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Cite This: ACS Omega 2018, 3, 13928−13934 http://pubs.acs.org/journal/acsodf

Synthesis of Multiarm Star Polymer Based on Hyperbranched

Polyester Core and Poly(ε-caprolactone) Arms and Its Application in
UV-Curable Coating
Yuying Chen,† Nan Wang,† Gangsheng Tong,† Dong Wu,‡ Xin Jin,*,† and Xinyuan Zhu*,†
†
School of Chemistry & Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China
‡
Shanghai ANOKY Group Co., Ltd., 881 Songhua Road, Qingpu Export Processing Zone, Shanghai 201703, P. R. China
*
S Supporting Information
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ABSTRACT: Hyperbranched polymers have attracted much

attention in the field of UV-curable coatings because of its low
viscosity, highly branched structure, and rich functional
Downloaded via 45.148.124.140 on September 2, 2020 at 11:55:14 (UTC).

moieties. However, hyperbranched polymers also have some

limitations. For example, the spherical structure increases the
crosslinking hindrance, resulting in surplus functional
moieties. In this study, a multiarm star polymer with
hyperbranched polyester core and linear polymer arms was
synthesized and used as UV-curable coating. H40, the fourth
generation of the hyperbranched polyester, was chosen as the
core owing to its low viscosity and high chemical reactivity.
Poly(ε-caprolactone) (PCL) arms were introduced to
increase the content of flexible segments and reduce the
cross-linking hindrance. The terminal hydroxyls were then replaced with methacrylate groups to endow the star polymer with
UV curable ability, yielding HPCLn-M. This multiarm star polymer was considered as a promising candidate to make up for the
shortcomings of UV-curable coating made from the hyperbranched polymer. The properties, such as hardness, adhesion, acid
resistance, and alkali resistance of cured films were enhanced obviously after the grafting of PCL. Moreover, to further explore
the effect of the length of PCL grafts on the coating, star polymers with different degree of polymerization (DP) were
synthesized. Through the performance tests of cured films, it was found that the multiarm star polymer HPCLn-M could make
up for the limitations of the hyperbranched polymer when the DP of PCL was suitable, and the comprehensive performance of
cured film reached the best when the DP of PCL was 20. Overall, this multiarm star polymer could combine the advantages of
the hyperbranched polymer and linear polymer and has the potential to be the next environmentally friendly UV-curable
coating.

1. INTRODUCTION the unique structural characteristics. The three-dimensional

UV-curable coating is considered as a kind of energy-saving
and environmentally friendly coating developed from 1960s.1,2
UV curing of the polymers can be accomplished in tens of
seconds, even faster. UV-curable coatings contain less solvent,
which reduces the emission of volatile organic compounds
(VOC). Besides, because no heating is required, UV-curable
coating avoids thermal damage and has a wide range of
applications. UV curing also consumes less energy than
thermal curing.3−7
Generally, the oligomers for UV-curable coatings are
composed of linear polymers, but the viscosity of linear
polymers usually increases dramatically with the increase of
molecular weight. In order to obtain the appropriate viscosity,
plenty of reactive diluents or solvents are often added, resulting
in an increase in systemic toxicity.8−11 Therefore, polymers
with low viscosity are necessary for UV-curable coatings.
In recent years, hyperbranched polymers have attracted
much attention of being used as UV-curable coating because of
spherical structure endows hyperbranched polymers with lower
viscosity and higher solubility in many solvents, compareds to
linear polymers with the same molecular weight. The
application of hyperbranched polymers in UV-curable coating
can reduce the content of reactive diluent and solvent, which
can reduce the emission of VOC. In addition, the abundant
functional moieties on the surface of spherical hyperbranched
polymers can increase the density of cross-linking sites, which
results in a high-density cross-linked network structure and a
faster UV-curing speed.12−18 Besides, functional coatings, such
as protective coatings19 and antifouling coatings20 can be made
by modifying the ending groups of hyperbranched polymers.
However, the spherical structure of the hyperbranched
polymers increases the cross-linking hindrance to a certain
Received: August 22, 2018
Accepted: October 11, 2018
Published: October 23, 2018

