A3-Type Star Polymers via Click Chemistry

O. ALTINTAS, B. YANKUL, G. HIZAL, U. TUNCA

Department of Chemistry, Istanbul Technical University, Maslak 34469, Istanbul, Turkey

Received 3 July 2006; accepted 8 August 2006

DOI: 10.1002/pola.21728
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: We report a simple preparation of three-armed (A3-type) star polymers

based on the arm-first technique, using a click-reaction strategy between a well-defined
azide-end-functionalized polystyrene, poly(tert-butyl acrylate), or poly(ethylene glycol)
precursor and a trisalkyne-functional initiator, 1,1,1-tris[4-(2-propynyloxy)phenyl]-
ethane. The click-reaction efficiency for A3-type star formation has been investigated
with gel permeation chromatography measurements (refractive-index detector). The
gel permeation chromatography curves have been split with the deconvolution method
(Gaussian area), and the efficiency of A3-type star formation has been found to be 87%.
V
C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6458–6465, 2006

Keywords: atom transfer radical polymerization (ATRP); click reactions; poly(ethyl-

ene glycol); polystyrene, poly(tert-butyl acrylate); star polymers

INTRODUCTION has quickly increased because of the variety of ap-

A star structure is defined as a nonlinear polymer
that consists of multiple backbone chains existing
from junction points.1 Star polymers show differ-
ent crystalline, mechanical, and viscoelastic prop-
erties in comparison with their corresponding lin-
ear analogues.
There are two general strategies used to pro-
duce star polymers: the arm-first and core-first
techniques. In the arm-first strategy, a polymer
with a proper end-group functionality is reacted
with an appropriate multifunctional core to give a
star polymer. In the second strategy (core-first),
the polymer chain is simultaneously grown from
a multifunctional initiator.
Previously, living ionic polymerization2,3 was
the only system for the preparation of star poly-
mers with controlled structures. However, in re-
cent years, the use of controlled/living radical poly-
merization techniques in the synthesis of complex
macromolecules (star and dendrimeric polymers)
Correspondence to: U. Tunca (E-mail: tuncau@itu.edu.tr)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 6458–6465 (2006)
V
C 2006 Wiley Periodicals, Inc.
6458
plicable monomers and greater tolerance to ex-
perimental conditions in comparison with living
ionic polymerization routes. Nitroxide-mediated
radical polymerization4 based on the use of stable
nitroxide free radicals and Mtn(Metat)/ligand-cat-
alyst-mediated living radical polymerization,5–7
which is often called atom transfer radical poly-
merization (ATRP), are versatile methods among
living radical polymerizations.
Recently, Sharpless and coworkers used Cu(I)
as a catalyst in conjunction with a base in Huis-
gen’s 1,3-dipolar cycloadditions8 ([3 + 2] systems)
between azides and alkynes or nitriles and termed
them click reactions.9,10 Later, click-chemistry
strategy was successfully applied to macromolecu-
lar chemistry, affording polymeric materials vary-
ing from block copolymers11 to complex macromo-
lecular structures.12–25 Click reactions permit
C

