Polymer 286 (2023) 126402

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Synthesis of water-soluble tetrafunctional urethane acrylate bearing a

pentaerythritol core and its radical polymerization behaviors in an
aqueous solution
Shusuke Okamoto a, Yuii Watanabe b, Yoshiaki Yoshida b, **, Takeshi Endo c, *
a
School of Food and Nutritional Science, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka, Shizuoka, 422-8526, Japan
b
Department of Materials Science, Faculty of Engineering, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu, Fukuoka, 804-8550, Japan
c
Molecular Engineering Institute, Shiga University of Medical Science, Seta, Otsu, Shiga, 520-2192, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: A novel water-soluble tetrafunctional urethane acrylate (TUA) was successfully synthesized by addition reaction
Water-soluble acrylate of pentaerythritol to 2-isocyanatoethyl acrylate. TUA efficiently underwent radical polymerization and its
Radical polymerization copolymerization with monofunctional acrylate monomers exhibiting hydrophilicity in an ethanol aqueous so­
Thermal property
lution, affording corresponding networked polymers in high yields. Notably, TUA exhibited much lower volume
Volume shrinkage
Network Polymer
shrinkage during the radical polymerization compared to a comparative pentaerythritol core based tetrafunc­
tional acrylate containing no urethane bonds. The thermal decomposition temperature of the networked ho­
mopolymer, synthesized from TUA, was much higher than those of the linear polymers, synthesized from
monofunctional urethane acrylate monomers. TUA is expected to be applied to the development of environ­
mentally sustainable polymer materials.

1. Introduction addition, water-soluble multifunctional monomers [14] and dendrimers

Polymers are indispensable materials in a wide variety of industries
to sustain our way of life, but the production of these polymer materials
heavily depends on fossil resources, which damage the environment. As
an alternative method for petroleum-based polymer materials, the
development of degradable polymers is worked on rapidly because of
the easy disposal of used plastics and the reduction in the use of
exhaustible resources [1–8]. Similarly, the creation of environmentally
sustainable polymerization systems is also demanded increasingly.
Among such polymerization systems, the polymerization in an aqueous
solution using water as a harmless solvent is much attractive from both
industrial and ecological perspectives. This polymerization system pro­
duces hydrophilic polymers which can be utilized in various applica­
tions such as metal-capture material [9], surfactant [10–12] and
macroinitiator [13] in water systems.
Although the use of hydrophilic monomers is an essential factor for
synthesizing water-soluble polymers, the number of synthetic examples
of such hydrophilic monomers is considerably fewer compared to those
of hydrophobic monomers due to fewer hydrophilic compounds. In
[15,16] are also valuable for establishing water-based materials as
coating and microcapsule, but these syntheses are more complicated
compared to monofunctional monomers. As a strategy to solve these
complications in synthesis, we have focused on the pentaerythritol,
which consists of a symmetrical structure with four hydroxy groups and
dissolves in water, as a building block for water-soluble multifunctional
monomers.
So far, the pentaerythritol is transformed into a bis(cyclic carbonate)
bearing two cyclic carbonate moieties [17,18] and multifunctional
monomers [19–23], as illustrated in Fig. 1. The bis(cyclic carbonate) ,
which is synthesized by carbonation of pentaerythritol, undergoes
ring-opening polymerizations of two cyclic carbonate moieties to yield a
networked polymer [17]. Recently, our group has reported that syn­
thesis of the sequence-controlled poly(hydroxyurethane) via the step­
wise polyaddition of two different diamines to the bis(cyclic carbonate)
[18]. Besides, multifunctional monomers based on the pentaerythritol
core can be easily synthesized through various chemical modifications
and are widely used as cross-linking reagents [19–23], suggesting that
the pentaerythritol has an enough potential for the production of

* Corresponding author.
** Corresponding author.
E-mail addresses: yoshiday@che.kyutech.ac.jp (Y. Yoshida), tendo@belle.shiga-med.ac.jp (T. Endo).

