Letter

pubs.acs.org/macroletters

One-Pot Synthesis of Block Copolymers by Orthogonal Ring-

Opening Polymerization and PET-RAFT Polymerization at Ambient
Temperature
Changkui Fu, Jiangtao Xu,* Mitchell Kokotovic, and Cyrille Boyer*
Centre for Advanced Macromolecular Design (CAMD) and Australian Centre for NanoMedicine (ACN), School of Chemical
Engineering, University of New South Wales, Sydney, NSW 2052, Australia
*
S Supporting Information
Downloaded via NORTHWESTERN POLYTECHNICAL UNIV on March 19, 2024 at 09:18:57 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Well-defined poly(ε-caprolactone)-b-poly-

(methyl acrylate) (PCL-b-PMA) block copolymers were
synthesized at ambient temperature by one-pot combination
of diphenyl phosphate (DPP)-catalyzed ring-opening polymer-
ization (ROP) and photoinduced electron/energy transfer-
reversible addition−fragmentation chain transfer (PET-RAFT)
polymerization. Full orthogonality of PET-RAFT polymer-
ization and DPP-catalyzed ROP was confirmed by kinetic
studies, which allowed facile synthesis of PCL-b-PMA block
copolymers without a specific polymerization sequence. The
resulting PCL-b-PMA block copolymers synthesized by either sequential or simultaneous ROP and PET-RAFT polymerization
showed remarkably low molecular weight distributions (≤1.15), indicating that both ROP and PET-RAFT polymerizations
proceeded in a controlled manner. In contrast to previous synthetic methods to prepare block copolymers, this facile one-pot
method allows for rapid synthesis of block copolymers controlled via visible light.

T he one-pot synthetic methodology, a concept from

organic chemistry, has been shifted to polymer chemistry
for rapid synthesis and postmodification of polymers.1 The
combination of different and compatible controlled polymer-
ization techniques performed in one-pot reactions to prepare
polymers avoids purifying intermediates, which saves time and
resources and thus provides facile access to polymers with
various functionalities and architectures.2 For instance, ring-
opening polymerization (ROP) has been combined with
controlled radical polymerization techniques, such as nitro-
xide-mediated polymerization or reversible addition−fragmen-
tation chain transfer (RAFT) polymerization to one-step
prepare block and graft copolymers, reported, respectively, by
Hedrick, Howdle, Barner-Kowollik, and others.2b,g,3 To achieve
this goal, orthogonality and compatibility of these polymer-
ization techniques are required. However, for most controlled
polymerization techniques, the conditions required are different
and often contradictory.4 For instance, Giacomelli and co-
workers2p demonstrated the combination of thermal initiated
RAFT and ROPs for the synthesis of polystyrene-b-poly(ε-
caprolactone) block copolymers using a one-pot polymer-
ization. The authors successfully showed the preparation of
copolymers; however, a relatively high polydispersity indice
(PDI) was observed. The authors attributed this to the possible
incompatibility issue of thermal initiated RAFT polymerization
with ROP conditions.
Recently, light mediated controlled radical polymerization
(CRP) has emerged as a new and attractive polymerization
technique for polymer synthesis.5 Compared with traditional
thermal polymerizations, the light-mediated CRP can be
performed at ambient temperature in a neat and efficient
way. Featuring temporal and spatial control, light-mediated
CRP is capable of attracting numerous applications in elegant
polymer synthesis,5j,n,s,6 bioconjugation,7 self-assembly,8 and
surface modification,5c,9 etc. Our group has developed a novel
visible-light-mediated CRP, namely, photoinduced electron/
energy transfer-RAFT (PET-RAFT) polymerization, for well-
defined polymer synthesis.5g Through comprehensive research,
we can now achieve smart control over polymer synthesis and
architectures of various monomer families through the use of
the PET-RAFT technique.10 This is achieved through the
thoughtful selection of photoredox catalysts from those
available, which cover a range of wavelengths from blue to
red/near-infrared light11 and are effective at low light intensities
and ambient temperature. The PET-RAFT polymerization can
be conducted in bulk, solution,5g dispersion,12 and even
miniemulsion,13 exhibiting great versatility, robustness, and
oxygen tolerance.10 Due to its mild reaction conditions and
versatility, we envisaged that PET-RAFT polymerization would
be an excellent platform for the combination of other
controlled polymerization techniques in the one-pot prepara-
tion of polymers with various functionalities and architec-
tures.14
Received: February 11, 2016
Accepted: March 7, 2016
Published: March 17, 2016