C (or C

N) bond formation in a quantitative
yield without side reactions or requirements for
additional purification steps.
In this article, we report a simple preparation of
three-armed (A3-type) star polymers based on the
arm-first technique, using a click-reaction strategy
between a well-defined azide-end-functionalized
 A3 -TYPE STAR POLYMERS VIA CLICK CHEMISTRY
polystyrene (PS–N3), azide-end-functionalized poly
(tert-butyl acrylate) (PtBA–N3), or azide-end-func-
tionalized poly(ethylene glycol) (PEG–N3) and a tri-
salkyne-functional initiator, 1,1,1-tris[4-(2-propyny-
loxy)phenyl]ethane (1). However, very recently,
during the preparation of this article, a study re-
lated to the formation of a polystyrene (PS) A3-type
star via a click-reaction strategy appeared.26
EXPERIMENTAL
Materials
Styrene (99%; Merck) and tert-butyl acrylate (tBA;
99%; Aldrich) were passed through a basic alumina
column to remove the inhibitor and then distilled
over CaH2 in vacuo before use. N,N,N0 ,N@,N@-Pen-
tamethyldiethylenetriamine (PMDETA; Aldrich)
was distilled over NaOH before use. Poly(ethylene
glycol) [PEG; number-average molecular weight
(Mn) ¼ 2000; Acros] with a monohydroxyl end group
was dried over anhydrous toluene by azeotropic dis-
tillation. Tetrahydrofuran (THF; 99.8%; J.T. Baker)
was dried and distilled over LiAlH4. Other solvents
were purified by conventional procedures. All other
reagents were purchased from Aldrich and used as
received.
Instrumentation
1 tated in a cold methanol/water (1:4) mixture. After
H NMR spectra were recorded on a Bruker NMR
spectrometer (250 MHz) in CDCl3. Gel permea-
tion chromatography (GPC) measurements were
obtained with an Agilent model 1100 instrument
consisting of a pump, a refractive-index (RI) de-
tector, and four Waters Styragel columns (HR 5E,
HR 4E, HR 3, and HR 2). THF was used as an elu-
ent at a flow rate of 0.3 mL/min at 30 8C. Toluene
was used as an internal standard. Data analyses
were performed with PL Caliber software. The
molecular weight of the polymers was calculated
on the basis of linear PS standards (Polymer Lab-
oratories). Peak Fit (version 4.12, Seasolve) was
used for the deconvolution of the GPC curves.
Fourier transform infrared (FTIR) analysis was
carried out with a PerkinElmer Spectrum One
FTIR spectrometer.
Synthesis of 1,1,1-Tris[4-(2-propynyloxy)phenyl]-
ethane (1)
1,1,1-Tris(4-hydroxyphenyl)ethane (0.75 g, 2.45
mmol) was dissolved in dimethylformamide (DMF;
10 mL), and propargyl bromide (80% in toluene;
0.97 mL, 9 mmol) and K2CO3 (2.4 g, 17.5 mmol)
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6459
were added to the mixture. The reaction mixture
was stirred for 24 h at 110 8C. After the reaction
was completed, the mixture was filtered and evap-
orated in vacuo to remove DMF. CH2Cl2 (200 mL)
was added, and the reaction mixture was washed
three times with distilled water (100 mL  3). The
combined organic phase was dried over Na2SO4, fil-
tered, and evaporated. The remaining product was
purified by column chromatography over silica gel
eluting with ethyl acetate/hexane (1:9) to obtain
pure 1 as a yellow-green liquid (0.684 g, 67%).
1
H NMR (CDCl3): 7.01–6.96 (m, 6H, ArH),
6.88–6.82 (m, 6H, ArH), 4.66 (d, J ¼ 2.4 Hz, 6H,
HCC

CH2) 2.50 (t, J ¼ 2.4 Hz, 3H, HCC

CH2),
2.09 (s, 3H, CH3).
Preparation of PtBA–N3
Poly(tert-butyl acrylate) (PtBA) was prepared by the
ATRP of tBA with ethyl-2-bromoisobutyrate (EiBr)
as an initiator. To a 10-mL Schlenk tube, tBA (8 mL,
54.6 mmol), PMDETA (0.057 mL, 0.27 mmol), CuBr
(0.04 g, 0.27 mmol), and EiBr (0.04 mL, 0.27 mmol)
were added in that order. The tube was degassed by
three freeze–pump–thaw cycles, left in argon, and
placed in a thermostated oil bath at 80 8C for
40 min. Subsequently, the polymerization mixture
was diluted with THF, passed through a basic alu-
mina column to remove the catalyst, and precipi-
the precipitation, it was decanted. CH2Cl2 was
added, and the reaction mixture was washed three
times with distilled water. The organic layer was
dried with anhydrous Na2SO4, and the solvent was
removed in vacuo; this yielded a white solid. The
polymer was dried for 24 h in a vacuum oven at
25 8C [Mn,GPC ¼ 6700; weight-average molecular
weight/number-average molecular weight (Mw/Mn)
¼ 1.29; initial monomer concentration/initial initia-
tor concentration ([M]0/[I]0) ¼ 200; conversion ¼ 25%;
Mn,theoretical ¼ 6600; Mn,NMR ¼ 7200].
Thus obtained, PtBA (2 g, 0.27 mmol) was dis-
solved in DMF (15 mL), and sodium azide (0.7 g,
10.8 mmol) was added. The reaction mixture was
stirred for 24 h at room temperature. It was fil-
tered and evaporated to remove DMF. CH2Cl2
(100 mL) was added, and the reaction mixture
was washed three times with distilled water. The
organic layer was dried with anhydrous Na2SO4,
and the solvent was removed in vacuo; this
yielded a white solid (1.9 g, 95%).
1
H NMR (CDCl3): 4.1 [2H, CH3CH2 OC¼ ¼OC
(CH3)2

