Synthesis and polymerization of styrene monomers bearing spiroorthoester structure and volume change during crosslinking by double ring-opening of the pendant spiroorthoesters of the obtained polymers

Article abstract of DOI:10.1002/pola.27184

Novel styrene monomers bearing a five or seven-membered spiroorthoester structure (SOE5, SOE7) were synthesized and their radical polymerizations as well as volume change during crosslinking of the obtained polymers were investigated. SOE5 and SOE7 were prepared from 4-vinylbenzyl glycidyl ether and γ-butyrolactone or ε-caprolactone using boron trifluoride diethyl ether complex as a catalyst, respectively. Radical polymerizations of these monomers using 2,2′-azobisisobutyronitrile (AIBN) gave the corresponding styrene-based polymers with keeping the spiroorthoester structures unchanged. These polymers could be transformed to networked polymers by heating with a sulfonium antimonate, a thermally latent cationic polymerization initiator. Copolymerization of SOE5 or SOE7 with styrene at various compositions was carried out to efficiently obtain the corresponding copolymers, respectively. These polymers and copolymers showed little volume shrinkage or slight volume expansion during the crosslinking. Copyright

Full text of DOI:10.1002/pola.27184

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
Synthesis and Polymerization of Styrene Monomers Bearing
Spiroorthoester Structure and Volume Change During
Crosslinking by Double Ring-Opening of the Pendant
Spiroorthoesters of the Obtained Polymers
Takahiro Miyata,1 Kozo Matsumoto,1,2 Shigeaki Yonemori,3,4 Takeshi Endo1
1Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka Prefecture 820-8555, Japan
2Department of Biological and Environmental Chemistry, Kinki University, 11-6 Kayanomori, Iizuka,
Fukuoka 820-8555, Japan
3Technical Development Division, AGC Seimi Chemical Co., Ltd., 3-2-10, Chigasaki, Chigasaki-shi,
Kanagawa Prefecture 253-8585, Japan
4Japan Association for Chemical Innovation, Sanbancho KS Bldg., 2F, 2, Sanban-cho, Chiyoda-ku,
Tokyo 102-0075, Japan
Correspondence to: T. Endo (E-mail: tendo@moleng.fuk.kindai.ac.jp)
Received 1 November 2013; accepted 22 March 2014; published online 11 April 2014
DOI: 10.1002/pola.27184
ABSTRACT: Novel styrene monomers bearing a five or seven-
membered spiroorthoester structure (SOE5, SOE7) were synthe-
sized and their radical polymerizations as well as volume change
during crosslinking of the obtained polymers were investigated.
SOE5 and SOE7 were prepared from 4-vinylbenzyl glycidyl ether
and c-butyrolactone or e-caprolactone using boron trifluoride
diethyl ether complex as a catalyst, respectively. Radical poly-
merizations of these monomers using 2,20-azobisisobutyronitrile
(AIBN) gave the corresponding styrene-based polymers with
keeping the spiroorthoester structures unchanged. These poly-
mers could be transformed to networked polymers by heating
with a sulfonium antimonate, a thermally latent cationic poly-
merization initiator. Copolymerization of SOE5 or SOE7 with sty-
rene at various compositions was carried out to efficiently obtain
the corresponding copolymers, respectively. These polymers
and copolymers showed little volume shrinkage or slight volume
C
V
expansion during the crosslinking. 2014 Wiley Periodicals, Inc.
J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1790–1795
KEYWORDS: 4-chloromethyl(styrene); epoxide; radical polymer-
ization; spiroorthoester; styrene
polymers and copolymers showed volume expansion of 1.3–
2.8% during the crosslinking. However, styrene-based poly-
mers having SOE structures have not been examined so far.
Polystyrene have been used in various fields due to their
unique physical and chemical properties such as chemical
resistance, weather resistance, electrical insulation proper-
ties. We consider that synthesis of styrene monomer bearing
SOE enable to expand the application range of the adhesives
and improve of the molding stability.
