Anionic Alternating Copolymerization Behavior

of Bifunctional Six-Membered Lactone

and Glycidyl Phenyl Ether
KAZUYA UENISHI, ATSUSHI SUDO, TAKESHI ENDO
Molecular Engineering Institute, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka 820-8555, Japan
Received 24 January 2009; accepted 29 March 2009
DOI: 10.1002/pola.23446
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: A copolymerization of 10-methyl-2H,8H-benzo-[1,2-b:5,4-b
0
]bipyran-2,8-
dione (1) and glycidyl phenyl ether (GPE) was studied. 1 was a bislactone designed
as a bifunctional analogue of 3,4-dihydrocoumarin (DHCM), of which anionic 1:1
alternating copolymerization with GPE has been reported by us, previously. This
alternating nature was inherited by the present copolymerization of 1 and GPE,
leading to an intriguing copolymerization behavior in contrast to the ordinary statis-
tical copolymerizations of monofunctional monomers and bifunctional monomers usu-
ally controlled by the proportional dependence of the crosslinking density on the
monomer feed ratio: (1) When the feed ratio [GPE]
0
/[1]
0
was 1, the two monomers
underwent the 1:1 alternating copolymerization. In this case, 1 behaved as a mono-
functional monomer, that is, only one of the two lactones in 1 participated in the
copolymerization allowing the other lactone moiety to be introduced into the side
chain almost quantitatively. (2) Increasing the feed ratio [GPE]
0
/[1]
0
to larger than 4
allowed almost all of the lactone moieties to participate in the copolymerization sys-
tem to give the corresponding networked polymers efciently. The compositions of
the copolymers [GPE unit]/[1-derived acyclic ester unit] were always biased to
smaller values than the feed ratios [GPE]
0
/[lactone moiety in 1]
0
by the intrinsic 1:1
alternating nature of the copolymerization. V VC
2009 Wiley Periodicals, Inc. J Polym Sci Part
A: Polym Chem 47: 36623668, 2009
Keywords: alternating sequence; copolymerization; crosslinking; networks; polyesters
INTRODUCTION
Epoxide exhibits high reactivity due to the distor-
tion energy of the three-membered ring, which
permits its efcient ring-opening polymerizations
under both cationic and anionic conditions.
1
The
high reactivity often allows its copolymerizations
not only with various polymerizable compounds
28
but also with robust compounds such as carbon
dioxide.
912
In other words, there could still exist
a wide variety of potential comonomers that have
been not exploited so far. Surveying such com-
pounds capable of copolymerizations with epoxide
is an attractive strategy for development of new
polymers having various main chain structures,
which are totally different from that of the
epoxy homopolymer and would accordingly exhibit
different chemical and physical properties.
Recently, we have reported the imidazole-initi-
ated copolymerization of 3,4-dihydrocoumarin
(DHCM) and glycidyl ethers such as phenyl
glycidyl ether (GPE) and allyl glycidyl ether
(Scheme 1).
1316
DHCM is a six-membered aromatic
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 36623668 (2009)
V VC 2009 Wiley Periodicals, Inc.
Correspondence to: T. Endo (E-mail: tendo@me-henkel.
fuk.kindai.ac.jp)
3662
lactone, which does not undergo cationic or ani-
onic homopolymerization at all. This robust lac-
tone underwent 1:1 alternating copolymerization
with GPE to give the corresponding polyester.
This unique reaction behavior of DHCM has
prompted us to develop various DHCM analogues
and apply them to copolymerization with epox-
ides. A bislactone 1 is one of the highly interesting
DHCM-analogues, and recently, we have reported
its practical application as an additive to the imid-
azole-initiated curing reactions of epoxy resins,
which remarkably improved the thermal stabil-
ities of the cured materials.
13,17,18
Besides this
practical aspect of 1, clarication of its reaction
behavior in its copolymerization with epoxide has
been remained unexplored.
Herein, we report the copolymerization behav-
ior of the bislactone 1 with GPE (Scheme 2). 1 is a
bifunctional monomer, of which copolymerization
with a monofunctional epoxide would potentially
afford polymers having networked structure. Our
particular interests in this polymerization system
are the effects of the intrinsic 1:1 alternating
nature of the copolymerization of DHCM and
GPE on the growth of the polymer network,
leading to the totally different mode from those
based on utilization of other monomers capable of
random copolymerizations with epoxides.
RESULTS AND DISCUSSION
Copolymerization of 1 and GPE in Various
Feed Ratios
The copolymerization of 1 and GPE was carried
out at 120