PtBA

], 3.6–3.8 [1H,

Pt BA

CH2CH
(C¼¼OOC(CH3)3)

N3].
6460 ALTINTAS ET AL.
Scheme 1
Preparation of PS–N3
PS was prepared by the ATRP of styrene with
EiBr as an initiator. To a 10-mL Schlenk tube,
styrene (9.36 mL, 81.6 mmol), PMDETA (0.086
mL, 0.41 mmol), CuBr (0.058 g, 0.41 mmol), and
EiBr (0.06 mL, 0.41 mmol) were added, and the
reaction mixture was degassed by three freeze–
pump–thaw cycles and left in vacuo. The tube
was then placed in a thermostated oil bath at
110 8C for 30 min. The dark green polymerization
mixture was diluted with THF, passed through a
basic alumina column to remove the catalyst, and
precipitated in methanol. The polymer was dried
for 24 h in a vacuum oven at 25 8C (Mn,GPC
¼ 3450; Mw/Mn ¼ 1.10; [M]0/[I]0 ¼ 200; conversion
¼ 15%; Mn,theoretical ¼ 3300; Mn,NMR ¼ 3500).
Previously obtained PS (1,9 g, 0.54 mmol) was dis-
solved in DMF (15 mL), and sodium azide (1.40 g,
21.71 mmol) was added. The reaction mixture was
stirred for 24 h at room temperature. It was filtered
and evaporated to remove DMF. CH2Cl2 (100 mL)
was added, and the reaction mixture was washed
three times with distilled water. The organic layer
was dried with anhydrous Na2SO4, and the solvent
was removed in vacuo. The polymerization mixture
was diluted with THF and precipitated in methanol.
The polymer was dried for 24 h in a vacuum oven at
25 8C, yielding a white solid (1.8 g, 95%).
1
H NMR (CDCl3): 3.9 [2H, CH3CH2OC¼ ¼ OC
(CH3)2

PS

], 3.5–3.8 [1H,

PS

CH2 CH(Ph)


N3].
Preparation of PEG–N3
PEG (Mn ¼ 2000; 2.00 g, 1 mmol) with a monohy-
droxyl group was dissolved in CH2CI2 (15 mL),
and triethylamine (2.78 mL, 20 mmol), 4-(dime-
thylamino)pyridine (DMAP; 1.22 g, 10 mmol),
and toluene-4-sulfonyl chloride (tosyl chloride;
1.91 g, 10.0 mmol) were added to the solution.
The reaction mixture was stirred for 24 h at room
temperature and then poured into a cold 4 M hy-
drochloric acid solution. The product was ex-
tracted with CH2Cl2, and the solvent was re-
moved in vacuo. The remaining product was puri-
Journal of Polymer Science: Part A: Polymer Chemistry
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 A3 -TYPE STAR POLYMERS VIA CLICK CHEMISTRY 6461

1
Figure 1. H NMR spectrum of 1 in CDCl3.

fied by column chromatography over silica gel left in argon, and stirred at room temperature for
eluting first with CH2CI2/ethylacetate (1:1) to 24 h. The solution was passed through an alu-
remove DMAP and tosyl chloride and then with mina column to remove the copper salt and pre-
methanol/CH2CI2 (1:10) to obtain the pure poly- cipitated in a cold methanol/water (4:1) mixture.
mer. The polymer was dissolved in THF, precipi- After the precipitation, it was decanted and ex-
tated in cold diethyl ether, and dried for 24 h in a tracted with CH2Cl2. The organic layer was dried
vacuum oven at 25 8C (1.84, 92%). with anhydrous Na2SO4 and filtered, and the sol-
Thus obtained, monotosylated PEG (1.84 g, vent was removed in vacuo. The product was
0.84 mmol) was dissolved in DMF (15 mL), and dried in a vacuum oven at 25 8C.
sodium azide (2.18 g, 0.033 mmol) was added to
the solution. The reaction mixture was stirred for
24 h at room temperature. CH2Cl2 (100 mL) was
added, and the reaction mixture was washed
three times with distilled water. The solvent was
removed in vacuo and precipitated in cold diethyl
ether. The polymer was dried in a vacuum oven
for 24 h at 25 8C (1.75 g, 95%).
1
H NMR (CDCl3): 3.9 (2H,