https://doi.org/10.1016/j.polymer.2023.126402
Received 20 May 2023; Received in revised form 29 August 2023; Accepted 1 October 2023
Available online 3 October 2023
0032-3861/© 2023 Elsevier Ltd. All rights reserved.
S. Okamoto et al.
Fig. 1. Pentaerythritol-based monomers: bis(cyclic carbonate) and multifunc­
tional monomer (previous work) and TUA 1 (this work).
functional polymer materials. Those researches motivate us to synthe­
size a water-soluble tetrafunctional monomer composed of the pen­
taerythritol core.
In this paper, we report the synthesis of a water-soluble tetrafunc­
tional urethane acrylate (TUA) 1 through addition reaction of pentaer­
ythritol to 2-isocyanatoethyl acrylate as shown in Fig. 1 and its radical
polymerization behaviors in an aqueous solution. Radical polymeriza­
tion of 1 and its radical copolymerizations with monofunctional acrylate
monomers in an ethanol aqueous solution efficiently proceeded with
high monomer conversion, producing corresponding networked poly­
mers in high yields. Interestingly, 1 exhibited much lower volume
shrinkage during the radical polymerization compared to a pentaery­
thritol core-based tetrafunctional acrylate containing no urethane
bonds. Furthermore, the networked polymer, which was synthesized
from 1, showed higher thermal stability compared to the linear poly­
mers, which were synthesized from urethane acrylates, owing to the
formation of a network structure.
2. Experimental section
2.1. Instruments
The NMR spectra were measured using a JEOL ECS-400 spectrometer
(400 MHz for 1H and 100 MHz for 13C) using a solvent residual peak as
the internal standard and a JNM-ECX 400 spectrometer (100 MHz for
13
C), respectively. The IR spectra were recorded using a Thermo Fisher
Scientific Nicolet iS10 spectrometer equipped with a Smart iTR diamond
attached total reflection (ATR) sampling accessory. The electrospray
ionization (ESI) spectra of TUA 1 and trifunctional urethane acrylate 8
were measured using a JEOL JMN-700 spectrometer. The thermogra­
vimetric analyses were measured using a Seiko Instrument TG-DTA
6200 under a nitrogen flow rate of 200 mL/min, in a range from 50 to
600 ◦ C at a heating rate of 10 C/min. The differential scanning calo­
◦
rimetry analyses were measured using a Seiko Instrument DSC-6200 R
under a nitrogen flow rate of 50 mL/min.
2
Polymer 286 (2023) 126402
2.2. Materials
Acrylamide monomer (AAm) (>98%),2,2′-azobis(isobutyronitrile)
(AIBN) (>98%), 2,2′-azobis(2-methylpropionamidine)dihydrochloride
(AAPH) (>98%), dibutyltin dilaurate (DBTDL) (>95%), 2-isocyana­
toethyl acrylate (>98%), pentaerythritol (>98%), petaerythritol tet­
raacrylate 5 (>80.0%) polyethylene glycol monomethyl ether acrylate
(PEGA) (>98%) and trimethylolethane (>98%) were purchased from
Tokyo Chemical Industries Co., Ltd. and used as received. Ethanol
(>99.5%), ethyl acetate (>99.5), hexane (>99.5), N,N-dimethylforma­
mide (DMF) (>99.5%), tetrahydrofuran (THF) (>99.5%) and triethyl­
amine (>99.5%) were purchased from FUJIFILM Wako Pure Chemical
Co., Ltd. and used as received. The reported poly-6 and poly-7 in our
previous work [24] were used. Synthesis of trifunctional urethane
acrylate 8 and poly-8 was described in the supporting information.
2.3. Synthesis of tetrafunctional urethane acrylate (TUA) 1
Pentaerythritol (681 mg; 5.00 mmol),tetrahydrofuran (25 mL; 0.20
M) and triethyl amine (40 mg; 0.40 mmol) were added to a 50 mL flask,
and the reaction system was degassed and replaced under a nitrogen
atmosphere. To the prepared suspension, 2-isocyanaterthyl acrylate
(3.11 g; 22.0 mmol) was slowly added via a syringe at room tempera­
ture, and the reaction mixture was stirred at 50 ◦ C. After 20 h, it was
confirmed that a white suspension was transformed into a colorless so­
lution. The resulting solution was concentrated under reduced pressure,
and the residue was chromatographed on a silica gel column (eluent:
hexane/ethyl acetate/dichloromethane = 15/5/1). The collected frac­
tions were evaporated and carefully dried at room temperature under
reduced pressure at 0.10 MPa for 4 h to afford tetrafunctional urethane
acrylate (TUA) 1 as a colorless liquid (1.60 g; 2.28 mmol; 46%).
1
H NMR (400 MHz, DMSO‑d6, at r. t., ppm) δ 7.37 (t, J = 5.6 Hz, 3H,
trans-NH), 7.04 (brs, 1H, cis-NH), 6.35 (dd, J = 1.2, 17.2 Hz, 4H), 6.13
(dd, J = 10.4, 17.2 Hz, 4H), 5.93 (dd, J = 1.2, 10.0 Hz, 4H), 4.08 (t, J =
5.6 Hz, 8H), 3.99–3.96 (m, 8H), 3.24 (dt, J = 5.6, 6.0 Hz, 8H). 13C NMR
(100 MHz, DMSO‑d6, at rt, ppm) δ 165.46, 156.02, 131.74, 128.23,
62.96, 62.35, 48.62, 42.43. IR (ATR, cm− 1) ν 3346, 2958, 2912, 1712,
1692, 1636, 1619, 1529, 1467, 1461, 1446, 1407, 1369, 1330, 1294,
1251, 1179, 1151, 1138, 1045, 1026, 975, 931, 893, 840, 820, 810, 778,
724, 670, 662. ESI (m/z) [M+Na]+ calc for [12C129H14 23 16
40N4 Na1 O16]
+
723.23370; found 723.23556.
2.4. Radical polymerization of TUA 1
Typical procedure: 1 (350 mg; 0.500 mmol) and AIBN (6.6 mg;
0.040 mmol) were dissolved in DMF (1.0 mL; 0.50 M) in a 10 mL flask.
The prepared solution was stirred at 65 ◦ C under a nitrogen atmosphere.
After 5 min, the reaction solution was transformed into a gel. The re­
action system was then heated for a total of 24 h. The resulting gel was
washed with methanol (100 mL), and the insoluble precipitate was
collected with a suction filtration and dried at 80 ◦ C under reduced
pressure at 0.10 MPa for 20 h to afford networked polymer 2 as a white
solid (303 mg; 87% of the theoretical weight).
According to the general procedure for the synthesis of 2, the radical
polymerization of 1 (350 mg; 0.500 mmol) in the presence of AIBN (6.6
mg; 0.040 mmol) was performed in THF (1.0 mL; 0.50 M) at 65 ◦ C for 24
h to obtain networked polymer 2 as a white solid (282 mg; 81% of the
theoretical weight).
According to the general procedure for the synthesis of 2, the radical
polymerization of 1 (350 mg; 0.500 mmol) in the presence of AAPH
(10.8 mg; 0.0400 mmol) was performed in an ethanol aqueous solution
(1.0 mL; 0.50 M, EtOH/H2O = 3/1) at 65 ◦ C for 24 h to obtain networked
polymer 2 as a white solid (315 mg; 90% of the theoretical weight).
13
C NMR (CP-MAS) (100 MHz, at rt, ppm) δ 176.75, 158.82, 65.80,
42.30, 34.00.13C NMR (DD-MAS) (100 MHz, at rt, ppm) δ 175.48,
157.50, 74.84, 63.85, 42.01, 31.65, 26.03. IR (ATR, cm− 1) ν 3566, 3358,
S. Okamoto et al. Polymer 286 (2023) 126402