C in bulk using 2-ethyl-4-methylimi-
dazole (EMI) as an initiator (Scheme 2). The
amount of EMI was calculated by the equation,
[EMI]
0
0.01(2[1]
0
[GPE]
0
). The resulting mix-
ture was separated into the tetrahydrofuran
(THF)-insoluble fraction 2
insol
and THF-soluble
one, and the latter was further separated into
hexane-insoluble fraction and soluble one. The
fraction soluble in THF and insoluble in hexane is
represented by 2
sol
. The corresponding results are
shown in Table 1. These fractions were analyzed
by
1
H NMR,
13
C NMR, and IR spectroscopies.
Particularly, the latter two were conveniently
used for detection of the ester groups inherited
from the bislactone 1.
1318
For the purpose of
more detailed investigation on the repeating units
that composed the obtained polymeric products,
reductive degradation of these products were per-
formed using lithium aluminum hydride (LAH) as
a reducing reagent that can cleave the ester bonds
in the polymers (Scheme 2).
13,16,17
The results are
shown in Table 2.
First, the copolymerization was performed with
setting the monomer feed ratio [GPE]
0
:[1]
0
to be
1:1 (entry 1). The corresponding copolymerization
behavior has been already reported by our previ-
ous short communication.
17
In this case, 1 and
Scheme 2. Copolymerization of 1 and GPE and
reductive cleavage of the ester linkage.
Scheme 1. Alternating copolymerization of DHCM
and glycidyl ethers.
COPOLYMERIZATION OF BISLACTONE & GPE 3663
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
GPE underwent the 1:1 alternating copolymeriza-
tion to give the linear polyester. The consumption
rates for the both monomers were virtually same,
and after 1 h, the conversions of 1 and GPE
reached to 60 and 59%, respectively. The resulting
mixture was composed of a THF-soluble polymer
2a
sol
(isolated as hexane insoluble parts in 60%
yield) and the residual monomers. Formation of a
THF-insoluble part was negligible, suggesting
that only one of the two lactone moieties in 1
would have participated in the copolymerization
with GPE. The copolymerization proceeded in the
1:1 alternating manner, giving the corresponding
linear polyester. The other lactone moiety in 1
remained intact and introduced into the side
chain of the copolymer. In
13
C NMR spectrum of
2a
sol
, two carbonyl signals were observed around
172 and 168 ppm, and attributed to the ester-link-
age in the main chain and the lactone moiety in
the side chain, respectively. The IR spectrum
showed two absorption signals at 1765 and 1735
cm
1
assigned to the lactone and a linear ester
moiety, respectively, [Fig. 1(a)].
Treatment of 2a
sol
with LAH resulted in com-
plete reduction of these ester moieties to give the
corresponding low-molecular weight products, of
which structural analyses claried the structure
of the polymer (Table 2, entry 1).
14,17
As the main
product, a triol 3 was obtained in 87% yield,
which was composed of the GPE-derived unit and
the 1-derived unit in a 1:1 ratio. 3 had a phenol
moiety in the core structure, which was obviously
Table 1. Results of Copolymerization of GPE and 1
Run
Feed Ratio
[GPE]
0
/[1]
0
Time
(min)
Products
THF Insoluble
Parts (%)
THF Soluble Parts
Hexane Insoluble
Parts (%)
Hexane Soluble
Parts (%)
1 1/1 60 trace 60 (2a
sol
)
a
28 (GPE:11:1)
b
2 2/1 30 35 (2b
insol
) 35 (2b
sol
)
c
18 (GPE:16:1)
b
3 4/1 30 88 (2c
insol
) 3 7 (GPE)
4 8/1 45 74 (2d
insol
) 2 22 (GPE)
5 18/1 120 0 82(2e
sol
)
d
17 (GPE)
a
2a
sol
: M
n
2240, M
w
4750.
b
Determined by
1
H NMR.
c
2b
sol
: M
n
1920, M
w
3620.
d
2e
sol
: M
n
1610, M
w
6330.
Table 2. Reductive Cleavage of Copolymers
2ae with LiAlH
4
Run Copolymers
Products
a
3 4
1 2a
sol
87 1
2 2B
insol
76 15
3 2c
insol
0 57
4 2d
insol
0 26
5 2e
sol
0 0
a
Tentative yield of the products is estimated according to
the following formula: Yield (%) [weight of each products
(3,4)]/[weight of 2], because the weight of proton is vanish-
ingly small in these products.
Figure 1. IR spectra of the polymers (a) 2a
sol
, (b)
2b
insol
, (c) 2c
insol
, and (d) 2d
insol
.
3664 UENISHI, SUDO, AND ENDO
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
derived from the intact lactone structure in the
side chain of the copolymer. Besides the main
product 3, a trace amount of a tetraol 4 was
obtained. This suggested that a very small part of
the lactone moiety in the side chain underwent
1:1 alternating copolymerization with GPE, lead-
ing to a negligible branching of the polymer.
Next, the copolymerizations were carried out
(in bulk, at 120