© 2018 American Chemical Society 13928 DOI: 10.1021/acsomega.8b02128

ACS Omega 2018, 3, 13928−13934
ACS Omega
extent simultaneously, resulting in excess unreacted functional
moieties; and the excess functional groups in coating will
reduce the stability and resistance of the film.21,22 Besides,
volume shrinkage occurs rapidly during the UV-curing process
of the polymer because of the spherical structure. As a result,
internal stress is generated and the adhesion between coating
and the substrate decreases. In contrast to hyperbranched
polymers, linear polymers have a higher reaction degree in
cross-linking.23,24 Thus, hyperbranched polymers have limi-
tations which could be compensated by linear polymers.25
In this study, we synthesized a multiarm star polymer with a
hyperbranched polyester core and poly(ε-caprolactone) (PCL)
arms (Scheme 1). The linear polymers are radially attached to
Scheme 1. Synthesis of MultiArm Star Polymer HPCLn-M
the central core, forming a star polymer.26−29 H40, the fourth
generation of the hyperbranched polyester, was chosen as the
core moiety owing to its low viscosity and high reactivity.30−33
PCL was chosen as the graft moiety because of its good
compatibility, good solubility, and safety. Linear PCL was
grafted onto H40 to obtain the multiarm star polymer
(designed as HPCLn) by ring-open polymerization.34,35
Methacrylation was then carried out to endue polymers with
cross-linking ability. Hyperbranched polymer cores could
provide low viscosity and rich functional groups, whereas
linear PCL arms could decrease the cross-linking hindrance
and increase the reaction degree of cross-linking. Also, this
multiarm star structure can prevent phase separation of the
polymer with the change of temperature. In addition, multiarm
star polymers (HPCL-M) with different degrees of polymer-
ization (DP) were synthesized to explore the effect of the
length of PCL arms on the coating. The viscosity, melting
temperature, thermal stability, and cured film properties (such
as hardness, adhesion, acid resistance, and alkali resistance) of
HPCL-M were also explored. Then, we demonstrated that this
multiarm star polymer had a good performance in UV-curable
coating applications and could compensate up for the
shortcomings of the hyperbranched polymer.
Table 1. Data of Synthesized Materials
sample PCL/H40 (n/n)a CC/H40 (n/n)b DP, aimc
HPCL10 0.61 0.33 10
HPCL15 0.58 0.29 15
HPCL20 0.54 0.26 20
HPCL25 0.53 0.25 25
HPCL30 0.50 0.22 30
a
The ratio of PCL arms and H40 end groups calculated by 1H NMR. bThe ratio of CC and H40 end groups calculated by 1H NMR.
c
Theoretical value of DP according to the feed ratio. dPractical value of DP calculated by 1H NMR. eMolecular weight calculated by 1H NMR.
13929
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2. RESULTS AND DISCUSSION
2.1. Synthesis of Multiarm Star Polymer H40-star-
PCLn (HPCLn) and H40-star-PCLn(10∼30)-MAC (HPCLn-M).
Ring-opening polymerization was used to synthesize five kinds
of HPCLn as depicted in Scheme 1. Owing to the different
feed ratios between H40 and ε-caprolactone, HPCLn
containing different lengths of PCL arms were obtained. The
DP and molecular weight of multiarm star polymers are listed
in Table 1.
Taking HPCL20 as an example, the DP of PCL chains, the
quantity of PCL arms in each H40 core, and the molecular
weights were obtained from the 1H NMR spectra (Figure 1a).
Figure 1. 1H NMR spectra of (a) HPCL20 and (b) HPCL20-M.
The small signals appear at about 1.27 ppm corresponding to
methyl protons of the hyperbranched polyester. The signals at
about 3.67 ppm can be assigned to the methylene protons next
to the hydroxyl terminus, whereas the signals at about 2.34
ppm can be attributed to protons on methylene groups
adjacent to ester groups in the repeating unit. The practical
quantity of PCL arms in each H40 were calculated by
comparing the peak area of methyl protons and the peak area
of methylene protons next to the hydroxyl terminus. In
addition, the DP was determined by calculating the ratio of the
integral of the signal of methylene protons next to ester groups
and the integral of the signal of methylene protons next to the
hydroxyl terminus. Then, the molecular weights were
calculated by the value of DP and the quantity of PCL arms
in each H40 core. The molar ratio of PCL arms and H40 end
groups (Table 1) is 0.50−0.61, meaning more than half of the
hydroxyl end groups successfully grafted PCL. In addition, the
practical DP of the PCL grafts is close to the targeted DP. The
DP, NMRd Mn, NMR (kDa)e Mn, GPC (kDa) Mw, GPC (kDa)
11 56 39 73
16 75 54 102
22 93 63 131
27 112 70 155
34 131 84 196
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length of PCL arms is closer to the targeted value with the
decrease of DP values. The calculation accuracy decreased
when the DP increased because of the weaker signal of the
methylene protons next to the hydroxyl terminus. Besides,
molecular weights were also determined by gel permeation