INTRODUCTION Polymerization of usual vinyl monomers such
as methyl methacrylate or styrene undergo 10–20% volume
shrinkage. Curing of epoxy or phenol resins are also known to
be accompanied by some degree of volume shrinkage. This
phenomenon causes serious problems when they are used in
practical applications that are deformation, decrease of adhe-
sion strength, crack formation, etc. However, spiroorthocarbon-
ates,1–5 bislactone,6 and spiroorthoesters (SOEs),7–13 which
undergo double ring-opening polymerizations, exhibit little
shrinkage or slight expansion in volume change during the pol-
ymerizations. Among them SOEs are particularly attracting
because of their easy accessibility. They can be prepared from
epoxides and lactones in one step using Lewis acid catalysts.14
In this study, we synthesized novel styrene monomers bearing
a five or seven-membered SOE structure from 4-vinylbenzyl
glycidyl ether with c-butyrolactone or e-caprolactone using
boron trifluoride diethyl ether complex as a catalyst, and
investigated radical polymerizations/copolymerizations with
styrene (Scheme 1). We further examined crosslinking of the
polymers by heating with a sulfonium antimonate, a thermally
latent cationic polymerization initiator.
Our research group have studied synthesis of (meth)acry-
lates monomers bearing SOE structures, their homopolymeri-
zation and copolymerization with styrene, and investigated
the volume changes during the crosslinking.15–17 These
C
V
2014 Wiley Periodicals, Inc.
1790
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
SCHEME 2 Polymerization of SOE5/SOE7.
SCHEME 1 Synthesis of SOE5/SOE7.
the residual protons as the internal standards. High resolu-
tion FAB mass spectra were obtained on a JEOL JSM-700
spectrometer. Number-averaged molecular weight (Mn) and
weight-averaged molecular weight (Mw) were estimated by
size exclusion chromatography (SEC) on a TOSOH HLC-8220
system equipped with refractive index and ultra violet
(k 5 254 nm) detectors, and three consecutive polystyrene
gel columns [TSKgels (bead size, exclusion limited molecular
weight); super-AW4000 (6 mm, >4 3 105), super-AW3000
(4 mm, >6 3 104), and super-AW2500 (4 mm, >2 3 103)].
The system was operated at a flow rate of 0.5 mL/min, using
a DMF solution of lithium bromide (10 mM) as an eluent at
40 ꢀC. Polystyrene standards were employed for calibration.
Measurement of monomer and polymer density was carried
out with SHIMADZU AccuPyc1340 gas pycnometer.
EXPERIMENTAL
Materials
4-Vinyl benzyl glycidyl ester (VBGE), derived from 4-(chloro-
methyl)styrene, was provided from AGC Seimi Chemical
(Kanagawa, Japan) and distilled in the presence of 3,5-dini-
trotoluene under reduced pressure. Styrene was purchased
from Wako Pure Chemical Industry (Osaka, Japan) and
washed three times with 1 M NaOH aqueous solution and
with distilled water, dried over anhydrous Na2SO4, and dis-
tilled over CaH2 under reduced pressure before use. c-
Butyrolactone and e-caprolactone was purchased from Wako
Pure Chemical Industry. BF3OEt2 was purchased from Kanto
Chemical (Tokyo, Japan). 2,20-Azobisisobutyronitrile (AIBN)
was purchased from Wako Pure Chemical Industry (Osaka,
Japan) and purified by recrystallization from methanol.
Methyl ethyl ketone (MEK), chlorobenzene, and dichlorome-
thane were purchased from Wako Pure Chemical Industry
(Osaka, Japan) and distilled before use. Benzyl 4-
hydroxyphenyl methyl sulfonium hexafluoroantimonate
(BPMS) was provided from Sanshin chemical Industry
(Yamaguchi, Japan).
Preparation of SOE5
A mixture of c-butyrolactone (3.44 g, 40 mmol), BF3OEt2
(0.25 mL, 2.0 mmol) in dichloromethane (25 mL) was kept 0
ꢀC, and VBGE (35 mmol, 6.66 g) was added dropwise over a
period of 1.5 h. After the mixture was allowed to react at
room temperature for 3 h, the reaction was quenched by
adding excess amount of triethylamine. The reaction mixture
was washed with water and the separated organic layer was
dried over anhydrous magnesium sulfate. Dichloromethane
was removed by evaporation, and then a part of the crude
product was purified by an alumina column chromatography
(hexane/ethyl acetate 5 8/1) to give pure monomer in 66%
total yield (colorless liquid). IR (ATR) 716, 823, 832, 905,
948, 1033, 1066, 1236, 1325, 1373, 1436, 1621, 2857, 2947
Characterization
IR spectra were recorded on a Thermo Scientific Nicolet iS10
spectrometer equipped with a Smart iTR Sampling Accessory.
1H (300 MHz) and 13C (75 MHz) NMR spectra were recorded
on a JEOL AL300 NMR spectrometer in CDCl3 or DMSO-d6.
Chemical shifts were determined using tetramethylsilane or
cm21 1H-NMR d (CDCl3) 1.93–2.24 (m, 4H),3.46–3.76 (m,
.
2H), 3.79–3.87 (m, 1H), 3.88–4.05 (m, 2H) 4.10–4.21 (m,
1H) 4.31–4.53 (m, 1H), 4.53–4.68 (m, 2H), 5.26 (d, J 5 10.8
Hz, 1H), 5.77 (d, J 5 17.7 Hz, 1H), 6.72 (dd, J 5 11.0, 17.7 Hz,
1H), 7.30 (d, J 5 8.1 Hz, 2H), and 7.40 (d, J 5 8.1 Hz, 2H). 13C
NMR d (CDCl3) 24.27, 24.37, 32.79, 33.01, 66.545, 67.01,
TABLE 1 Results of Radical Polymerization of SOE
Conversion (%)a
Yield (%)b
Mn
Mw/Mn
c
c
polySOE5
polySOE7
84
86
63
74
27,000
16,600
1.71
2.01
a
Determined by 1H NMR.
Methanol-insoluble parts.
FIGURE 1 1H NMR spectra of (a) VBGE, (b) SOE5, and (c) SOE7
b
c
Estimated by SEC (eluent . DMF, polystyrene standards).
measured in CDCl3.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795
1791

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
SCHEME 3 Copolymerization of SOE5 or SOE7 with styrene.
FIGURE 2 1H NMR spectra of (a) polySOE5 and (b) polySOE7
measured in CDCl3 or DMSO-d6.
white solid of polySOE5 in 72% yield. IR (ATR) 742, 804,
1062, 1166, 1232, 1363, 1412, 1505, 1719, 2845, 2895, and
1
3356 cm21. H NMR d (CDCl3) 0.92–1.75 (m, 3H), 1.81–2.18
70.24, 71.43, 73.26, 73.33, 74.41, 75.40, 114.00, 114.05,
126.36, 128.06, 128.16, 129.60, 129.82, 136.51, 136.54,
137.18, and 137.50.
(m, 4H), 3.15–3.65 (m, 3H), 3.66–3.78 (m, 1H), 3.78–3.95
(m, 2H), 3.95–4.14 (m, 1H), 4.14–4.51 (m, 3H), and 6.10–
7.12 (m, 4H). Mn 5 27,000, Mw 5 46,000, and Mw/Mn 5 1.71.
Preparation of SOE7
Homopolymerization of SOE7
By a similar procedure, SOE7 was obtained in 63% yield. IR
(ATR) 713, 755, 822, 903, 954, 1011, 1063, 1173, 1231,
PolySOE7 was obtained under the similar polymerization
condition to that of SOE5 in 66% yield. IR (ATR) 807, 953,
965, 1009, 1060, 1173, 1230, 1363, 1478, 1721, 2847, 2904,
1432, 2848, and 2195 cm21 1H-NMR d (CDCl3) 1.51–2.21
.
(m, 8H), 3.42–3.85 (m, 5H), 4.07–4.19 (m, 1H), 4.28–4.50
(m, 1H), 4.51–4.63 (m, 2H), 5.26 (d, J 5 11.4 Hz, 1H), 5.77
(d, J 5 17.7 Hz, 1H), 6.72 (dd, J 5 10.8, 17.7 Hz, 1H), 7.30 (d,
J 5 8.1 Hz, 2H), and 7.40 (d, J 5 8.1 Hz, 2H). 13C NMR d
(CDCl3) 22.72, 22.81, 29.24, 29.27, 30.55, 30.70, 37.25,
37.16, 64.12, 64.23, 67.14, 66.32, 67.14, 70.52, 72.13, 73.14,
73.17, 74.23, 75.25, 113.85, 113.88, 124.33, 124.48, 126.24,
126.25, 127.94, 128.01, 136.50, 137.07, 137.51, and 137.57.
1
and 3470 cm21. H NMR d (CDCl3) 0.92–1.75 (m, 2H) 1.48–
1.84 (m, 6H), 2.03–2.18 (m, 2H), 3.30–3.86 (m, 5H), 4.02–
4.20 (m, 1H), 4.21–4.61 (m, 3H), and 6.15–7.17 (m, 4H).