C, for 1 h) in the range of the
feed ratio [GPE]
0
:[1]
0
from 2:1 to 8:1 (Table 1,
entries 24). The copolymerization gave the corre-
sponding THF-soluble polymer 2b
sol
in 35%, of
which spectroscopic features were similar to those
of the 2a
sol
. Besides the formation of the 2a
sol
, a
THF-insoluble fraction 2b
insol
was also obtained
in 35%, suggesting that the bislactone 1 acted as
a crosslinker to give the networked polymer struc-
ture. As shown in Figure 1, the IR spectrum of
2b
insol
was quite similar to that of the linear poly-
ester 2a
sol
, conrming that it contained a signi-
cant amount of lactone moieties that remained
intact in the copolymerization. Reductive degra-
dation of 2b
insol
gave the triol 3 and the tetraol 4
in 76 and 15% yields, respectively. The total yield
was 91%, implying that the major sequence in the
insoluble polymer was that formed by the 1:1
alternating copolymerization. In other words, the
1:1 alternating tendency of the copolymerization
of GPE and DHCM was inherited by the present
copolymerization system. When the relative
amount of GPE was increased, contents of the
THF-insoluble parts became higher (entries 3 and
4). In these cases, almost all of the polymeric
products became insoluble. These results had
been unexpected and thus seemed to be unique
for the present copolymerization system, because
in general, increasing the relative amount of
monofunctional monomer to bifunctional mono-
mer leads to decrease in crosslinking density, and
the amount of insoluble parts would decrease
accordingly. The IR spectra of the THF-insoluble
fractions 2c
insol
and 2d
insol
revealed that the lac-
tone moiety was consumed almost quantitatively
allowing the bislactone 1 to act as a crosslinker
effectively [Figs. 1(c,d)]. In fact, the reductions of
2c
insol
and 2d
insol
did not give the triol 3. The
main product was tetraol 4, which was derived
from the crosslinking point having four arms. The
other products were oligomers having larger GPE
contents, which were formed by the copolymeriza-
tions out of control by the intrinsic 1:1 alternating
nature.
The copolymerization using 18 equiv. of GPE
gave a soluble polymer 2e
sol
in 82% (Table 1,
entry 5). Its M
n
and M
w
were 1610 and 6330,
respectively. Its IR and
13
C NMR spectra indi-
cated no trace of the lactone moiety. The selective
formation of the THF-soluble polymer was well
explained by the decrease in the number of
the 1-derived crosslinking points. Reduction of
2e
sol
did not give 3 or 4 at all, but gave the corre-
sponding oligomers (M
n
480, M
w
590) rich in
GPEGPE sequence.
More detailed structures of the polymers and
their schematic representations are shown in Fig-
ure 2. (1) The copolymerization of 1 and GPE in a
1:1 feed ratio selectively gave a linear alternating
polyester 2a
sol
having lactone moiety in the side
chain. The lactone in the side chain would be less
reactivity than the lactone in 1, because the ring-
opening reaction of one of the two lactones in 1
and its subsequent reaction with epoxide would
result in a slight increase in the electron density
of the molecule to reduce the reactivity of the
other lactone moiety. (2) When [GPE]
0
/[1]
0
was
increased to 2, the lactone in the side chain was
allowed to nd its comonomer GPE and undergo
the copolymerization, leading to the formation of
crosslinking points. In the case of the increased
relative amount of GPE, the main chain would be
contaminated by GPEGPE sequence. (3) When
[GPE]
0
/[1]
0
was increased to 48, almost all of
the lactone moieties in the side chain were
consumed by their copolymerization with exces-
sively existing GPE. Although the intrinsic 1:1
alternating nature of the copolymerization is
resisting to the formation of GPEGPE sequence,
the content of 1:1 alternating sequence decreased
signicantly. (4) When [GPE]
0
/[1]
0
was large as
18, the formed polymer was virtually the homo-
polymer of GPE, which was occasionally cross-
linked by the 1-derived structure and thus totally
having a branched shape. In addition, the 1-1
homo sequence would be absent in these copoly-
mers, because a phenoxy anion generated from
ring opening of the lactone moiety can not undergo
the ring-opening reaction of the lactone moiety to
give the corresponding homo sequence.
14
Thermal Properties of the Polymers
The thermal properties of the polymers 2 were
examined with a differential scanning calorimeter
(DSC) and a thermo gravimetric analyzer (TG).
The polyester obtained by the 1:1 alternating
copolymerization of GPE and DHCM (M
n
2840,
M
w
4480) was also analyzed similarly, to nd
that it did not exhibit clear T
g
in the temperature
COPOLYMERIZATION OF BISLACTONE & GPE 3665
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
range from 40