© 2016 American Chemical Society 444 DOI: 10.1021/acsmacrolett.6b00121

ACS Macro Lett. 2016, 5, 444−449
ACS Macro Letters Letter

Scheme 1. One-Pot Synthesis of PCL-b-PMA Block Copolymer by Combining DPP-Catalyzed ROP of CL and PET-RAFT
Polymerization of MA

Figure 1. (a) Conversions of MA and CL versus polymerization time; (b) ln([M]0/[M]t) of MA and CL versus polymerization time; (c) GPC traces
of polymers obtained at 4 h, 8 h, and 12 h; (d) Mn,RI of polymers versus polymerization time in the synthesis of PMA-b-PCL block copolymers via
one-pot sequential PET-RAFT polymerization of MA and DPP-catalyzed ROP of CL.

In this communication, we demonstrate, for the first time,
the preparation of block copolymers in one pot and at ambient
temperature by combining diphenyl phosphate (DPP)-
catalyzed ROP of ε-caprolactone (ε-CL) and iridium-catalyzed
PET-RAFT polymerization of methyl acrylate (MA) using low
intensity visible light (λmax = 460 nm, 0.7 mW/cm2). In our
approach, we demonstrated that the iridium catalyst is
compatible with the diphenyl phosphate (DPP)-catalyzed
ROP condition and allows a spatial and temporal control of
the polymerization using visible light. As shown in Scheme 1,
three synthetic routes toward synthesis of polyCL-b-polyMA
(PCL-b-PMA) block copolymers are comprehensively imple-
mented: (i) to conduct PET-RAFT polymerization of MA first,
sequentially followed by ROP of CL; (ii) to conduct ROP of
CL first, sequentially followed by PET-RAFT polymerization of
MA; (iii) to conduct ROP of CL and PET-RAFT polymer-
ization of MA simultaneously to form PCL-b-PMA block
copolymer. In all three synthetic routes, well-defined PCL-b-
445
PMA block copolymers with low molecular weight distributions
(PDI < 1.15) are successfully prepared. More importantly, no
intermediate purifications are essentially required in all three
synthetic routes, indicating full orthogonality of DPP-catalyzed
ROP of CL and PET-RAFT polymerization of MA. To the best
of our knowledge, such one-pot polymerization to prepare
block copolymers by combining two mechanistically distinct,
but fully orthogonal, polymerization techniques without
needing to consider the sequence of polymerizations has not
yet been reported. In comparison with the seminal work of
Goto, Kaji, and co-workers,5e which shows the first example of a
combination of UV-initiated ROP and visible-light-mediated
iodine transfer polymerization for the synthesis of diblock
copolymer using a sequential reaction (i.e., MMA first, and then
δ-valerolactone), in our approach, we demonstrate that the
diblock copolymer could be prepared via a simultaneous or
sequential approach (without the need of specific order). Both
simultaneous and sequential approaches result in the synthesis
DOI: 10.1021/acsmacrolett.6b00121
ACS Macro Lett. 2016, 5, 444−449
ACS Macro Letters
Figure 2. (a) Conversions of CL and MA versus polymerization time; (b) ln([M]0/[M]t) of CL and MA versus polymerization time; (c) GPC traces
of polymer obtained at 3 h, 5 h, 7 h, and 11 h; (d) Mn,RI of polymers versus polymerization time in the synthesis of PCL-b-PMA block copolymer via
one-pot sequential DPP-catalyzed ROP of CL and PET-RAFT of polymerization of MA.
of well-defined block copolymers, indicating excellent compat-
ibility and orthogonality of these two polymerization
techniques without the formation of byproducts. The current
method provides a facile, versatile, and efficient way of
preparing block copolymers, making block copolymer synthesis
more easily accessible and industrially applicable.
As shown in Scheme 1, modified chain transfer agent
containing a hydroxyl group, 2-hydroxyethyl 2-(((butylthio)-
carbonothioyl)thio)propanoate (HEBCP), is used to initiate a
ROP and PET-RAFT polymerization. The hydroxyl group of
HEBCP is the initiator for DPP-catalyzed ROP, whereas the
trithiocarbonate group mediates PET-RAFT polymerization.
For synthesis of PMA-b-PCL block copolymer by Route 1,