3395, 2924, 1705, 1514, 1444, 1387, 1345, 1226.1151, 1140, 1028,
960, 897, 853, 768.

2.5. Radical copolymerization of TUA 1 with PEGA

According to the general procedure for the synthesis of 2, the radical

copolymerization of 1 (350 mg; 0.500 mmol) with PEGA (1.93 g; 4.00
mmol) in the presence of AAPH (32.5 mg; 0.120 mmol) was performed
in an ethanol aqueous solution (9.0 mL; 0.50 M, EtOH/H2O = 3/1) at
65 ◦ C for 24 h to obtain networked copolymer 3 as a white solid (2.01 g;
88% of the theoretical weight).
13
C NMR (CP-MAS) (100 MHz, at rt, ppm) δ 181.00, 175.58, 155.06,
72.98, 66.09, 43.57. IR (ATR, cm− 1) ν 3579, 2862, 1726, 1624, 1548,
1444, 1363, 1264, 1247, 1091, 1028, 941, 843.

2.6. Radical copolymerization of TUA 1 with AAm

According to the general procedure for the synthesis of 2, the radical

copolymerization of 1 (188 mg; 0.269 mmol) with AAm (153 mg; 2.15
mmol) in the presence of AAPH (17.5 mg; 0.0645 mmol) was performed
in an ethanol aqueous solution (4.8 mL; 0.50 M, H2O/EtOH = 1/3) at
65 ◦ C for 24 h to obtain networked copolymer 4 as a white solid (289
mg; 84% of the theoretical weight).
13
C NMR (CP-MAS) (100 MHz, at rt, ppm) δ 180.27, 159.02, 66.14,
42.84. IR (ATR, cm− 1) ν 3579, 3396, 3356, 3177, 2919, 1717, 1653,
1635, 1522, 1456, 1397, 1307, 1254, 1170, 1143, 1032, 914, 765.