C to 250

C and its T
d10
was
326

C. On the other hand, T
g
s of the crosslinked
polymers 2c
insol
and 2d
insol
appeared at around
150

C, and their T
d10
was around 340

C higher
than that of the GPE-DHCM copolymer, suggest-
ing that the crosslinked structure would have con-
tributed to the improved thermal stability of the
copolymers.
SUMMARY
The bifunctional lactone 1 underwent the imidaz-
ole-initiated copolymerization with GPE. The
copolymerization inherited the 1:1 alternating
tendency from that of 1,3-dihydrocoumarin and
GPE. In addition, reactivity of the lactone moiety
in 1 decreased upon ring-opening reaction of the
Figure 2. Detailed structures of the polymers and their schematic representations
(a) [1]
0
:[GPE]
0
1:1, (b) [1]
0
:[GPE]
0
1:2, (c) [1]
0
:[GPE]
0
1:8, and (d) [1]
0
:[GPE]
0
1:18.
3666 UENISHI, SUDO, AND ENDO
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
lactone moiety in the other side of the same mole-
cule. Based on these two characteristic factors,
the present polymerization of the bifunctional lac-
tone and the monofunctional epoxide exhibited
unique behaviors, which are not attained by sta-
tistic copolymerizations of other combinations of
bifunctional and monofunctional monomers, that
is, by changing the feed ratio [GPE]
0
/[1]
0
, the
shape of the copolymer varied from linear to net-
worked ones.
EXPERIMENTAL
Materials
10-Methyl-2H,8H-benzo[1,2-b:5,4-b
0
]bipyran-2,8-
dione (1) was synthesized from 2-methylresorcinol
(Tokyo Chemical Industry) and acrylic acid (Wako
Pure Chemical Industries) according to the litera-
ture.
13,16
Glycidyl phenyl ether (GPE), 2-ethyl-4-
methylimidazole (EMI), phosphate buffer powder
(pH 7.4), LiAlH
4
, and the other solvents were
purchased from Wako Pure Chemical Industries,
and were used as received.
Measurements
NMR spectra (400 MHz for
1
H, d
CHCl3
7.26
ppm; 100.6 MHz for
13
C, d
CHCl3
77.00 ppm)
were obtained on a Varian NMR spectrometer
model Unity INOVA. Chemical shift d and cou-
pling constant J are given in ppm and Hz, respec-
tively. IR spectra were obtained on a JASCO
FTIR-460 plus. Number average molecular weight
(M
n
) and weight average molecular weight (M
w
)
