure 4. The chemical
shifts at d 6.377.08 ppm (a in Fig. 4) are
attributed to the aromatic protons in the PEBr
initiator moieties and PS main chains. The chemi-
cal shift at d 1.03 ppm (b in Fig. 4) is corre-
sponded to the methyl protons in the initiator
PEBr, which indicates that the initiator PEBr
moieties were successfully attached to the poly-
mer chain ends. The chemical shifts at 1.42
2.06 ppm (c in Fig. 4) are assigned to the methyl-
ene and methyne protons in the PS main chains.
The chemical shifts at 4.24.5 ppm (d in Fig. 4)
are assigned to the methyne protons in the chain
ends of PSs because of the electron-attracting
function of x-Cl atom.16 In addition, the percent-
age of chain-end functionality f(f 97%) can be
estimated by a comparison of the integrals of the
peaks Hb (protons corresponding to the initiator
Figure 5. GPC traces of before and after Chain exten-
sion using PS prepared by AGET ATRP of St as the
macroinitiator. Polymerization conditions: [St]0/[PS]0/
[FeCl3
6H2O]0/[TDA-1]0/[VC]0 1000/1/1/2/1, [St]0
3 mL, temperature 110  C, time 13.5 h, conver-
sion 14.5%.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
IRON(III)-MEDIATED AGET ATRP OF STYRENE 2007
CH3ACH groups) and Hd (proton CH located in
the a-position of the chlorine chain end).6(j) There-
fore, the obtained PS can be used as macroinitia-
tors to conduct chain-extension reaction. The PS
(Mn,GPC 17,860 g/mol, Mw/Mn 1.24) obtained
in the presence of a limited amount of air was
used as the predecessor in the chain-extension
experiment. As shown in Figure 5, there is a peak
shift from the macroinitiator to the chain-
extended PS with Mn,GPC 43,070 g/mol and Mw/
Mn 1.35. These results further demonstrate the
features of the living/controlled polymerization
of St mediated by iron catalyst using TDA-1 as
the ligand in despite of the presence of a limited
amount of air.
CONCLUSIONS
In this work, the Fe(III)-mediated AGET ATRP of
styrene using a cheap and commercially available
TDA-1 as a novel ligand is demonstrated. The
polymerization can be successfully carried out in
the presence of a limited amount of air even at a
lower catalyst concentration (5 mol % relative to
the initiator PEBr), and the polymerizations show
nature of living/controlled free-radical polymer-
ization. The use of oxidatively stable catalyst pre-
cursors (FeCl3
6H2O) and commercially available
ligand combination of operation in the presence of
air can potentially allow the more facile prepara-
tion, storage, and shipment of ATRP catalyst sys-
tems as well as its commercialization.
The nancial supports of this work by the National Nat-
ural Science Foundation of China (Nos. 20874069 and
50803044), the Science and Technology Development
Planning of Jiangsu Province (Nos. BK2007702 and
BK2007048), the International Cooperation Founda-
tion of Jiangsu Province (No.BZ2007037), Qing Lan
Project, and the Natural Science Key Basic Research of
Jiangsu Province for Higher Education (No.
05KJA15008) are gratefully acknowledged.
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DOI 10.1002/pola