3. Results and discussion

Fig. 2. 1H NMR spectra in DMSO‑d6 and D2O of TUA 1.

3.1. Synthesis of water-soluble tetrafunctional urethane acrylate based on
a pentaerythritol core 1
protons of four urethane bonds appeared at 7.04 ppm and 7.37 ppm.
Tetrafunctional urethane acrylate (TUA) 1 was synthesized by Those integral ratios were in agreement with the expected values for 1,
addition reaction of pentaerythritol to 2-isocyanatoethyl acrylate in the suggesting the successful formation of 1. The 1H NMR spectrum in D2O
presence of triethyl amine (TEA) as a base catalyst at 50 ◦ C for 20 h also clarifies that the presence of the signals attributable to 1. In the 13C
under a nitrogen atmosphere (Scheme 1). The white suspension was NMR spectrum in DMSO‑d6 (Fig. 3), the signal attributable to the qua­
transformed into a colorless solution before and after the reaction, and ternary carbon of the pentaerythritol core was observed at 42.4 ppm,
thin layer chromatography analysis of the reaction solution supported while those attributable to the methylene moieties derived from the
the progress of the addition reaction. The resulting solution was isolated pentaerythritol core and the urethane acrylate moieties were confirmed
using a silica gel column chromatography, affording 1 in 52% yield. 1 is
soluble in both water and organic solvents including chloroform, THF,
DMSO, methanol and ethanol. Particularly, 1 is well soluble in a 1:3
aqueous solution of water and ethanol.
The structure of 1 was studied by NMR (Fig. 2 and S1-2), IR Fig. S4
(Fig. S7) and ESI Fig. S6 (Fig. S9) analyses. In the 1H NMR spectrum in
DMSO‑d6 (Fig. 2), signals attributable to three types of methylene
moieties derived from 1 were confirmed. The signals attributable to the
C–– C bonds derived from the acrylate moieties were observed in a range
from 5.83 ppm to 6.35 ppm. In addition, two signals attributable to the

13
Scheme 1. Synthesis of TUA 1 based on a pentaerythritol core. Fig. 3. C NMR spectra of TUA 1 and networked polymers 2.

3
S. Okamoto et al. Polymer 286 (2023) 126402

Table 2
Volume change during polymerization.
Entry Monomer Density of Polymer Density of Volume
Monomer (g/ Polymer (g/ Change
cm3)a cm3)a (%)b

1 1 1.309 2 1.338 − 2.22

2 5 1.171 poly-5 1.441 − 23.1
c
3 6 0.9983 poly-6 1.086 − 8.78
c
4 7 1.028 poly-7 1.106 − 7.59
5 8 1.185 poly-8 1.269 − 7.09
a
Measured by a pychnometer under a helium atmosphere.
b
Volume change is calculated by (Densitymonomer-Densitypolymer)/Densitymo­
nomer × 100.
c
Cited from Ref.24.

Scheme 2. Radical polymerizations of TUA 1 and its
copolymerizations.
at 48.6 ppm, 62.3 ppm, and 62.9 ppm. Additionally, two signals
attributable to the C–– C bonds derived from the urethane acrylate
moieties were observed at 128.2 ppm and 131.7 ppm. The carbonyl
groups in the urethane bonds and the ester bonds in 1 were confirmed at
156.0 ppm and 165.4 ppm, respectively. The 1H–1H and 1H–13C spectra
in Figs. S1–2 also support further evidence for the structure of 1. In the
IR spectrum Fig. S4 (Fig. S7) of 1, the peaks corresponding to the amine
and carbonyl groups derived from the four urethane bonds were
observed as a single peak, suggesting that the formation of hydrogen
bonding among the monomer molecules and there would be few ure­
thane bonds that do not form hydrogen bonding.
3.2. Radical polymerization of TUA 1
Radical polymerizations under various polymerization conditions of
1 were investigated (Scheme 2). Their obtained results were summa­
rized at Table 1. We performed its radical polymerization using AIBN as
a radical initiator in DMF at 65 ◦ C for 24 h under a nitrogen atmosphere
(Entry 1). According to the progress of the radical polymerization, the
reaction solution was gradually transformed into a gel, implying that the
formation of insoluble networked polymer. The structure of the obtained
networked polymer was analyzed by solid-state 13C NMR (CP-MAS
(Fig. 3) and DD-MAS (Fig. S3)) techniques and IR (Fig. S7) spectros­
copies. The CP- and DD-MAS spectra clarify that the quantitative con­
sumption of signals in the 120–140 ppm region, which are attributable
to the C–
– C bonds derived from 1. In addition, a new signal attributable
to the carbonyl carbons in the ester bonds derived from 2 was confirmed
at 175.5 ppm (DD-MAS) and 176.8 ppm (CP-MAS). The IR spectrum
shows that the presence of characteristic peaks attributable to the
structure of 2. Focusing on the amine groups in urethane bonds, the
much stronger peak at 3358 cm− 1 than that at 3566 cm− 1 was observed,
most likely suggesting that 2 also forms strong hydrogen bonding among
the polymer chains. Those analytic results demonstrate the successful
formation of networked polymer 2.
radical When the radical polymerization of 1 was carried out in THF under
the similar conditions for Entry 1, 2 was obtained in a good yield (Entry
2). Furthermore, the radical polymerization of 1 using 2,2′-azobis[2-
aminodipropane] dihydrochloride (AAPH) as a radical initiator in an
ethanol aqueous solution also gave 2 in a good yield (Entry 3).
Next, we conducted the radical copolymerizations of 1 with poly­
ethylene glycol acrylate (PEGA) or acryl amide (AAm) in an ethanol
aqueous solution (Scheme 2). Those polymerizations proceeded
smoothly to give the corresponding networked copolymers 3 and 4 in
good yields. Their structures were analyzed by CP-MAS (Fig. S4) and IR
(Fig. S7) spectroscopies, clarifying that the complete consumption of the
C–– C bonds of the acrylate moieties derived from two types of
monomers.
Volume change during polymerization is an important factor for an
application to polymer materials, and its value can be calculated by the
density difference between monomer and polymer. We have previously
revealed that an isocyanurate core-based monofunctional urethane
acrylate with three urethane bonds inducing hydrogen bonding shows
almost zero volume shrinkage during radical polymerization due to the
formation of dense packing between monomer molecules [24] and
recently found that isocyanurate core-based monofunctional urethane
acrylates with substituents enabling the higher packing formation
exhibit volume expansion [25]. Densities of 1 and 2, which was obtained
in Entry 3 of Table 1, were measured by using a gas pychnometer under
a helium atmosphere (Table 2 and S1). The volume change value of 1
during the radical polymerization was estimated to be − 2.22%,
implying that 1 undergoes the radical polymerization with volume
shrinkage. In order to clearly reveal the degree of volume change of 1
among other acrylates, we compared the volume change value of 1 with
those of comparative acrylate monomers 5–8 as shown in Fig. 4 (Table 2
and S2-3). The synthetic procedures and spectral data of trifunctional
urethane acrylate 8 and poly-8 were described in the supporting infor­
mation (Schemes S1-2, Figures S5-6 and S8). 8 and poly-8 are also be
expected to form hydrogen bonding via urethane bonds from the IR
spectra (Fig. S8). Interestingly, the much smaller volume shrinkage

Table 1
Results of radical polymerizations of TUA 1.
Entry Monomer(s) Solvent Initiator Networked Yield (%)a Conv. (%)b
(Molar ratio) Polymer

1 1 DMF AIBN 2 87 >95

2 1 THF AIBN 2 81 >95
3 1 EtOH: H2O (3 : 1) AAPH 2 90 >95
4 1: PEGA (1 : 2) EtOH: H2O (3 : 1) AAPH 3 88 >95
5 1: AAm (1 : 2) EtOH: H2O (3 : 1) AAPH 4 84 >95
a
Insoluble-parts in methanol.
b
Estimated by CP-MAS spectra of isolated networked polymers 2–4.

4
S. Okamoto et al. Polymer 286 (2023) 126402

radical polymerization was estimated to be − 7.09% and much larger

compared to that of 1 (Entry 1 vs Entry 5), suggesting that the molecular
design of monomer with symmetric structure is an important factor in
restricting volume change.
The thermal properties of the synthesized polymers were subjected
by TG and DSC analyses. The resulting profiles are shown in Fig. 5A–D.
Decomposition temperatures for 5% weight loss (Td5) of the resulting
polymers are extracted from Fig. 5A–C, and those values are summa­
rized at Table 3. The Td5 value of the networked polymer 2, which was
obtained in Entry 3 of Table 1, was much larger than those of poly-6 and
poly-7, most likely due to the suppression of molecular motion by the
formation of rigid network structures (Fig. 5A, Entry 1 vs Entries 2–3).
The higher Td5 value of 2 compared to poly-8 indicates that the degree of
cross-linking density strongly influences thermal stability (Fig. 5A, Entry
1 vs Entry 4). The networked copolymer 3, which consists of 1 and
PEGA, showed higher Td5 than poly-PEGA (Fig. 5B, Entry 5 vs Entry 6).
Similarly, the Td5 value of the networked copolymer 4, which consists of
1 and AAm, was much higher than that of poly-AAm (Fig. 5C, Entry 7 vs
Entry 8). The results suggest that cross-linkable 1 can be used as a
comonomer to increase the thermal stability of polymer.

Fig. 4. Structure of comparative monomers 5–8. Table 3

Thermal decomposition temperatures of polymers.
value of 1 than that of the pentaerythritol derived tetrafunctional Entry Polyacrylate Structure of the side chain Td5 (oC)a
acrylate 5 with no urethane bonds clarifies that the incorporation of
1 2 (Networked Polymer) Urethane Bond 314
urethane bond inducing intermolecular interactions into monomer 2 poly-6 (Linear Polymer) Urethane Bond 267
molecule is effective in the restriction of volume change during poly­ 3 poly-7 (Linear Polymer) Urethane Bond 264
merization owing to the formation of highly dense packing between 4 poly-8 (Networked Polymer) Urethane Bond 236
5 3 (Networked Copolymer) Urethane Bond 307
monomer molecules (Entry 1 vs Entry 2). The volume shrinkage value of
Ether Bond
1 was much lower than those of monofunctional urethane acrylates 6–7 6 poly-PEGA (Linear Polymer) Ether Bond 298
(Entry 1 vs Entries 3–4), although multifunctional monomer generally 7 4 (Networked Copolymer) Amide Bond 276
tends to exhibit larger volume shrinkage than monofunctional mono­ Urethane Bond
mer, implying that 1 is one of multifunctional acrylate monomers which 8 poly-AAm (Linear Polymer) Amide Bond 233

induce low volume shrinkage. The volume change value of 8 during the a
Determined by TG analysis.

Fig. 5. TG charts of A) 2 and poly-6, poly-7 and poly-8, B) 3 and poly-PEGA, C) 4 and poly-AAm, and DSC charts D) 2–4, poly-8 and poly-AAm.

5
S. Okamoto et al.
As shown in the DSC charts of Fig. 5D, temperatures for glass tran­
sition and melting of the synthesized polymers 2–4 and poly-8 were not
confirmed clearly until 250 ◦ C, which is before their thermal decom­
position temperatures. In contrast, the glass transition temperature (Tg)
value of poly-AAm was 180 ◦ C. The comparison of Tgs between 4 and
poly-AAm suggests that a significant suppression in the mobility of
polymer, due to the formation of a network structure.
4. Conclusion
We described that the synthesis of a water-soluble tetrafunctional
urethane acrylate 1 by addition reaction of pentaerythritol to 2-isocya­
natoethyl acrylate and its radical polymerization behaviors in an ethanol
aqueous solution. Radical polymerization of 1 in an ethanol aqueous
solution smoothly proceeded with high monomer conversion, affording
corresponding networked polymer 2. Furthermore, radical co­
polymerizations of 1 with water-soluble acrylates such as PEGA and
AAm in an ethanol aqueous solution produced corresponding networked
copolymers 3–4 in good yields. Interestingly, 1 exhibited much lower
volume shrinkage during radical polymerization compared to a pen­
taerythritol core-based tetrafunctional acrylate 5 without urethane
bonds, owing to the formation of hydrogen bonding between urethane
bonds. Temperature for 5% weight loss of 2 was much higher than those
of comparative poly-6-8, due to the influence of the formed network
structures from four acrylate moieties of 1 on the suppression of the
mobility of polymer. This research provides us that 1 can be expected as
a novel water-soluble cross-linking reagent for an application to the
development of environmentally sustainable polymer materials.
Notes
The authors declare no competing financial interest.
CRediT authorship contribution statement
Shusuke Okamoto: Conceptualization, Methodology, Validation,
Formal analysis, Investigation, Data curation, Writing – original draft,
Writing – review & editing, Visualization. Yuii Watanabe: Formal
analysis, Data curation. Yoshiaki Yoshida: Conceptualization, Writing
– review & editing, Supervision. Takeshi Endo: Conceptualization,
Writing – review & editing, Supervision, Funding acquisition.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Takeshi Endo reports financial support was provided by Adeka Corp.
Data availability
Data will be made available on request.
Acknowledgements
This research was financially supported by ADEKA Corporation. We
thank Mr. Toshihiko Murai and Dr. Toyofumi Shinozuka (ADEKA Cor­
poration) for helpful suggestions. We also thank Mr. Masayuki Hashi­
moto and Dr. Yasuyuki Mori for technical assistance with the
measurements in Molecular Engineering Institute, Shiga University of
Medical Science. High-resolution mass analyses of 1 and 8 were carried
out by the Cooperative Research Program of “Network Joint Research
Center for Materials and Devices” and in the Center for Instrumental
Analysis, Kyushu Institute of Technology (KITCIA).
6
Polymer 286 (2023) 126402
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2023.126402.
References
[1] T. Narancic, F. Cerrone, N. Beagan, K.E. O’Connor, Recent advances in bioplastics:
application and biodegradation, Polymers 12 (2020) 920. https://doi:10.3390
/polym12040920.
[2] A. Larrañaga, E. Lizundia, A review on the thermomechanical properties and
biodegradation behavior of polyesters, Eur. Polym. J. 121 (2019), 109296, https://
doi.org/10.1016/j.eurpolymj.2019.109296.
[3] V. Delplace, J. Nicolas, Degradable vinyl polymers for biomedical applications,
Nat. Commun. 7 (2015) 771–784, https://doi.org/10.1038/NCHEM.2343.
[4] H.K. Webb, J. Arnott, R.J. Crawford, E.P. Ivanova, Plastic degradation and its
environmental implications with special reference to poly(ethylene terephthalate),
Polymers 5 (2013) 1–18, https://doi.org/10.3390/polym5010001.
[5] A. Loredo-Treviño, G. Gutiérrez-Sánchez, R. Rodríguez-Herrera, C.N. Aguilar,
Microbial enzymes involved in polyurethane biodegradation: a review, J. Polym.
Environ. 20 (2012) 258–265, https://doi.org/10.1007/s10924-011-0390-5.
[6] G. Pasparakis, T. Manouras, P. Argitis, M. Vamvakaki, Photodegradable polymers
for biotechnological applications, Macromol. Rapid Commun. 33 (2012) 181–198.
https://doi:10.1002/marc.201100637.
[7] I. Armentano, M. Dottori, E. Fortunati, S. Mattioli, J.M. Kenny, Biodegradable
polymer matrix nanocomposites for tissue engineering: a review, Polym. Degrad.
Stabil. 95 (2010) 2126–2146. https://doi:10.1016/j.polymdegradstab.2010.06.00
7.
[8] B.C. Daglen, D.R. Tyler, Photodegradable plastics: end-of-life design principles,
Green Chem. Lett. Rev. 3 (2010) 69–82. https://doi:10.1080/1751825090350
6723.
[9] T.-M. Geng, D.-Y. Wu, Water-soluble polymeric chemosensor for selective detection
of Hg2+ in aqueous solution using rhodamine-based modified poly
(acrylamide–acrylic acid), Luminescence 30 (2015) 1263–1268. https://d
oi:10.1002/bio.2890.
[10] I. Capek, On inverse miniemulsion polymerization of conventional water-soluble
monomers, Adv. Colloid Interface Sci. 156 (2010) 35–61, https://doi.org/10.1016/
j.cis.2010.02.006.
[11] I. Dimitrov, B. Trzebicka, A.H.E. Müller, A. Dworak, C.B. Tsvetanov,
Thermosensitive water-soluble copolymers with doubly responsive reversibly
interacting entities, Prog. Polym. Sci. 32 (2007) 1275–1343, https://doi.org/
10.1016/j.progpolymsci.2007.07.001.
[12] G.A. Mun, Z.S. Nurkeeva, A.B. beissegul, A.V. Dubolazov, P.I. Urkimbaeva, K. Park,
V.V. Khutoryanskiy, Temperature-responsive water-soluble copolymers based on 2-
hydroxyethyl acrylate and butyl acrylate, Macromol. Chem. Phys. 208 (2007)
979–987, https://doi.org/10.1002/macp.200600555.
[13] G. Delaittre, J. Nicolas, C. Lefay, M. Save, B. Charleux, Aqueous suspension of
amphiphilic diblock copolymer nanoparticles prepared in situ from a water-soluble
poly(sodium acrylate) alkoxyamine macroinitiator, Soft Matter 2 (2006) 223–231.
https://doi:10.1039/b515267d.
[14] C.-Y. Lee, J.-W. Kim, K.-D. Suh, Water-soluble urethane acrylate ionomers: effect of
molecular structure on ultraviolet coating properties, J. Appl. Polym. Sci. 78
(2000) 1853–1860, https://doi.org/10.1002/1097-4628(20001209).
[15] X. Wang, J. Tang, M. Sui, X. Wang, J. Xu, Y. Shen, J. Nicolas, Degradable water
soluble hyperbranched polymers for drug delivery, J. Contr. Release 152 (2011)
e76–e78. https://doi:10.1016/j.jconrel.2011.08.134.
[16] G. Li, S. Jiang, Y. Gao, X. Liu, F. Sun, Synthesis and property of water-soluble
hyperbranched photosensitive polysiloxane urethane acrylate, Ind. Eng. Chem.
Res. 52 (2013) 2220–2227. https://doi:10.1021/ie303084w.
[17] D.W. Grijpma, E. Kroeze, A.J. Nijenhuis, A.J. Pennings, Poly(l-lactide) crosslinked
with spiro-bis-dimethylene-carbonate, Polymer 34 (1993) 1496–1503, https://doi.
org/10.1016/0032-3861(93)90868-B.
[18] N. Osaka, T. Endo, One-pot nonisocyanate synthesis of sequence-controlled poly
(hydroxy urethane)s from a bis(six-membered cyclic carbonate) and two different
diamines, Macromolecules 54 (2021) 2059–2067, https://doi.org/10.1021/acs.
macromol.1c00045.
[19] P. Niedermann, G. Szebényi, A. Toldy, Effect of epoxidized soybean oil on curing,
rheological, mechanical and thermal properties of aromatic and aliphatic epoxy
resins, J. Polym. Environ. 22 (2014) 525–536. https://doi:10.1007/s10924-014-0
673-8.
[20] D. Zhou, A. Tkacheva, X. Tang, B. Sun, D. Shanmukaraj, P. Li, F. Zhang,
M. Armand, G. Wang, Stable conversion chemistry-based lithium metal batteries
enabled by hierarchical multifunctional polymer electrolytes with near-single ion
conduction, Angew. Chem. Int. Ed. 58 (2019) 6001–6006. https://doi:10.
1002/anie.201901582.
[21] G. Yang, S.L. Kristufek, L.A. Link, K.L. Wooley, M.L. Robertson, Thiol− ene
elastomers derived from biobased phenolic acids with varying functionality,
Macromolecules 49 (2016) 7737–7748. https://doi:10.1021/acs.macromo
l.6b01018.
[22] M. Liu, D. Zhou, Y.-B. H, Y. Fu, X. Qin, C. Miao, H. Du, B. Li, Q.-H. Yang, Z. Lin, T.
S. Zhao, F. Kang, Novel gel polymer electrolyte for high-performance
lithium–sulfur batteries, Nano Energy 22 (2016) 278–289. https://doi:10.1016/j.
nanoen.2016.02.008.
S. Okamoto et al.
[23] A. Toldy, B. Szolnoki, Gy Marosi, Flame retardancy of fibre-reinforced epoxy resin
composites for aerospace applications, Polym. Degrad. Stabil. 96 (2011) 371–376,
https://doi.org/10.1016/j.polymdegradstab.2010.03.021.
[24] S. Okamoto, T. Shinozuka, T. Endo, Molecular design of acrylates containing
isocyanurate moiety undergoing low volume shrinkage during their radical
Polymer 286 (2023) 126402
photopolymerization, Macromolecules 54 (2021) 5806–5814, https://doi.org/
10.1021/acs.macromol.1c00885.
[25] S. Okamoto, T. Shinozuka, T. Endo, Molecular design of acrylates containing
isocyanurate core-based acrylates undergoing volume expansion on radical photo-
photopolymerization, Macromol. Rapid Commun. 43 (2022), 2200014, https://
doi.org/10.1002/marc.20220001.