Mn 5 16,600, Mw 5 33,400, and Mw/Mn 5 2.01.
Copolymerization of SOE5 and Styrene
A typical procedure for a copolymerization of SOE5 and sty-
rene is as follows. A mixture of SOE5 (415 mg, 1.50 mmol),
styrene (156 mg, 1.50 mmol), AIBN (14.4 mg, 0.090 mmol),
and MEK (3 mL) was charged in a 20 mL Schlenk tube
equipped with a magnetic stirring bar and a three-way stop-
cock. After the mixture was degassed by three melt and
throw cycles under vaccum, the flaꢀsk was filled with nitro-
gen. The mixture was heated at 60 C for 24 h with stirring.
Precipitation of the product with methanol followed by vac-
uum drying gave a white solid of poly(St-co-SOE5) in 77
wt% yield. The copolymer composition was determined by
Homopolymerization of SOE5
A typical solution polymerization procedure is as follows. A
mixture of SOE5 (828 mg, 3.0 mmol), AIBN (14.7 mg, 0.090
mmol), and MEK (3 mL) was charged in a 20 mL Schlenk
tube equipped with a magnetic stirring bar and a three-way
stopcock. After the mixture was degassed under reduced
pressure, the flask was filled with nitrogen. The mixture was
heated at 60 ꢀC for 24 h with stirring. Precipitation of the
product with methanol followed by vacuum drying gave a
1
the H NMR measurement in CDCl3.
TABLE 2 Results of Radical Copolymerization of SOE with Styrene
Feed Ratio (mol %)
Compositiona
Polymer
Styrene
SOE
x
y
Yieldb (%)
Mn (Mn/Mw)c
Poly(St-co-SOE5)
0
100
77
0
100
76
63
60
56
44
74
65
59
47
27,000 (1.71)
19,200 (2.27)
15,000 (1.87)
5900 (1.55)
23
51
74
0
24
52
72
0
49
48
36
28
Poly(St-co-SOE7)
100
73
100
68
16,600 (2.01)
17,200 (3.51)
15,300 (2.60)
6900 (1.61)
27
51
76
32
51
73
49
49
24
27
a
c
Determined by 1H NMR.
Methanol-insoluble parts.
Estimated by SEC (eluent: DMF, polystyrene standards).
b
1792
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
Crosslinking of PolySOE7, Poly(St-co-SOE5), or Poly(St-co-
SOE7) with Sulfonium Antimonite
NW-SOE7, NW-(St-co-SOE5), or NW- (St-co-SOE7) were
obtained under the similar crosslinking condition to that of
NW-SOE5. Measurement of polymer and networked polymer
densities was carried out with AccuPyc1340 at 25 ꢀC,
respectively.
RESULTS AND DISCUSSION
SCHEME 4 Crosslinking reaction of SOE and styrene.
Monomer Synthesis
A styrenic monomer having a SOE moiety (SOE5 and SOE7)
was successfully synthesized by the reaction of VBGE and c-
butyrolactone or e-caprolactone in the presence of boron tri-
fluoride diethyl ether complex, respectively (Scheme 1).
Figure 1 showed the 1H NMR spectra of the desired SOE5
and SOE7 purified by alumina column chromatography.
Three protons in the vinyl group of the styrenic moiety were
clearly observed at 5.26, 5.77, and 6.72 ppm while the peak
of the epoxy group (a, b, and c) were disappeared. The mul-
tiplet peaks of 1.90–2.30 ppm and 3.30–4.50 ppm (SOE5
and SOE7 in Fig. 1.) were assigned to methylene protons of
the cyclic ester of SOE moiety.
Crosslinking of PolySOE5 with Sulfonium Antimonite
A mixture of polySOE5 (4 mmol, 1.01 g) and BPMS (0.1
mmol, 94 mg) in chlorobenzene (8 mL) was charged in a 20
mL Schlenk tube equipped with a magnetic stirring bar and
a three-way stopcock. After the mixture was degassed by
three melt and throw cycles under vaccum, the flask was
filled with nitrogen. The mixture was heated at 120 ꢀC for
2 h with stirring. A swollen solid was precipitated, which
was washed with methanol and chlorobenzene, followed
by drying in vacuo, gave a white solid of Networked-SOE5
(NW-SOE5) in 87% yield.
FIGURE 3 FT-IR spectra of (a) polySOE5/NW-SOE5 and (b) polySOE7/NW-SOE7. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]
TABLE 3 Results of Density Measurement of the Polymers Having SOE Structures and Their Volume Change During Crosslinking
Composition (%)a
Styrene SOE
Polymer
Networked polymer
Density (g/cm3)b Volume change (%)c
Polymer
Density (g/cm3)b
Poly(St-co-SOE5)
72
52
24
0
28
1.142
1.190
1.198
1.213
1.097
1.151
1.188
1.221
1.176
1.201
1.205
1.223
1.143
1.174
1.183
1.186
22.89
20.92
20.58
20.89
24.02
21.96
10.42
12.78
48
76
100
27
Poly(St-co-SOE7)
73
51
32
0
49
68
100
a
c
Determined by 1H NMR.
Measured by gas pycnometer at 25 ꢀC.
Volume change. [volume of networked polymer 2 volume of polymer]/
[volume of polymer] 3 100.
b
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795
1793

JOURNAL OF
POLYMER SCIENCE
ARTICLE
WWW.POLYMERCHEMISTRY.ORG
FIGURE 4 Photographs of (a) the networked polymer film SOE7 poly(St-co-SOE7) (St:SOE7 5 3:1) and (b) it under a bending load.
[Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]
Homopolymerization
the presence of catalytic amount of sulfonium antimonite
(BPMS), a thermally latent cationic polymerization initiator
(Scheme 4). Swollen products were precipitated, which were
isolated by washing methanol and chlorobenzene and drying
in vacuo to obtain crosslinked polymers. Figure 3(a) shows
typical IR spectra of polySOE5 and networked polySOE5 (NW-
polySOE5). The strong absorption of NW-SOE5 at 1719 cm21
attributed to the C@O stretching of structure which was gener-
ated by double ring-opening of SOE is clearly observed. Figure
3(b) also shows typical IR spectra of polySOE7 and networked
polySOE7 (NW-SOE7). Absorption of NW-SOE7 at 1722 cm21
[Fig. 3(b)] of the C@O stretching was also observed.
Homopolymerizations of SOE5 and SOE7 were carried out at
60 ꢀC using AIBN as an initiator in MEK (Scheme 2). The
polymerization results are summarized in Table 1. The
monomer conversion was estimated by monitoring the poly-
merization mixture with 1HNMR. The polymeric products
were collected by precipitation with methanol, and the iso-
lated yields were determined.
Figure 2 shows the 1H NMR spectra of the obtained poly-
SOE5 and polySOE7, respectively. Signals at 1.81–2.18 ppm
[Fig. 2(a)] assigned to protons on the 5-membered cyclic
ester of SOE5 structure are clearly observed, and the
broad signals around 0.92–1.75 ppm assigned to the
methyne and methylene protons in the main chain are
also observed, while all vinyl protons at 5.26, 5.77, and
6.72 ppm disappeared. These observations indicate that
the vinyl polymerization proceeded without changing of
SOE5 structure. Similarly, two signals at 1.48–1.84 ppm
and 2.03–2.18 ppm [Fig. 2(b)] assigned to protons on the
7-membered cyclic ester of SOE7 structure are clearly
observed, and the broad signals around 0.92–1.75 ppm
assigned to the methyne and methylene protons in the
main chain were also observed, whereas the vinyl protons
at 5.26, 5.77, and 6.72 ppm disappeared in the polymer-
ization product of SOE7. Results of the polymerization of
SOE7 also are summarized in Table 1.
Density measurements of polySOE5, poly(St-co-SOE5), poly-
SOE7, poly(St-co-SOE7), and their networked polymers were
carried out with AccuPyc1340 at 25 ꢀC. Table 2 summar-
ized the results of volume change for the homopolymers
and copolymers during the crosslinking reaction. Homopoly-
mer of SOE7 showed the large volume expansion (2.78%),
reaction. While homopolymer of SOE5 showed volume
shrinkage of 0.89% during crosslinking, the shrinkage was
quite smaller than general crosslinking reactions (Table 3).
In the case of copolymers with styrene, the volume shrink-
age decreases or volume expansion increases as the SOE
content increases. It is noteworthy that volume expansion
in polySOE7 was higher than that in polySOE5. This is
because the ratio of double ring-opening to single ring-
opening may be higher in the crosslinking of polySOE7
than in that of polySOE5. Since the five-membered cyclic
compounds are more stable than seven membered cyclic
compounds, the ratio of double ring-opening to single ring-
opening is higher in SOE7.
Copolymerization
Copolymerization of SOE5 or SOE7 with styrene was exam-
ined in MEK using AIBN as a radical initiator (Scheme 3).
Copolymerization proceeded smoothly to give the corre-
sponding copolymers in 44–72% yield. The copolymer com-
positions were determined by 1H NMR analysis of the
obtained polymers. Results of the copolymerizations are
summarized in Table 2.
Film forming of polySOE7 and poly(St-co-SOE7) were investi-
gated. Polymer films were prepared by a solution casting
method using chloroform solution of polySOE7 and BPMS.
Heating of the polymer film (polySOE7) at 120 ꢀC for 2 h
gave the corresponding the networked polymer film NW-
SOE7. Figure 4(a) shows the photographs of the film of NW-
SOE7. All homopolymer and copolymers gave crosslinked
Crosslinking of the Polymers Having SOE Structures
The cationic crosslinking reactions were carried oꢀut by heating
a chlorobenzene solution of the polymer at 120 C for 2 h in
1794
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795

JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
5 T. Takata, F. Sanda, T. Ariga, H. Nemoto, T. Endo, Macromol.
Rapid Commun. 1997, 18, 461–469.
films and in particular a flexible film [Fig. 4(b)] was obtained
in the case of NW-(St-co-SOE7) (St:SOE7 5 1:3).
6 S. Ohsawa, B. Barkakaty, A. Sudo T. Endo, J. Polym. Sci. Part
A: Polym. Chem. 2012, 50, 1281–1289.
CONCLUSIONS
7 S. Chikaoka, T. Takata, T. Endo, Macromolecules 1991, 24,
331–332.
We demonstrated that styrene-based monomers having a
SOE structure could be easily synthesized by a mild and effi-
cient manner. The monomers could be readily polymerized
to afford polymers having SOE structures with keeping the
SOE structures unchanged. The new styrenic monomers syn-
thesized here can be copolymerized with usual vinyl mono-
mers such as styrene, which implies that the monomers
have high applicability to various purposes. These polymers
and copolymers showed little volume shrinkage or slight vol-
ume expansion during the crosslinking reaction. Further
applications of these monomers and polymers to flexible
film formation and adhesive materials are in progress.
8 H. Tagoshi, T. Endo, J. Polym. Sci. Part A: Polym. Chem.
1989, 27, 4319–4328.
9 S. Chikaoka, T. Takata, T. Endo, Macromolecules 1994, 27,
2380–2382.
10 M. Igarashi, T. Takata, T. Endo, Macromolecules 1994, 27,
2628–2631.
11 S. Komatsu, T. Takata, T. Endo, Macromolecules 1993, 26,
875–878.
12 S. Chikaoka, T. Takata, T. Endo, Macromolecules 1991, 24,
6557–6562.
13 J. Canadell, A. Mantecon, V. Cadiz, J. Polym. Sci. Part A:
Polym. Chem. 2007, 45, 1920–1930.
14 Expanding Monomers. Synthesis, Characterization and
Applications; R. K. Sadhir, M. R. Luck, Eds.; CRC Press: Boca
Raton, 1992.
REFERENCES AND NOTES
1 H. Tagoshi, T. Endo, Macromolecules 1991, 24, 2132–2133.
15 N. Kitamura, T. Takata, T. Endo, T. Nishikubo, J. Polym. Sci.
Part A: Polym. Chem. 1991, 29, 1151–1155.
2 D. Nagai, M. Nishida, B. Ochiai, K. Miyazaki, T. Endo,
J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 3233–3241.
16 W. Bailey, J. Gu, Y. Lin, Z. Zheng, L. Zhou, Makromol.
Chem. Macromol. Symp. 1991, 43, 195–203.
3 G. Rokicki, Prog. Polym. Sci. 2000, 25, 259–342.
4 M. Sangermano, R. Acosta Ortiz, Puente Urbina, A. Bertha,
et al. Eur. Polym. J. 2008, 44, 1046–1052.
17 J. Canadell, A. Mantecon, A. Mantecon, V. Cadiz, Polym.
Degrad. Stab. 2008, 93, 59–67.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 1790–1795
1795