chromatography (GPC). The different structures between
hyperbranched and linear polymers led to results deviations
from 1H NMR data. Polymer dispersity was shown by GPC
data, which increased with the increase of molecular weights.
The second step in the synthesis was methacrylation in order
to transform hydroxyls to methacrylate moieties. As shown in
Figure 1b, the signals at about 6.12 and 5.57 ppm correspond
to protons on double bonds. The small signals appear at about
1.91 ppm attributed to methyl protons. The result of the 1H
NMR spectrum demonstrates that methacrylate groups were
grown onto HPCL20 successfully. The amount of methacrylate
moieties could be calculated by comparing the signal area of
methyl protons in methacrylate moieties and the signal area of
methyl protons in H40. In addition, the results show that
about half hydroxyls were transformed to methacrylate
moieties (Table 1).
2.2. Shear Viscosity. Viscosity is a key factor for UV-
curable systems because of its direct effects on leveling
properties and coating methods. Generally, the viscosity of
UV-curable systems is determined by the oligomer, which is
mainly related to segment density of polymer, intermolecular
chain entanglement, and hydrogen bonding interactions. The
tests need to be performed while HPCLn-M are in a molten
state in order to determine the bulk viscosity. The melting
temperature was determined by differential scanning calorim-
etry (DSC). As shown in Table 2, the melting temperature of
Table 2. DSC Analysis of Polymers
degree of onset of melting peak of melting
sample crystallization (%) (°C)
H40-M
HPCL10-M 23 42.6
HPCL15-M 28 46.2
HPCL20-M 31 48.3
HPCL25-M 34 54.6
HPCL30-M 36 52.1
HPCLn-M was 50.3−60.6 °C. Thus, 70 °C was chosen as the
test temperature at which point HPCLn-M could be
completely melted. Figure 2 shows the typical plots of viscosity
as a function of shear rate. At the same shear rate, the shear
viscosity increases with the increase of the molecular weight
Figure 2. Shear viscosity of polymers as a function of shear rate at 70
°C.
Article
because linear arms provided chain entanglement and
interactions. All polymers show shear thinning behavior. H40
shows low viscosity and weak shear thinning because of its
three-dimensional spherical structure. Polymers with longer
PCL grafts exhibit more significant shear thinning when the
shear rates increased, which indicates more physical entangle-
ments and wider molecular weight distribution in these
systems. At low shear rates, the entanglement and disentangle-
ment were in dynamic equilibrium, showing a basically
constant viscosity. Macromolecules were in a highly entangled
network structure at this period, so the shear stress and
viscosity were high. At high shear rates, the rate of
disentanglement of the molecular chains was greater than the
rate of entanglement, resulting in less molecular chains
entangled structure. PCL grafts were oriented in the direction
of flow. When the shear rate was higher, the degree of
orientation became higher, exhibiting the lower shear stress
and lower viscosity. Polymers with longer PCL arms
underwent more orientation at high shear rates, thus showing
more pronounced shear thinning. The low melting temper-
ature and viscosity show the potential for HPCLn-M to be
used in high solids or even powder coatings.
2.3. DSC Analysis. DSC tests were executed to determine
degree of crystallization and melting temperature. As shown in
Table 2, polymers crystallized to varying degrees (23−36%)
with the increase of the DP of PCL due to the crystallinity of
PCL. The degree of crystallization was calculated by setting
166.5 J/g to the fusion heat of 100% crystallinity.37 With the
growth of PCL grafts, the molecular weight and flexibility of
the hyperbranched star polymer increased, leading to a higher
melting temperature (Figure 3).
(°C)
50.3
53.5
54.5
58.5
60.6
Figure 3. DSC curves of H40-M and HPCLn-M.
2.4. Thermal Stability. Thermogravimetric curves of
HPCLn and HPCLn-M are shown in Figure 4. The
temperature of 10, 50, and 90% weight loss of polymers are
listed in Table 3. All polymers could stay stable until 250 °C,
suggesting a general good thermal stability. The spherical
structure of H40 protected the ester bond in the inner layer,
enabling H40 and H40-M with a little higher thermal
degradation temperature. Flexible PCL grafts were easier to
be degraded than spherical H40. The thermal decomposition
curves of HPCLn star polymers are divided into two sections,
the degradation of PCL and H40, obviously shown in Figure
4b, which also implies the successful grafting of PCL.
Methacrylate groups endowed HPCLn with cross-linking
function. Cross-linking occurred during heating, so the thermal
stability of HPCLn-M samples is universally better than
HPCLn. The temperature of 50% weight loss of HPCLn-M is
13930 DOI: 10.1021/acsomega.8b02128
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ACS Omega Article

Figure 4. (a) TGA curves and (b) weight change curves of H40 and HPCLn; (c) TGA curves and (d) weight change curves of H40-M and
HPCLn-M.

Table 3. TGA Data of Polymers made. The hardness, adhesion, acid resistance, and alkali
sample T10% (°C) T50% (°C) T90% (°C)
resistance of films were tested. The viscosity was determined
H40 261 359 433
by the results in Figure 2. The results are listed in Table 4.
HPCL10 274 337 418 When the length of PCL arms grew, flexible segments
HPCL15 305 338 400 increased and the cross-linking steric hindrance reduced,
HPCL20 311 341 400 facilitating the crosslinking reaction. As a result, remaining
HPCL25 314 342 400 carbon−carbon double bonds reduced and the reaction degree
HPCL30 296 329 379
of cross-linking improved, leading to better hardness, adhesion,
H40-M 327 414 447
HPCL10-M 303 399 430 acid resistance, and alkali resistance of films. However, the
HPCL15-M 310 378 424 viscosity of films increased significantly with the growth of
HPCL20-M 318 389 417 PCL arms. When the DP of PCL grafts exceeded 20, the
HPCL25-M 350 390 403 hardness, adhesion, and resistance no longer increased with the
HPCL30-M 343 383 397 growth of PCL arms, but the viscosity still increased
significantly. Thus, HPCL20-M exhibited the best compre-
higher than HPCLn by about 50 °C, implying successful
methacrylation. hensive performance in comparison.
2.5. Properties of HPCLn-M-Cured Films. In this study, To sum up, the abundant functional moieties of H40
PCL was grafted onto H40 to reduce the steric cross-linking brought high reactivity and large cross-linking density, but also
hindrance of hyperbranched polymers. Some coating proper- led to unreacted moieties, which had a bad effect on the
ties were determined to evaluate the effectiveness of PCL arms. stability of cured films. Linear PCL grafts with suitable length
Cured films were prepared by polymers HPCLn-M, photo
could make up for the shortcomings of films made from H40.
initiators, and solvent. The mole fraction of H40 was same at
3.0 mol/L, whereas the length of PCL grafts was different, Besides, the properties were affected by the DP of PCL, and
highlighting the features of linear grafts. Six kinds of films with the comprehensive performance reached the best when the DP
the DP of PCL at 0, 10, 15, 20, 25, and 30, respectively, were of PCL was 20.

Table 4. Properties of Cured Films (3.0 mol/L H40 with Different Lengths of PCL Arms)

property H40-M HPCL10-M HPCL15-M HPCL20-M HPCL25-M HPCL30-M

viscosity (Pa·s) 2.18 19.5 53.8 89.4 194 324
hardness B HB HB H H H
adhesion/grade 2 1 1 0 0 0
acid resistance bubble bubble bubble no change no change no change
alkali resistance bubble bubble bubble no change no change no change
saline water resistance no change no change no change no change no change no change

13931 DOI: 10.1021/acsomega.8b02128

ACS Omega 2018, 3, 13928−13934
ACS Omega
3. CONCLUSIONS
Multiarm star polymers (HPCLn-M) were prepared with a
simple procedure and a high yield. H40 was chosen as the core
owing to its low viscosity and high reactivity. PCL was grafted
onto H40 by means of ring-opening polymerization, and the
terminal hydroxyls were substituted by methacrylate groups.
This multiarm star polymer was applied to UV-curable
coating. The effect of H40 and PCL on the coating was
explored. H40 could improve the hardness, adhesion, and
viscosity of films because of its three-dimensional spherical
structure and rich functional groups. However, weak acid
resistance and alkali resistance were caused at the same time.
PCL grafts could make up for this shortcoming by increasing
the content of flexible segments and the reaction degree of
cross-linking. Moreover, the performance is affected by the DP
of PCL, and the suitable DP of PCL grafts for the sake of great
performance was determined as 20 in this study. HPCLn-M
have low melting temperature and low shear viscosity, reducing
the usage of solvent and showing a potential for powder
coating. Thus, this multiarm star polymer could be an
environmentally friendly UV-curable coating, which combines
the advantages of the hyperbranched polymer and linear
polymer.
4. EXPERIMENTAL SECTION
4.1. Materials. Boltorn H40 regular purchased from Seebio
is the fourth generation of the hyperbranched polyester and
has about 64 hydroxyl end groups per molecule on average.
The theoretical molecular weight of H40 is 7214 g/mol. H40
was dried at room temperature in a vacuum oven for 24 h
before experiments. Methacrylic anhydride, ε-caprolactone,
Sn(Oct)2, and (3-aminopropy)trimethoxysilane were pur-
chased from Sigma-Aldrich. ε-Caprolactone was distilled
under reduced pressure before experiments.
4.2. Characterization and Instruments. 1H NMR and
13
C NMR were carried out on an AVANCE III HD 400
spectrometer at 400 and 100 MHz, respectively, using CDCl3
as the solvent. The molecular weight was determined by GPC
HLC-8320 GPC using tetrahydrofuran (THF) as the eluent.
The flow rate was 1 mL/min. Linear polystyrene standards are
used as calibrations, which is a relative measurement method.
Rheological properties of polymers were performed on an AR-
G2 rotary rheometer (TA, USA) at 70 °C in the shear rate
range of 0.01−200 s−1. 25 mm diameter and 2 mm thickness
compression molded sample platens were prepared using a
laboratory hot press at 70 °C under 15 MPa pressure for 15
min. In addition, the gap was adjusted to 1.0 mm. The degree
of crystallization and melting temperature were determined by
DSC Pyris 1. Samples (about 7 mg) were heated in N2
atmosphere from −50 to 150 °C, stayed for 1 min, cooled
down to −50 °C, stayed for 1 min, and then heated to 150 °C
again. The heating rate and cooling rate both were 10 °C/min.
Thermal stability was determined via thermogravimetric
analysis (TGA) Q5000IR. Samples (approximate 5 mg) were
heated from 50 to 600 °C with a heating rate of 20 °C/min in
N2 atmosphere. The hardness of cured films was determined
according to GB/T 6739-2006. Adhesion strength of cured
films was determined according to GB/T 9286-1998.
Resistance to chemical reagents of cured films was determined
according to GB/T 1763-79.
4.3. Experimental Methods and Procedures. The
synthesis can be divided into two parts: grafting and end-
13932
Article
capping. The graft polymers were obtained by grafting ε-
caprolactone onto hydroxyls end groups. Then, the hydroxyls
of PCL were capped with methacrylate moieties. Five kinds of
macromonomers containing different lengths of PCL grafts
were synthesized.
4.4. General Procedure for Grafting PCL onto H40.
Taking the synthesis of HPCL20 as an example according to a
previous report,36 the fourth generation H40 (0.800 g, ∼7.10
mmol hydroxyl groups) and dry ε-caprolactone (16.0 g, 142
mmol) was added to a round-bottomed flask. H40 completely
dissolved in ε-caprolactone. After the temperature raised to
130 °C, a catalytic amount of Sn(Oct)2 (catalyst/hydroxyl
groups = 1/20, n/n) was added. The ring-opening polymer-
ization was triggered under the protection of N2 (g). The
mixture was stirred for 5 h, turning into viscous liquid. Then,
the mixture was dissolved in THF after cooling down to room
temperature. The polymer was precipitated into a 10-fold
mixed solution of cold methanol and ether (1:1), before dried
at 35 °C for 24 h. Finally, 14.0 g (yield, 83.2 wt %) white
crystalline powders were obtained.
1
H NMR (CDCl3) data, δ (ppm): 4.08 (m, −CH2−O−
CO−, bis-MPA), 4.02 (m, −CH2−O−CO−, ε-PCL), 3.67 (m,
−CH2−OH), 2.34 (m, −CH2−CO−O−, ε-PCL), 1.67 (m,
−CH2−CH2−CO−O− or −CH2−CH2−O−CO−), 1.40 (m,
−CH2−CH2−CH2−), 1.27 (s, −CH3).
4.5. General Procedure for Methacrylation. Methacry-
lation was performed according to the previous literature.37 A
star-branched polyester HPCL20 (5.00 g, containing 2.00
mmol hydroxyl end groups) was dissolved in CH2Cl2 (15 mL)
in a double-neck round-bottom flask. Triethylamine (0.607 g,
6.00 mmol) and 4-dimethylaminopyridine (0.100 g, 0.82
mmol) were added to the solution. The flask was equipped
with a drying tube filled with calcium chloride anhydrous and
cooled on a water/ice-bath. Then, methacrylic anhydride
(0.617 g, 4.00 mmol) diluted with CH2Cl2 (3 mL) was added
dropwise. The mixture was stirred for 3 h under the protection
of N2 (g). After further being diluted with CH2Cl2, the reaction
mixture was precipitated into 10-fold cold ether. At last, the
product was dried at 35 °C for 24 h to give 4.6 g (yield 92 wt
%) of white crystalline powder.
1
H NMR (CDCl3) data, δ (ppm): 6.09 (s, CCH2, cis to
methyl), 5.54 (s, CCH2, trans to methyl), 4.06 (m, −CH2−
O−CO−, bis-MPA), 3.87 (m, −CH2−O−CO−, ε-PCL), 3.67
(m, −CH2−OH), 2.34 (m, −CH2−CO−O−, ε-PCL), 1.94 (s,
−CH3, methacrylate), 1.64 (m, −CH2−CH2−CO−O− or
−CH2−CH2−O−CO−), 1.38 (m, −CH2−CH2−CH2−), 1.25
ppm (s, −CH3, bis-MPA).
4.6. Preparation of UV-Cured Film. In order to explore
the effect of hyperbranched polymer, linear polymer and its DP
on the properties of the coating, one group of UV-cured films
was made. The group contained six kinds of films with the DP
of PCL at 0, 10, 15, 20, 25, and 30, respectively. The content of
H40 was controlled at the same mole fraction. A certain
concentration of the polymer and 3 wt % of photo initiators
were dissolved in CH2Cl2. The solution was coated on the
tinplate using a coating bar with 30 μm and then exposed to
ultraviolet light at the wavelength of 365 nm, cured several
minutes. The distance between the tinplate and ultraviolet light
was 9 cm. The solvent was evaporated finally.
DOI: 10.1021/acsomega.8b02128
ACS Omega 2018, 3, 13928−13934
ACS Omega
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.8b02128.
1
H NMR spectra of H40 and H40-M (Figure S1), 1H
NMR spectra of HPCL10 and HPCL10-M (Figure S2),
1 (8) Zhou, X. Y.; Ma, J.; Jiang, L. Research and composition of UV
H NMR spectra of HPCL15 and HPCL15-M (Figure
S3), 1H NMR spectra of HPCL25 and HPCL25-M
(Figure S4), 1H NMR spectra of HPCL30 and
HPCL30-M (Figure S5), GPC curves of polymers
(Figure S6), and FTIR spectra of (a) HPCLn and (b)
HPCLn-M (Figure S7) (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jxcindy@sjtu.edu.cn (X.J.).
*E-mail: xyzhu@sjtu.edu.cn (X.Z.).
ORCID
Xin Jin: 0000-0003-1779-6407
Xinyuan Zhu: 0000-0002-2891-837X
Author Contributions
X.Z. and X.J. contributed the original idea and supervised the
project. Y.C. performed all the experiments and participated in
results analysis. All authors contributed to discussion regarding
the research. D.W. and G.T. provided technical support for the
enterprise and increased the practicality of the project. Y.C.
wrote the manuscript with inputs from all authors.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (51690151, 51503122, 51473093), the
National Basic Research Program of China (2015CB931801),
the Shanghai Rising-Star Program (17QC1401100), the
Shanghai Municipal Government (18JC1410800), Shanghai
Jiao Tong University (15X110070008, 16X100100019,
17X100040070), and the Qingpu Scientific Research Project
(no. 2018-5).
■
ABBREVIATIONS
H40, the fourth generation of the hyperbranched polyester;
PCL, poly(ε-caprolactone); HPCLn, multiarm star polymer
H40-star-PCLn(10−30); HPCLn-M, multiarm star polymer H40-
star-PCLn(10−30)-MAC
■
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13934 DOI: 10.1021/acsomega.8b02128

ACS Omega 2018, 3, 13928−13934