PEG

O

CH2
CH2N3), 3.35 (3H, CH3

O

PEG

).

Preparation of the PtBA3 Star via a Click Reaction

between 1 and PtBA–N3
1 (0.007 g, 0.0162 mmol) and PtBA–N3 (0.35 g, 0.048
mmol) were dissolved in nitrogen-purged DMF
(5 mL) in a Schlenk tube. CuBr (3.58  10
3 g,
0.025 mmol) and PMDETA (5.2 lL, 0.025 mmol)
were added in order, and the reaction mixture Figure 2. GPC curves of PS–N3 and a click-reaction
was degassed by three freeze–pump–thaw cycles, mixture of PS–N3 and 1 (RI detector).
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6462 ALTINTAS ET AL.

Figure 3. GPC curves of PtBA–N3 and a click-reaction mixture of PtBA–N3 and 1 (RI
detector).

Preparation of the PS3 Star via a Click Reaction were added, and the reaction mixture was degassed
between 1 and PS–N3 by three freeze–pump–thaw cycles, left in argon,
and stirred at room temperature for 24 h. The poly-
1 (0.008 g, 0.0189 mmol) and PS–N3 (0.198 g, 0.056
mer solution was passed through an alumina col-
mmol) were dissolved in 5 mL of nitrogen-purged
umn to remove the copper salt, precipitated in cold
DMF in a Schlenk tube. CuBr (4.0  10
3 g, 0.028
diethyl ether, and dried in a vacuum oven at 25 8C.
mmol) and PMDETA (6 lL, 0.028 mmol) were
added, and the reaction mixture was degassed by
three freeze–pump–thaw cycles, left in argon, and
stirred at room temperature for 24 h. The polymer RESULTS AND DISCUSSION
solution was passed through an alumina column to
remove the copper salt, precipitated in methanol, We used a click-chemistry strategy to obtain A3-
and dried in a vacuum oven at 25 8C. type star polymers via the arm-first method
(Scheme 1).

Preparation of the PEG3 Star via a Click Reaction

between 1 and PEG–N3
1 (0.014 g, 0.033 mmol) and PEG–N3 (0.198 g,
0.99 mmol) were dissolved in 5 mL of nitrogen-
purged DMF in a Schlenk tube. CuBr (7.2  10
3 g,
0.05 mmol) and PMDETA (12 lL, 0.05 mmol)

Figure 5. Splitting of the GPC curves (a click-reac-

Figure 4. GPC curves of PEG–N3 and a click-reac- tion mixture of PS–N3 and 1) with the deconvolution
tion mixture of PEG–N3 and 1 (RI detector). method (Gaussian area).
Journal of Polymer Science: Part A: Polymer Chemistry
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 A3 -TYPE STAR POLYMERS VIA CLICK CHEMISTRY 6463

Figure 6. Splitting of the GPC curves (a click-reaction mixture of PtBA–N3 and 1)

with the deconvolution method (Gaussian area).

First of all, trisalkynyl-functional compound 1 copolymer and A1 homopolymer (Figs. 2–4). The
was prepared in a 67% yield via an etherification molar percentages of A3, A2, and A1 were calcu-
reaction between 1,1,1-tris(4-hydroxyphenyl)eth- lated from the GPC traces with the deconvolution
ane and propargyl bromide. The structure of 1 was method (Gaussian area) via the Peak Fit program.
confirmed by 1H NMR and elemental analysis. In Moreover, the splitting of GPC traces with the
the 1H NMR spectrum of 1, it was evident that deconvolution method (Gaussian area) is dis-
CH2 protons of propargyl bromide at 3.86 were played in Figures 5–7.
shifted to 4.66 ppm as a doublet signal of CH2O All data for star formation via click cycloaddi-
indicating an etherification reaction (Fig. 1). tion reactions are collected in Table 1.
As a second step, well-defined PS and PtBA Eighty seven percent of the PS–N3 chains were
were obtained from the ATRP of the related reacted with 1 to give the PS3 star, and the
monomers. Their bromide end groups were quan- remaining 8 and 5% represented the PS2 block co-
titatively converted to the azide form with a well- polymer and PS homopolymer, respectively.
known procedure. The x-azide end functionality Highly efficient click reactions were also ob-
of both PS and PtBA was confirmed with 1H served for PtBA3 and PEG3 star formation. The
NMR. For PS–N3, a signal at 4.5 ppm, assigned to A3-type star formation efficiency was found to be
CH

Br, disappeared, and a new peak appeared 85 and 82% for PtBA and PEG, respectively.
at 3.9 ppm, indicating CH linked to the azide end
group. For PtBA–N3, the CH

N3 end-functional
group was detected at 3.6–3.8 ppm, whereas
CH

Br was detected at 4.1 ppm.
Commercially available PEG with a monohy-
droxyl end group was first tosylated and then con-
verted to azide. The CH

N3 end group of PEG was
observed at 3.9 ppm from the 1H NMR spectrum.
As a last step, well-defined PS, PtBA, or PEG
with azide-end-functional groups was reacted
with 1 to give the corresponding star polymers.
Click reactions were carried out with equimolar
amounts of the reactants ([azide]/[trisalkyne] ¼ 3/1)
in DMF with CuBr/PMDETA for 24 h at room tem-
perature.
Star formation in all cases was monitored with
GPC measurements. From GPC traces, it was Figure 7. Splitting of the GPC curves (a click-reac-
clearly observed that the reaction mixture con- tion mixture of PEG–N3 and 1) with the deconvolution
tained mainly A3 star polymer and less A2 block method (Gaussian area).
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
6464 ALTINTAS ET AL.

Table 1. A3 Star Polymers via Click Reactions between Azide-End-Functionalized

Polymers and 1

Azide-End-
Functionalized Area (%) in GPC
Polymer Traces from
Precursor Click Reactions

A3 A2 A1
Polymer Mn Mw/Mn (Star Polymer) (Block Copolymer) (Homopolymer)

PS 3450 1.10 87 8 5
PtBA 6700 1.29 85 10 5
PEG 2650 1.07 82 12 6

Star formation through the coupling of azide
and alkyne groups was also confirmed by 1H
NMR measurements. From the spectrum of the
PS3 star, CH linked to the azide end group of PS
at 3.9 ppm was removed, and a new broad signal
assigned to CH

of PS and OCH2

of the core,
both linked to the triazole ring, was detected at
5.0 ppm.
Moreover, the

OCH2CCH group was noted at
4.6 ppm, due to the remaining unreacted alkyne
group of the core. For the PtBA3 star, a new peak
was assigned to CH of the triazole ring (d ¼ 7.7
ppm), along with the appearance of the CH signal
as an end group of PtBA and the OCH2

signal
of the core at 5.1 ppm, both linked to the triazole
ring. The 1H NMR spectrum of the PEG3 star
clearly displayed signals at 7.8, 5.1, and 4.5 ppm
assignable to CH of the triazole ring, OCH2

of
the core, and the CH2

end group of PEG,
respectively (Fig. 8).
Notably, FTIR analysis of the star polymers
revealed the complete disappearance of the azide
Figure 8. 1H NMR spectrum of the PEG3 star poly-
mer (through a click reaction between PEG–N3 and 1)
in CDCl3.
stretching frequencies ranging from 2094 to 2112
cm
1.
Several parameters may affect the efficiency of
the click reaction for A3-type star formation, such
as the reaction solvent, alkyne/azide ratio, molec-
ular weight of the azide-end-functionalized poly-
mers, catalyst, base, and temperature.
CONCLUSIONS
Here we applied a click-chemistry strategy to the
formation of A3-type star polymers such as PS3,
PtBA3, and PEG3. The A3-type star polymers
were recovered in yields as high as 87% because
of the highly efficient click reaction.
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