were estimated from size exclusion chromatogra-
phy (SEC), performed on a Tosoh chromatograph
model HLC-8120GPC equipped with Tosoh TSK
gel-Super HM-H styrogel columns (6.0 mm /
15 cm), using THF as an eluent at the ow rate of
0.6 mL/min after calibration with polystyrene
standards. Preparative SEC was performed on a
Japan Analytical Industry (JAI) LC-908 system
equipped with a combination of JAIGEL-1H and
2H styrogel columns (20 mm / 60 cm), using
chloroform as an eluent with a ow rate of 3.0
mL/min. Differential scanning calorimetric analy-
sis (DSC) and thermogravimetric analysis (TGA)
were performed on a Seiko EXSTAR6000 at a
heating rate of 10

C/min under air.
Copolymerization of 1 with GPE
Typical procedure: To a mixture of GPE (0.624 g,
4.15 mmol) and 1 (0.477 g, 2.05 mmol), EMI (12.8
mg, 0.116 mmol) was added, and stirred at
120

C. The stirring was stopped by increasing its
viscosity until 30 min. After cooling, tetrahydrofu-
ran (THF) (10 mL) was added to the resulting
mixture, and the insoluble parts were separated
by ltration. The insoluble parts were washed by
THF (50 mL) twice. The insoluble parts (2b
insol
:
0.381 g) in THF as a yellow solid were obtained in
35% yield. The soluble parts in THF were con-
densed and poured into hexane (300 mL) to sepa-
rate between hexane-insoluble part (2b
sol
: 0.386
g, M
n
1920, M
w
3620, 35%) and hexane-sol-
uble part (0.193 g). 2b
insol
: IR (KBr) 3456, 1766,
1737, 1599, 1496, 1242, 753, 691. 2b
sol
: M
n

1920, M
w
3620;
1
H NMR (CDCl
3
, 20

C) d 7.35
7.10 (br), 7.036.68 (br), 5.525.11 (br), 4.403.72
(br), 3.383.16 (br), 3.022.40 (br), 2.221.99 (br),
1.901.67 (br);
13
C NMR (CDCl
3
, 20

C) d 172.5,
168.6, 158.4, 158.1, 154.1, 152.0, 149.4, 129.5,
128.7, 125.9, 124.5, 121.3, 120.7, 119.8, 118.5,
114.4, 78.5, 78.1, 70.6, 65.3, 35.0, 34.4, 28.9, 24.9,
23.3, 9.5, 9.0, 8.6; IR (KBr) 3492, 1766, 1739,
1599, 1496, 1242, 755, 692. 2c
insol
, 2d
insol
, and
2e
sol
were similarly synthesized according to the
aforementioned method. 2c
insol
: IR (KBr) 3471,
1737, 1599, 1497, 1244, 753, 691. 2d
insol
: IR (KBr)
3504, 1735, 1599, 1497, 1244, 752, 690. 2e
sol
: M
n
1610, M
w
6330;
1
H NMR (CDCl
3
, 20