PET-RAFT polymerization of MA was conducted first,
followed by ROP of CL. For PET-RAFT polymerization of
MA, Ir(ppy)3 was used as the photocatalyst and toluene as
solvent. A ratio of [HEBCP]:[MA]:[Ir(ppy)3] = 1:100:0.001
was used in the polymerization. The PET-RAFT polymer-
ization was conducted at ambient temperature under blue light
(λmax = 460 nm). As shown in Figure 1a, the PET-RAFT
polymerization of MA proceeded smoothly and achieved 73%
conversion of MA in 8 h. Ln([M]0/[M]t) value also increased
linearly with time, indicative of a well-controlled PET-RAFT
polymerization process (Figure 1b). A PMA homopolymer
with Mn,RI of 6 430 g/mol was obtained after 8 h of
polymerization (Figure 1d). The blue light was then switched
off, followed by the addition of 50 equiv of CL and 1 equiv of
DPP with respect to HEBCP to activate ROP. After addition of
CL and DPP for 6 h, the conversion of CL was observed to
reach 96% (Figure 1a). The linear, first-order kinetics in the
ROP of CL showed a well-controlled ROP process (Figure 1b).
The GPC trace of polymer after addition of CL and DPP also
shifted to lower retention time, indicating an obvious increase
in molecular weight (Figure 1c). Throughout the whole
polymerization, the molecular weights of polymers increased
446
Letter
continuously with polymerization time, and the polydispersity
indices (PDIs) of polymers remained very narrow ranging from
1.08 to 1.18 (Figure 1d). This evidence indicates the successful
formation of well-defined block copolymers. A PMA-b-PCL
block copolymer with Mn,RI of 11 350 g/mol and PDI of 1.11
was obtained after a total of 14 h of polymerization. The
structure and composition of PMA-b-PCL block copolymers
were characterized by 1H NMR spectroscopy, which confirmed
the successful synthesis of block copolymers (SI, Figure S1).
For synthesis of PCL-b-PMA block copolymer by Route 2,
DPP-catalyzed ROP of CL was conducted first followed by
subsequent PET-RAFT of MA. Unlike Route 1, all chemicals
were mixed together prior to the start of polymerization with a
ratio of [HEBCP]:[MA]:[CL]:[Ir(ppy) 3 ]:[DPP] =
1:100:50:0.001:1. The polymerization was conducted in the
absence of light and at ambient temperature. As shown in
Figure 2a, DPP-catalyzed ROP of CL was observed to proceed
very fast with conversion of CL reaching 88% in 5 h. A linear
first-order relationship between ln([M]0/[M]t) and polymer-
ization time can be seen during the ROP of CL, showing
excellent control over polymerization (Figure 2b). Meanwhile,
no polymerization of MA was observed according to the 1H
NMR spectrum of the reaction mixture (SI, Figure S2). PET-
RAFT polymerization is capable of being switched “on/off”
under visible-light irradiation, which enables instant manipu-
lation of polymerization. Thus, at the time of 5 h, the reaction
mixture was irradiated under blue light to start PET-RAFT
polymerization of MA. The polymerization of MA was
successfully conducted as indicated by a kinetic study. The
conversion of MA reached 56% after irradiation under blue
light for 6 h (Figure 2a). The PET-RAFT polymerization of
MA also exhibited controllable character as reflected by the
linear first-order polymerization kinetics (Figure 2b). The GPC
traces of polymers produced after addition of the MA block
shifted to lower retention time, indicating a continuous increase
DOI: 10.1021/acsmacrolett.6b00121
ACS Macro Lett. 2016, 5, 444−449
ACS Macro Letters
Figure 3. (a) Conversions of CL and MA versus polymerization time; (b) ln([M]0/[M]t) of CL and MA versus polymerization time; (c) GPC traces
of polymer obtained at 1 h, 2 h, 3 h, and 5 h; (d) Mn,RI and Mn,theo of polymers versus polymerization time in the synthesis of PCL-b-PMA block
copolymer via one-pot simultaneous PET-RAFT polymerization of MA and DPP-catalyzed ROP of CL.
of molecular weight (Figure 2c). The molecular weight of
polymer increased from 6240 g/mol to 11 020 g/mol after
irradiation under blue light for 6 h (Figure 2d). The molecular
weight distributions throughout the whole process remained
narrow, ranging from 1.11 to 1.24. The successful formation of
block copolymers was confirmed by 1H NMR spectroscopy (SI,
Figure S3). It is worth to note that that after beginning the
PET-RAFT polymerization the ROP of CL continued, with
conversion of CL increasing from 88% to 98% (Figure 2a).
This indicated that PET-RAFT polymerization would not
interfere with DPP-catalyzed ROP. The two polymerizations
were seemingly compatible, which inspired us to further explore
the synthesis of PCL-b-PMA block copolymers via one-pot
simultaneous PET-RAFT polymerization and ROP.
For synthesis of PCL-b-PMA block copolymer by Route 3,
the one-pot simultaneous PET-RAFT polymerization of MA
and DPP-catalyzed ROP of CL to/from PCL-b-PMA block
copolymers was conducted under irradiation of blue light at
ambient temperature with a ratio of [HEBCP]:[MA]:[CL]:
[Ir(ppy)3]:[DPP] = 1:100:50:0.001:1. 1H NMR spectroscopy
was used to monitor the polymerization process. The ester
group of CL at 4.25 ppm and methyl group of MA at 3.79 ppm
decreased, while the ester group of PCL at 4.15 ppm and the
methyl group of PMA at 3.68 ppm increased gradually (SI,
Figure S4), indicating the PET-RAFT polymerization of MA
and ROP of CL occurred successfully. Figure 3a shows the
time−conversion curve in one-pot polymerization. The ROP of
CL proceeded slightly faster than PET-RAFT polymerization of
MA. Both the PET-RAFT and DPP-catalyzed ROP polymer-
izations resulted in high monomer conversions. After polymer-
ization for 5 h, the conversion of CL was 93%, while the
conversion of MA reached 75%. The kinetic curves of PET-
RAFT polymerization and ROP showed a linear dependence of
ln([M]0/[M]t) on the polymerization time, indicating both
polymerizations proceeded in a controlled manner despite the
presence of each other (Figure 3b). The GPC traces of
447
Letter
polymers synthesized during polymerization were monomodal
and clearly shifted to higher molecular weight with increasing
reaction time (Figure 3c). The molecular weights of polymers
increased continuously, while the PDIs of polymers remained
narrow (≤1.15) throughout the whole polymerization process
(Figure 3d). Furthermore, the molecular weights of polymers
(Mn,RI) were close to their theoretical molecular weights
(Mn,theo) which was indicative of excellent control over both
polymerization processes. After 5 h, a PCL-b-PMA block
copolymer with Mn,RI of 11 960 g/mol and PDI of 1.15 was
obtained.
The structure and composition of PCL-b-PMA block
copolymer obtained from one-pot simultaneous PET-RAFT
polymerization of MA and ROP of CL was characterized by 1H
NMR spectroscopy (SI, Figure S5). The characteristic peaks at
δ 4.15, 2.32, 1.68, and 1.42 ppm corresponding to PCL and
characteristic peak of the methyl group of PMA at 3.68 ppm
can be clearly seen on the spectrum. The methene group of
HEBCP at 3.38 ppm can also be clearly observed. According to
the comparison of the integrals of peaks at 4.15, 3.68, and 3.38
ppm, the PCL-b-PMA block copolymer contained 52 repeating
units of CL and 67 repeating units of MA. The molecular
weight of the block copolymer was calculated as 11 970 g/mol
which was close to the theoretical molecular weight of 12 120
g/mol.
The temporal control of PET-RAFT polymerization in the
presence of ROP was demonstrated by exposing the reaction
mixture to an alternating light “ON” and “OFF” environment.
When the light was on, the PET-RAFT polymerization
proceeded as expected (SI, Figure 6a). However, in the
absence of light (light “OFF”), the PET-RAFT stopped.
Whether the light was on or off, the DPP-catalyzed ROP of CL
proceeded continuously, showing great orthogonality with
PET-RAFT polymerization (SI, Figure 6a and 6b). The on/off
feature of PET-RAFT polymerization offered a simple way to
DOI: 10.1021/acsmacrolett.6b00121
ACS Macro Lett. 2016, 5, 444−449
ACS Macro Letters Letter

Table 1. Characteristics of PCL-b-PMA Block Copolymers Obtained in This Work

[MA]:[CL] theoretical [MA]:[CL] experimental
entry [MA]:[CL] feed ratio MA/CL conversion (%)a ratiog ratioh Mn,RIb Mn,NMRc Mn,theod PDIe
1 100:50 73/96 73/48 78/51 11 350 12 630 12 260 1.11
2 100:50 56/98 56/49 60/45 11 020 10 400 10 680 1.11
3 100:50 76/93 76/46 78/45 11 960 11 970 12 120 1.15
4f 100:100 84/92 84/92 86/91 16 050 17 850 17 770 1.08
5f 50:100 81/99 40/99 42/101 14 510 15 200 15 010 1.10
a,c
Determined by 1H NMR b,eDetermined by THF GPC. cCalculated by the equation: Mn,NMR = MWHEBCP + m × MWMA + n × MWCL. dCalculated
by equation: Mn,theo = MWHEBCP + α1 × DPMA × MWMA+ α2 × DPCL × MWCL, where m and n represent the number of MA and CL units in the
PCL-b-PMA block copolymers, respectively, and α1 and α2 represent the conversion of MA and CL, respectively. DPMA and DPCL represent the
targeted degree of polymerization of MA and CL, and MWHEBCP, MWMA, and MWCL represent the molecular weights of HEBCP, MA, and CL,
respectively. fThe polymerization was conducted for 8 h. gTheoretical ratio of [MA]/[CL] in polymer calculated by conversion. hExperimental ratio
of [MA]/[CL] in polymer calculated by 1H NMR.

regulate the block length ratio of block copolymers in one-pot

polymerization.
■ ACKNOWLEDGMENTS
CB acknowledges the Australian Research Council (ARC) for
The block lengths of block copolymers can be also easily
his Future Fellowship.

adjusted by varying the feed ratios of MA and CL. Well-defined
PCL-b-PMA block copolymers with different block lengths of
PMA and PCL were prepared using this simple one-pot,
simultaneous PET-RAFT polymerization and DPP-catalyzed
ROP technique (Table 1, entries 3−5; SI, Figures S7−S10).
In summary, we have developed, for the first time, a facile
one-pot method to prepare PCL-b-PMA block copolymers by
utilizing DPP-catalyzed ROP and iridium-catalyzed PET-RAFT
polymerization. Due to the full orthogonality and compatibility
of ROP and PET-RAFT polymerization, PCL-b-PMA block
copolymers were synthesized at room temperature by either
one-pot sequential PET-RAFT polymerization of MA followed
by ROP of CL, one-pot sequential ROP of CL followed by
PET-RAFT polymerization of MA, or one-pot simultaneous
PET-RAFT polymerization of MA and ROP of CL. The
polymerization kinetics of the three synthetic routes was
thoroughly investigated by NMR and GPC analysis and
demonstrated the well-controlled manner of both DPP-
catalyzed-ROP and PET-RAFT polymerization. To the best
of our knowledge, this is the first example showing the three
synthetic routes to prepare a series of well-defined PCL-b-PMA
block copolymers with remarkably low molecular weight
distributions (PDIs ≤ 1.15) using a visible-light-mediated
polymerization. Considering the facile nature and versatility of
the current method, the combination of PET-RAFT and ROP
appears an attractive method for the synthesis of polymers with
complex architectures and advanced properties.
■
REFERENCES
(1) (a) Gody, G.; Rossner, C.; Moraes, J.; Vana, P.; Maschmeyer, T.;
Perrier, S. J. Am. Chem. Soc. 2012, 134, 12596−12603. (b) Wang, S.;
Fu, C.; Zhang, Y.; Tao, L.; Li, S.; Wei, Y. ACS Macro Lett. 2012, 1,
1224−1227. (c) Fu, C.; Tao, L.; Zhang, Y.; Li, S.; Wei, Y. Chem.
Commun. 2012, 48, 9062−9064. (d) Geng, J.; Lindqvist, J.; Mantovani,
G.; Haddleton, D. M. Angew. Chem., Int. Ed. 2008, 47, 4180−4183.
(e) Reinicke, S.; Espeel, P.; Stamenović, M. M.; Du Prez, F. E. ACS
Macro Lett. 2013, 2, 539−543. (f) Kan, X. W.; Deng, X. X.; Du, F. S.;
Li, Z. C. Macromol. Chem. Phys. 2014, 215, 2221−2228. (g) Li, Q.;
Wang, T.; Dai, J.; Ma, C.; Jin, B.; Bai, R. Chem. Commun. 2014, 50,
3331−3334. (h) Hrsic, E.; Keul, H.; Möller, M. Macromol. Rapid
Commun. 2015, 36, 2092−2096. (i) Zhang, Y.; Fu, C.; Zhu, C.; Wang,
S.; Tao, L.; Wei, Y. Polym. Chem. 2013, 4, 466−469.
(2) (a) Zhang, Y.; Li, C.; Liu, S. J. Polym. Sci., Part A: Polym. Chem.
2009, 47, 3066−3077. (b) Mecerreyes, D.; Moineau, G.; Dubois, P.;
Jérôme, R.; Hedrick, J. L.; Hawker, C. J.; Malmström, E. E.; Trollsas,
M. Angew. Chem., Int. Ed. 1998, 37, 1274−1276. (c) Wolf, F. F.;
Friedemann, N.; Frey, H. Macromolecules 2009, 42, 5622−5628.
(d) Lu, H.; Wang, J.; Lin, Y.; Cheng, J. J. Am. Chem. Soc. 2009, 131,
13582−13583. (e) Zou, P.; Yang, L. P.; Pan, C. Y. J. Polym. Sci., Part A:
Polym. Chem. 2008, 46, 7628−7636. (f) Kang, H. U.; Yu, Y. C.; Shin,
S. J.; Kim, J.; Youk, J. H. Macromolecules 2013, 46, 1291−1295.
(g) Duxbury, C. J.; Wang, W.; de Geus, M.; Heise, A.; Howdle, S. M. J.
Am. Chem. Soc. 2005, 127, 2384−2385. (h) Yuan, Y.-Y.; Du, Q.; Wang,
Y.-C.; Wang, J. Macromolecules 2010, 43, 1739−1746. (i) Chagneux,
N.; Trimaille, T.; Rollet, M.; Beaudoin, E.; Gerard, P.; Bertin, D.;

■
*
ASSOCIATED CONTENT
S Supporting Information
Gigmes, D. Macromolecules 2009, 42, 9435−9442. (j) Jiang, W.; An,
N.; Zhang, Q.; Xiang, S.; Bai, Z.; Han, H.; Li, X.; Li, Q.; Tang, J.
Macromol. Chem. Phys. 2015, 216, 2107−2114. (k) Cheng, C.;
Khoshdel, E.; Wooley, K. L. Macromolecules 2007, 40, 2289−2292.
The Supporting Information is available free of charge on the (l) Cheng, C.; Khoshdel, E.; Wooley, K. L. Nano Lett. 2006, 6, 1741−
ACS Publications website at DOI: 10.1021/acsmacro- 1746. (m) Petzetakis, N.; Dove, A. P.; O’Reilly, R. K. Chem. Sci. 2011,
lett.6b00121. 2, 955−960. (n) Kang, H. U.; Yu, Y. C.; Shin, S. J.; Youk, J. H. J. Polym.
Experimental details, NMR spectra, GPC traces (Figures Sci., Part A: Polym. Chem. 2013, 51, 774−779. (o) Yu, Y. C.; Li, G.;
Kang, H. U.; Youk, J. H. Colloid Polym. Sci. 2012, 290, 1707−1712.
S1−S10) (PDF) (p) de Freitas, A. G.; Trindade, S. G.; Muraro, P. I.; Schmidt, V.; Satti,

■
A. J.; Villar, M. A.; Ciolino, A. E.; Giacomelli, C. Macromol. Chem. Phys.
2013, 214, 2336−2344.
AUTHOR INFORMATION
(3) Le Hellaye, M.; Lefay, C.; Davis, T. P.; Stenzel, M. H.; Barner-
Corresponding Authors Kowollik, C. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3058−3067.
*E-mail: cboyer@unsw.edu.au. (4) (a) Chiefari, J.; Chong, Y.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T.
*E-mail: j.xu@unsw.edu.au. P.; Mayadunne, R. T.; Meijs, G. F.; Moad, C. L.; Moad, G.; et al.
Macromolecules 1998, 31, 5559−5562. (b) Matyjaszewski, K. Macro-
Notes molecules 2012, 45, 4015−4039. (c) Hawker, C. J.; Bosman, A. W.;
The authors declare no competing financial interest. Harth, E. Chem. Rev. 2001, 101, 3661−3688.

448 DOI: 10.1021/acsmacrolett.6b00121

ACS Macro Lett. 2016, 5, 444−449
ACS Macro Letters Letter

(5) (a) Shanmugam, S.; Xu, J.; Boyer, C. J. Am. Chem. Soc. 2015, 137, (13) Jung, K.; Xu, J.; Zetterlund, P. B.; Boyer, C. ACS Macro Lett.
9174−9185. (b) Treat, N. J.; Sprafke, H.; Kramer, J. W.; Clark, P. G.; 2015, 4, 1139−1143.
Barton, B. E.; Read de Alaniz, J.; Fors, B. P.; Hawker, C. J. J. Am. Chem. (14) Xu, J.; Shanmugam, S.; Fu, C.; Aguey-Zinsou, K.-F.; Boyer, C. J.
Soc. 2014, 136, 16096−16101. (c) Poelma, J. E.; Fors, B. P.; Meyers, Am. Chem. Soc. 2016, DOI: 10.1021/jacs.5b12408.
G. F.; Kramer, J. W.; Hawker, C. J. Angew. Chem. 2013, 125, 6982−
6986. (d) Fors, B. P.; Hawker, C. J. Angew. Chem., Int. Ed. 2012, 51,
8850−8853. (e) Ohtsuki, A.; Lei, L.; Tanishima, M.; Goto, A.; Kaji, H.
J. Am. Chem. Soc. 2015, 137, 5610−5617. (f) Konkolewicz, D.;
Schröder, K.; Buback, J.; Bernhard, S.; Matyjaszewski, K. ACS Macro
Lett. 2012, 1, 1219−1223. (g) Xu, J.; Jung, K.; Atme, A.; Shanmugam,
S.; Boyer, C. J. Am. Chem. Soc. 2014, 136, 5508−5519. (h) Treat, N. J.;
Fors, B. P.; Kramer, J. W.; Christianson, M.; Chiu, C.-Y.; Alaniz, J. R.
d.; Hawker, C. J. ACS Macro Lett. 2014, 3, 580−584. (i) Ribelli, T. G.;
Konkolewicz, D.; Bernhard, S.; Matyjaszewski, K. J. Am. Chem. Soc.
2014, 136, 13303−13312. (j) Anastasaki, A.; Nikolaou, V.; Pappas, G.
S.; Zhang, Q.; Wan, C.; Wilson, P.; Davis, T. P.; Whittaker, M. R.;
Haddleton, D. M. Chem. Sci. 2014, 5, 3536−3542. (k) Zhou, H.;
Johnson, J. A. Angew. Chem., Int. Ed. 2013, 52, 2235−2238. (l) Miyake,
G. M.; Theriot, J. C. Macromolecules 2014, 47, 8255−8261. (m) Zhao,
Y.; Yu, M.; Zhang, S.; Liu, Y.; Fu, X. Macromolecules 2014, 47, 6238−
6245. (n) Anastasaki, A.; Nikolaou, V.; McCaul, N. W.; Simula, A.;
Godfrey, J.; Waldron, C.; Wilson, P.; Kempe, K.; Haddleton, D. M.
Macromolecules 2015, 48, 1404−1411. (o) Anastasaki, A.; Nikolaou,
V.; Brandford-Adams, F.; Nurumbetov, G.; Zhang, Q.; Clarkson, G. J.;
Fox, D. J.; Wilson, P.; Kempe, K.; Haddleton, D. M. Chem. Commun.
2015, 51, 5626−5629. (p) Chen, M.; MacLeod, M. J.; Johnson, J. A.
ACS Macro Lett. 2015, 4, 566−569. (q) Yang, Q.; Dumur, F.; Morlet-
Savary, F.; Poly, J.; Lalevée, J. Macromolecules 2015, 48, 1972−1980.
(r) Perkowski, A. J.; You, W.; Nicewicz, D. A. J. Am. Chem. Soc. 2015,
137, 7580−7583. (s) McKenzie, T. G.; Wong, E. H.; Fu, Q.; Sulistio,
A.; Dunstan, D. E.; Qiao, G. G. ACS Macro Lett. 2015, 4, 1012−1016.
(t) McKenzie, T. G.; Fu, Q.; Wong, E. H.; Dunstan, D. E.; Qiao, G. G.
Macromolecules 2015, 48, 3864−3872. (u) Ogawa, K. A.; Goetz, A. E.;
Boydston, A. J. J. Am. Chem. Soc. 2015, 137, 1400−1403. (v) Hill, M.
R.; Carmean, R. N.; Sumerlin, B. S. Macromolecules 2015, 48, 5459−
5469. (w) Shi, Y.; Gao, H.; Lu, L.; Cai, Y. Chem. Commun. 2009,
1368−1370. (x) Pan, X.; Malhotra, N.; Simakova, A.; Wang, Z.;
Konkolewicz, D.; Matyjaszewski, K. J. Am. Chem. Soc. 2015, 137,
15430−15433. (y) Dadashi-Silab, S.; Doran, S.; Yagci, Y. Chem. Rev.
2016, DOI: 10.1021/acs.chemrev.5b00586. (z) Yagci, Y.; Tasdelen, M.
A.; Kiskan, B.; Ciftci, M.; Dadashi-Silab, S.; Taskin, O. S.; Yilmaz, G.
Visible Light-induced Atom Transfer Radical Polymerization for Macro-
molecular Syntheses. ACS Symp. Ser. Vol: 1187; America Chemical
Society: Washington, DC, 2015; Chapter 8, pp 145−158.
(6) (a) Fu, C.; Xu, J.; Tao, L.; Boyer, C. ACS Macro Lett. 2014, 3,
633−638. (b) Shanmugam, S.; Boyer, C. J. Am. Chem. Soc. 2015, 137,
9988−9999. (c) Huang, T.; Cui, Z.; Ding, Y.; Lu, X.; Cai, Y. Polym.
Chem. 2016, 7, 176−183. (d) Shi, Y.; Liu, G.; Gao, H.; Lu, L.; Cai, Y.
Macromolecules 2009, 42, 3917−3926. (e) Tong, J.; Shi, Y.; Liu, G.;
Huang, T.; Xu, N.; Zhu, Z.; Cai, Y. Macromol. Rapid Commun. 2013,
34, 1827−1832. (f) Xu, J.; Jung, K.; Corrigan, N. A.; Boyer, C. Chem.
Sci. 2014, 5, 3568−3575.
(7) (a) Li, X.; Wang, L.; Chen, G.; Haddleton, D. M.; Chen, H.
Chem. Commun. 2014, 50, 6506−6508.
(8) Tan, J.; Sun, H.; Yu, M.; Sumerlin, B. S.; Zhang, L. ACS Macro
Lett. 2015, 4, 1249−1253.
(9) (a) Fors, B. P.; Poelma, J. E.; Menyo, M. S.; Robb, M. J.;
Spokoyny, D. M.; Kramer, J. W.; Waite, J. H.; Hawker, C. J. J. Am.
Chem. Soc. 2013, 135, 14106−14109. (b) Pester, C. W.; Poelma, J. E.;
Narupai, B.; Patel, S. N.; Su, G. M.; Mates, T. E.; Luo, Y.; Ober, C. K.;
Hawker, C. J.; Kramer, E. J. J. Polym. Sci., Part A: Polym. Chem. 2016,
54, 253−262. (c) Discekici, E. H.; Pester, C. W.; Treat, N. J.;
Lawrence, J.; Mattson, K. M.; Narupai, B.; Toumayan, E. P.; Luo, Y.;
McGrath, A. J.; Clark, P. G.; et al. ACS Macro Lett. 2016, 5, 258−262.
(10) Xu, J.; Jung, K.; Boyer, C. Macromolecules 2014, 47, 4217−4229.
(11) (a) Shanmugam, S.; Xu, J.; Boyer, C. Angew. Chem., Int. Ed.
2016, 55, 1036−1040. (b) Xu, J.; Shanmugam, S.; Boyer, C. ACS
Macro Lett. 2015, 4, 926−932.
(12) Yeow, J.; Xu, J.; Boyer, C. ACS Macro Lett. 2015, 4, 984−990.

449 DOI: 10.1021/acsmacrolett.6b00121

ACS Macro Lett. 2016, 5, 444−449