C) d
7.317.11 (br), 6.986.72 (br), 5.335.11 (br), 4.23
3.50 (br), 3.473.18 (br), 2.932.72 (br), 2.652.44
(br), 2.192.07 (br), 1.781.69 (br);
13
C NMR
(CDCl
3
, 20

C) d 172.4, 172.3, 158.4, 158.3, 154.3,
129.3, 127.7, 124.5, 120.9, 120.7, 114.4, 78.5, 78.1,
72.165.9, 34.7, 25.1, 9.8; IR (KBr) 3465, 1736,
1599, 1496, 1246, 754, 691.
Reductive Cleavage of 2 with LiAlH
4
Typical procedure: To 2b
insol
(0.122 g) immersed
in THF (5 mL), suspension of LiAlH
4
(0.0880 g,
2.32 mmol) in THF (5 mL) was added dropwise at
0

C for 5 min, and the resulting mixture was
stirred at room temperature for 16 h. Then, the
solution was carefully poured into a phosphate
buffer solution (200 mL, pH 7.4) at 0

C. The
mixture was extracted with ether (100 mL), and
the organic layer was washed by distilled water,
dried over magnesium sulfate, ltered, and con-
centrated under reduced pressure. The residue
was fractionated with the preparative SEC to give
3 (0.0923 g, 0.236 mmol; 76%) and 4 (0.0180 g,
0.0333 mmol; 15%). 3: Colorless oil;
1
H NMR
(CDCl
3
, 20

C) d 7.29 (t, 2H, J 7.2), 6.97 (t, 1H,
J 7.2), 6.94 (d, 2H, J 7.2), 6.76 (s, 1H), 4.37
COPOLYMERIZATION OF BISLACTONE & GPE 3667
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
(quintet, 1H, J
a
4.8, J
b
5.6), 4.16 (d, 2H, J
b

5.6), 3.97 (d, 2H, J

a
4.8), 3.64 (t, 2H, J 5.6),
3.56 (t, 2H, J 5.6), 2.70 (m, 4H), 2.18 (s, 3H),
1.85 (quintet, 2H, J 5.6), 1.77 (quintet, 2H, J
5.6);
13
C NMR (CDCl
3
, 20

C) d 158.3, 153.6,
151.8, 129.4, 128.4, 125.9, 123.5, 121.0, 118.1,
114.4, 73.5, 69.2, 68.2, 61.0, 60.5, 34.0, 32.0, 25.4,
25.2, 9.6; IR (neat) 3365, 1244, 1108, 1047, 755,
733, 691. 4: White crystal;
1
H NMR (CDCl
3
, 20

C): 7.29 (t, 4H, J 7.2), 6.97 (t, 2H, J 7.2),

6.93 (d, 4H, J 7.2), 6.85 (s, 1H), 4.36 (quintet,
2H, J
a
4.8, J
b
5.6), 4.16 (d, 4H, J
b
5.6), 3.98
(d, 4H, J
a
4.8), 3.80 (br, 2H), 3.57 (t, 4H, J
c

5.6), 2.72 (t, 4H, J
d
7.2), 2.41 (br, 2H), 2.20 (s,
3H), 1.78 (quintet, 4H, J
c
5.6, J
d
7.2);
13
C NMR
(CDCl
3
, 20

C) 158.4, 153.9, 130.8, 129.5, 129.0,
124.2, 121.1, 114.4, 73.5, 69.2, 68.2, 61.0, 34.0, 25.6,
9.9; IR (neat) 3389, 1247, 1102, 1047, 753, 691.
This work was nancially supported by Henkel KGaA
in Germany.
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3668 UENISHI, SUDO, AND ENDO
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola