Rigid diol bearing 6-6-6 fused ring system derived from naturally occurring myo-inositol and its polyaddition with diisocyanates

Article abstract of DOI:10.1002/pola.28765

Naturally occurring myo-inositol was developed into a highly rigid diol by converting its 3,4- and 1,6-vicinal diols in trans configuration into the corresponding butane-2,3-diacetals. The resulting diol bearing 6-6-6 fused ring system, in which conformational change is strictly suppressed, was combined with diisocyanates to perform polyadditions. The resulting polyurethanes were analyzed by differential scanning calorimetry, and it was found that their glass transition temperatures were much higher than those of the previously reported myo-inositol-derived polyurethanes, which were synthesized from a myo-inositol-derived diol bearing 5-6-5 fused ring system.

Full text of DOI:10.1002/pola.28765

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Rigid Diol Bearing 6-6-6 Fused Ring System Derived From Naturally
Occurring Myo-Inositol and Its Polyaddition With Diisocyanates
Arata Yoshida, Atsushi Sudo
Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, Higashi-Osaka, Osaka, 577-8502, Japan
Correspondence to: A. Sudo (E-mail: asudo@apch.kindai.ac.jp)
Received 4 August 2017; accepted 16 August 2017; published online 00 Month 2017
DOI: 10.1002/pola.28765
ABSTRACT: Naturally occurring myo-inositol was developed
into a highly rigid diol by converting its 3,4- and 1,6-vicinal
diols in trans configuration into the corresponding butane-2,3-
diacetals. The resulting diol bearing 6-6-6 fused ring system, in
which conformational change is strictly suppressed, was com-
bined with diisocyanates to perform polyadditions. The result-
ing polyurethanes were analyzed by differential scanning
calorimetry, and it was found that their glass transition
temperatures were much higher than those of the previously
reported myo-inositol-derived polyurethanes, which were syn-
thesized from a myo-inositol-derived diol bearing 5-6-5 fused
ring system. VC
2017 Wiley Periodicals, Inc. J. Polym. Sci., Part
A: Polym. Chem. 2017, 00, 000–000
KEYWORDS: butane-2,3-diacetal; myo-inositol; polyurethanes;
renewable resources; step-growth polymerization
INTRODUCTION Monomers bearing rigid cores derived from
non-fossil and renewable feed stocks have been attracting
great attention because their polymerization is expected to
sources of myo-inositol because they contain phytic acid, a
3
3,34
hexaphosphate of myo-inositol.
So far, for the derivation
of myo-inositol into bioactive molecules in well-defined ways,
1
–10
be an efficient approach to high-performance polymers.
several efficient methods for regioselective protection of
3
5
In particular, rigid diols derived from naturally occurring
compounds are attractive monomers that can be variously
used for polycondensations and polyadditions. Such diols
include isosorbide, isomannide, and isoidide, which are
sugar-derived diols with a conformationally constrained 5–5
myo-inositol have been developed. One of these efficient
protection methods is bisketalization with 1,1-dimethoxycy-
clohexane, which permits the ketalization of 2,3-cis-diol and
5,6-trans-diol to give a rigid diol, 1, with a 5–6-5 fused ring
3
6
system. In our previous work, diol 1 was used as a mono-
mer for polyurethane synthesis to afford polyurethanes 2,
the repeating units of which inherited the 5–6-5 fused ring
1
1–14
fused ring structure.
They can be used as rigid diol-type
monomers to synthesize polymers with rigid structures
inherited from the monomers. The rigidity of the repeating
units enhances the mechanical strength and thermal stability
of the polymers. Another interesting family of renewable
3
2
system from 1 (Scheme 1). Because of the rigidity of the
repeating unit, the polyurethanes had high glass transition
temperatures (T values), which in some cases were higher
g
than those of the polyurethanes synthesized from isosorbide
and some other monosaccharide-derived diols.
1
5–18
diols is the diacetals of sugars such as mannitol.
Because they also have rigid bicyclic structures, the corre-
sponding polymers exhibit excellent thermal properties. In
addition, these diols, namely dianhydrohexitols and diacetals
of sugars, are useful not only as monomers but also as pre-
cursors of other types of monomers, such as dicarboxylic
Another frequently used protected myo-inositol is diol
3
7–39
3
,
the utilization of which for polymer synthesis is the
focus of this article. Diol 3 can be easily synthesized from
myo-inositol by treating it with 2,3-butanedione and metha-
nol in the presence of an acid catalyst. By this method, the
1
9–21
22,23
24,25
acids,
diamines,
and vinyl monomers,
among
2
6,27
others.
3,4-trans- and 1,6-trans-diols of myo-inositol can be pro-
Our research interest has been focused on the utilization of
tected to afford diol 3, which is more symmetric than diol 1.
In addition, diol 3 has a highly rigid 6–6-6 fused ring system,
in which conformational change is inhibited more strictly
than in the 5–6-5 fused ring system of diol 1. These struc-
tural features led us to expect that the polyaddition of diol 3
myo-inositol, a naturally occurring cyclic hexaol, as a starting
2
8–32
material for polymer synthesis.
myo-Inositol and its
derivatives can be found abundantly in various plants and
animal organs. Rice bran and bean skins are especially useful
Additional Supporting Information may be found in the online version of this article.
2017 Wiley Periodicals, Inc.
V
C
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after calibration with polystyrene standards. Thermogravi-
metric analyses (TGA) were performed with a SHIMADZU
analyzer (model DTG-60) under a nitrogen flow. Each sample
was heated from 50 to 500 8C, at a rate of 10 8C/min. Differ-
ential scanning calorimetry (DSC) was performed with a SHI-
MADZU instrument (model DSC-60 Plus) under a nitrogen
flow. Each sample was heated from room temperature (rt) to
230 or 250 8C, then cooled to 250 8C at a rate of 20 8C/min.
The sample was then heated from 250 to 230 or 250 8C at
a rate of 10 8C/min with acquisition of the DSC data.
Synthesis of Diol 3
To a dispersion of myo-inositol (20.38 g, 113.1 mmol) in
methanol (500 mL), trimethyl orthoformate (80 mL), 2,3-
butanedione (20 mL, 230 mmol), and CSA (0.43 g, 1.8
mmol) were added. The resulting mixture was stirred at 80
8C for 24 h. After cooling, the resulting precipitate was sepa-
rated by filtration with suction. The precipitate was dis-
persed in water (300 mL), washed with stirring the
dispersion for 24 h, filtered with suction, and dried under
SCHEME 1 Outline of this work.
vacuum to obtain diol 3 (9.25 g, 22.7 mmol, 20%) as a white
1
powder: H NMR (in DMSO-d at rt): d 5 5.04 (d, J 5 5.9 Hz,
6
with diisocyanates would give the corresponding polyur-
ethanes 4, the glass transition temperatures of which are
higher than those of polyurethanes 2. Herein, we report the
use of diol 3 as a monomer for polyurethane synthesis and
the thermal properties of the resulting polyurethanes 4.
1
H), 4.98 (d, J 5 4.4, 1H), 3.77 (m, 1H), 3.67 (dd, J 5 9.7, 9.8
Hz, 2H), 3.36 (m, 1H), 3.25 (m, 2H), 3.15 (s, 6H), 3.13 (s,
6
d 5 99.96, 98.40, 69.31, 69.13, 68.57, 67.57, 47.39, 47.11,
13
H), 1.19 (s, 6H), 1.17 (s, 6H); C NMR (in DMSO-d at rt):
6
21
17.61; IR (KBr): m 5 3363, 2948, 2864, 1718, 1508 cm
.
EXPERIMENTAL
Polyaddition of Diol 3 with Diisocyanates
Typical procedure: Compound 3 (617 mg, 1.51 mmol), HMDI
254 mg, 1.51 mmol), and DBTDL (112 mg, 0.117 mmol)
were placed in a 10-mL flask and flushed with argon. 1,4-
Dioxane (1.5 mL) was added, and the resulting mixture was
stirred at 80 8C for 24 h. After cooling, the solution was
poured into diethyl ether (80 mL). The resulting precipitates
were collected by filtration with suction and dried under
Materials
(
myo-Inositol, 2,3-butanedione, (1)-10-camphorsulfonic acid
(
CSA), trimethyl orthoformate, neopentyl glycol (NPG), and
dibutyltin dilaurate (DBTDL) were purchased from Wako
Pure Chemical Industries Co., Ltd., and used as received. Hex-
amethylene diisocyanate (HMDI), isophorone diisocyanate
(
IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane (BICMC)
vacuum to obtain polyurethane 4a3 (840 mg, 97%) as a
were purchased from Wako Pure Chemical Industries Co.,
Ltd., and distilled under vacuum prior to use. 1,4-Dioxane
was purchased from Wako Pure Chemical Industries Co.,
Ltd., dried over calcium hydride, and distilled prior to use
for the polyurethane synthesis. Other reagents including
methylene diphenyl diisocyanate (MDI) and solvents were
purchased from Wako Pure Chemical Industries Co., Ltd., and
used as received.
1
white solid: H NMR (400 MHz, DMSO-d , at rt): d 5 7.1–6.7
6
(
33 br s, total 2H), 5.1 (br s, 1H), 4.8–4.6 (br m, 1H), 3.9–
3
4
.6 (br m, 4H), 3.13 (br s, 6H), 3.10 (br s, 6H), 2.9 (br m,
H), 1.5–1.0 ppm (br m, 20H); C NMR (100 MHz, DMSO-
13
d6, at rt): d 5 156–154, 99.1, 98.5, 68.7, 68.1, 67.9, 67.7,
7.6, 67.3, 66.5, 47.7, 47.2, 40.1, 29.5, 25.8, 17.6, 17.4 ppm;
6
21
IR (KBr): m 5 3363, 2948, 2864, 1718, 1508 cm
.
By following the typical procedure, polyaddition of diol 3
616 mg, 1.51 mmol) with IPDI (335 mg; 1.51 mmol) was
Instruments
(
1
13
NMR spectra (400 MHz for H; 100.6 MHz for C) were
recorded on a JEOL NMR spectrometer (model JNM-AL400).
Chemical shifts, d, and coupling constants, J, are given in
ppm and Hz, respectively. IR spectra were obtained with a
JASCO FT/IR-470 spectrometer, and the wave number, m, is
carried out to obtain polyurethane 4b (771 mg, 81%) as a
1
white solid: H NMR (400 MHz, DMSO-d , at rt): d 5 7.2–6.4
6
(
(
(
br m, 2H), 5.2–5.0 (br m, 1H), 4.9–4.6 (br m, 1H), 4.0–3.4
br m, 4H), 3.14 (br s, 12H), 3.2–2.6 (br m, 2H), 1.7–0.8 ppm
13
br m, 27H); C NMR (100 MHz, DMSO-d , at rt): d 5 156–
6
2
1
given in cm . Number-average molecular weights (M ) and
n
1
2
1
55, 99.1, 98.5, 71–66, 47.71, 47.5–47.3, 44.1, 35.1, 31.3,
weight-average molecular weights (M ) were estimated by
w
7.5, 22.8, 17.6 ppm; IR (KBr): m 5 3359, 2952, 2836, 1731,
size-exclusion chromatography (SEC), performed on a Tosoh
chromatograph (model HLC-8320GPC) equipped with Tosoh
TSK gel-Super HM-H styrogel columns (6.0 mm ø 3 15 cm),
by using N,N-dimethylformamide (DMF) containing 1 wt %
lithium bromide as the eluent at a flow rate of 0.6 mL/min
21
509 cm
.
By following the typical procedure, polyaddition of diol 3
(636 mg, 1.56 mmol) with BICMC (303 mg; 1.56 mmol) was
carried out to obtain polyurethane 4c (868 mg, 92%) as a
2
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m, 4H), 5.4–5.1 (br m, 1H), 4.90 (br t, J 5 9 Hz, 0.8H), 4.81
br t, J 5 9 Hz, 0.2H), 4.0–3.6 (br m, 6H), 3.2–3.1 (3 3 br s,
(
1
3
total 12H), 1.2–1.1 ppm (3 3 br s, total 12H); C NMR (100
MHz, DMSO-d , at rt): d 5 153–152, 138–135, 129, 119, 118,
6
9
9, 98, 71–66, 48–47, 17.6, 17.5 ppm; IR (KBr): m 5 3328,
2
1
2951, 2834, 1735, 1520 cm
.
Polyaddition of NPG with HMDI
NPG (157 mg, 1.51 mmol), HMDI (254 mg, 1.51 mmol), and
DBTDL (98.8 mg, 0.156 mmol) were placed in a 10-mL flask
and flushed with argon. 1,4-Dioxane (3.0 mL) was added,
and the resulting solution was stirred at 80 8C for 24 h. After
cooling, the solution was poured into diethyl ether (100 mL).
The resulting precipitates were collected by filtration with
suction and dried under vacuum to obtain polyurethane 5a
1
(
358 g, 87%) as a white solid: H NMR (400 MHz, DMSO-d ,
6
at rt): d 5 7.1 (br s, 1.7H), 6.8 (br s, 0.3H), 3.72 (br s, 4H),
3
0
.0–2.9 (br m, 4H), 1.4–1.3 (br m, 4H), 1.3–1.2 (br m, 4H),
1
3
.85 ppm (br s, 6H); C NMR (100 MHz, DMSO-d , at rt):
6
d 5 156, 68.6, 40.2, 35.0, 26.0, 21.3 ppm; IR (KBr): m 5 3340,
2
1
2933, 2858, 1702, 1542 cm
.
Ternary Polyaddition System Composed of NPG, Diol 3,
and HMDI
SCHEME 2 Polyaddition of diol 3 with diisocyanates.
Typical procedure: NPG (235 mg, 2.25 mmol), diol 3
1
white solid: H NMR (400 MHz, DMSO-d , at rt): d 5 7.4–6.6
(
3
6
(
307 mg, 0.750 mmol), HMDI (505 mg, 3.00 mmol), and
33 br s, total 2H), 5.2–5.0 (br m, 1H), 4.8–4.6 (br m, 1H),
.9–3.6 (br m, 4H), 3.14 (br s, 6H), 3.12 (br s, 6H), 3.0–2.6
br m, 4H), 1.7–1.5 (br s, 3H), 1.5–1.2 (br m, 4H), 1.1 (br s,
2H), 0.8–0.6 (br s, 2H), 0.6–0.3 ppm (br s, 1H); C NMR
100 MHz, DMSO-d , at rt): d 5 156–155, 99.1, 98.5, 71–66,
6
DBTDL (19.2 mg, 0.303 mmol) were placed in a 10-mL flask
and flushed with argon. 1,4-Dioxane (3.0 mL) was added,
and the resulting solution was stirred at 80 8C for 24 h. After
cooling, the solution was poured into diethyl ether (100 mL).
The resulting precipitates were collected by filtration with
(
1
1
3
(
4
(
7.7, 47.3, 46.6, 38.1, 37.7, 30.0, 25.1, 17.7–17.3 ppm; IR
KBr): m 5 3366, 2925, 2837, 1729, 1510 cm
2
1
suction and dried under vacuum to obtain polyurethane 5b
.
1
(
1.03 g, 99%) as a white solid: H NMR (400 MHz, DMSO-d ,
6
By following the typical procedure, polyaddition of diol 3
612 mg, 1.50 mmol) with MDI (375 mg; 1.50 mmol) was
at rt): d 5 7.2–6.7 (br m, 2H), 5.2–5.0 (br m, 0.25H), 4.9–4.6
(br m, 0.25H), 3.9–3.7 (br m, 1H), 3.72 (br s, 3H), 3.14 (br s,
1.5H), 3.12 (br s, 1.5H), 2.9 (br s, 4H), 1.4 (br s, 4H), 1.2 (br
(
carried out to obtain polyurethane 4d (880 mg, 89%) as a
1
13
white solid: H NMR (400 MHz, DMSO-d , at rt): d 5 9.7–9.3
s, 4H), 1.12 (br s, 3H), 0.86 ppm (br s, 4.5H); C NMR (100
6
(
br m, 1.5H), 8.5 (br s, 0.5H), 7.5–7.3 (br m, 4H), 7.2–7.0 (br
MHz, DMSO-d , at 60 8C): d 5 156, 99.1, 98.5, 70–66, 68.6,
6
TABLE 1 Syntheses and Properties of myo-Inositol-Derived Polyurethanes
a
b
c
c
d
Entry
Diol
Diisocyanate
HMDI
Solvent
PhCl
4
Yield (%)
M
n
(M
w
/M
n
)
T
d5 (8C)
T
d10 (8C)
g
T (8C)
e
e
e
1
2
3
4
5
6
3
3
3
3
3
3
1
1
1
4a
4a
4a
1
2
3
93
92
97
84
98
86
99
73
84
11,300 (6.3)
13,700 (5.0)
9,700 (1.5)
8,000 (1.8)
10,300 (1.7)
10,000 (1.5)
61,600 (1.6)
41,300 (1.5)
19,300 (2.1)
–
–
–
–
e
e
e
THF
–
–
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
DMF
234
266
230
233
302
283
302
252
278
249
249
316
301
309
162
211
189
213
143
159
248
IPDI
4b
4c
4d
2a
2b
2d
BICMC
MDI
f
7
HMDI
IPD
f
8
DMF
f
9
MDI
DMF
a
d
Diethyl ether insoluble fractions.
Determined by DSC analysis.
Not measured.
b
e
f
Estimated by SEC (eluent 5 DMF 1 1 wt % LiBr, calibrated with poly-
styrene standards).
c
Data presented in a previous report of ours (ref. 32).
Determined by TGA.
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methanol. By filtration, washing with water, and drying
under vacuum, highly pure diol 3 was isolated. Diol 3 was a
major isomer, owing to anomeric effects making the axial
orientation of the methoxy groups thermodynamically favor-
3
8
1
13
able. The H- and C NMR spectra are shown in Support-
ing Information Figure S1.
SCHEME 3 Conformational changes of the 5–6-5 and 6–6-6
fused ring systems.
Polyaddition with Diisocyanates
Polyadditions of diol 3 with four diisocyanates, HMDI, IPDI,
BICMC, and MDI, were performed to obtain the correspond-
ing polyurethanes 4 (Scheme 2). These polyurethanes were
isolated as diethyl ether insoluble fractions. The yields and
molecular weights of polyurethanes 4 are shown in Table 1.
4
8–47, 40.16, 35.0, 29.5, 26.1, 21.3, 17.7–17.3 ppm; IR
2
1
(
KBr): m 5 3338, 2932, 2858, 1703, 1529 cm
.
By following the typical procedure, polyaddition of NPG
157 mg, 1.50 mmol), diol 3 (614 mg, 1.50 mmol), and
(
HMDI (505 mg, 3.00 mmol) was carried out to obtain poly-
urethane 5c (1.12 g, 88%) as a white solid: H NMR (400
First, the polyaddition of 3 with HMDI was performed with
various solvents (Entries 1–3). Chlorobenzene, tetrahydrofu-
ran (THF), and 1,4-dioxane were employed. Diol 3 was insol-
uble in these solvents. According to the progress of its
reaction with HMDI, dispersed 3 was consumed and disap-
peared gradually. However, it was not completely consumed
in chlorobenzene or THF. In these solvents, part of the
resulting polymer, 4a, precipitated, and thus, its reactive
chain-end isocyanate moieties were excluded from the solu-
tion. At the same time, the precipitated polymer stuck to diol
1
MHz, DMSO-d , at rt): d 5 7.2–6.7 (br m, 2H), 5.1 (br s,
6
0
2
.5H), 4.8–4.6 (br m, 0.5H), 3.9–3.7 (br m, 2H), 3.72 (br s,
H), 3.2–3.1 (4 3 br s, total 6H), 3.0–2.9 (br m, 4H), 1.4–1.3
(
br s, 4H), 1.3–1.2 (br s, 4H), 1.12 (br s, 6H), 0.86 ppm (br s,
1
3
3
9
1
1
H); C NMR (100 MHz, DMSO-d , at 60 8C): d 5 156, 99.1,
6
8.5, 70–66, 68.6, 48–47, 40.2, 35.0, 29.4, 26.0, 25.8, 21.3,
7.6, 17.4 ppm; IR (KBr): m 5 3354, 2936, 2858, 1722,
2
1
530 cm
.
3
and prevented its dissolution. On the other hand, in 1,4-
By following the typical procedure, polyaddition of NPG
78.8 mg, 0.76 mmol), diol 3 (919 mg, 2.25 mmol), and
dioxane, the resulting polymer was soluble and diol 3 was
consumed completely. The resulting polyurethane, 4a , was
isolated as the diethyl ether-insoluble fractions in excellent
yield. DMF was also studied as a candidate solvent; however,
a significant amount of diol 3 remained unconsumed.
(
3
HMDI (505 mg, 3.00 mmol) was carried out to obtain poly-
1
urethane 5d (1.43 g, 95%) as a white solid: H NMR (400
MHz, DMSO-d , at rt): d 5 7.2–6.7 (br m, 2H), 5.1 (br s,
6
0
1
4
0
.75H), 4.8–4.6 (br m, 0.75H), 3.9–3.7 (br m, 3H), 3.72 (br s,
H), 3.2–3.1 (43 br s, total 6H), 3.14 (br s, 4.5H), 3.11 (br s,
.5H), 1.4–1.3 (br s, 4H), 1.3–1.2 (br s, 4H), 1.12 (br s, 9H),
With 1,4-dioxane as the optimum solvent, polyadditions
were performed with other diisocyanates (Entries 4–6). In
all cases, diol 3 was consumed completely, and the corre-
sponding polyurethanes 4b–4d were obtained in good to
excellent yields. Their Mn values ranged from 8000 to
10,300.
1
3
.85 ppm (br s, 1.5H); C NMR (100 MHz, DMSO-d , at 60
6
8C): d 5 156, 99.1, 98.5, 70–66, 68.6, 48–47, 40.2, 35.0, 29.4,
2
6.0, 21.3, 17.6, 17.4 ppm; IR (KBr): m 5 3357, 2948, 2859,
2
1
1723, 1517 cm
.
1
13
H and C NMR analyses of polyurethanes 4 confirmed their
RESULTS AND DISCUSSION
1
13
chemical structures. The H and C NMR spectra of the poly-
urethanes are shown in Supporting Information Figures S2–S5.
Synthesis of Diol 3
Diol 3 was synthesized from myo-inositol by treatment with
2
,3-butanedione, methanol, and CSA, according to the
Table 1 also shows the thermal properties of the polyur-
ethanes, namely the temperatures for 5% weight loss (Td5)
and temperatures for 10% weight loss (Td10) measured by
3
7
reported procedure. The reaction gave a mixture of various
isomers; then, only 3 precipitated out from the reaction mix-
ture because it is highly symmetric and thus less soluble in
g
TGA under a nitrogen flow and the T values measured by
SCHEME 4 Ternary polyaddition system composed of NPG, myo-inositol-derived diol 3, and HMDI.
4
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TABLE 2 Ternary Polyaddition System Composed of NPG, Diol 3, and HMDI
Feed ratio
Yield
Composition
M
n
(M
w
/
T
d5
d
T
d10
d
T
g
a
b
c
e
Entry
([NPG] :[3]
0 0
)
5
(%)
(m:n)
M
n
)
(8C)
(8C)
(8C)
1
2
3
4
100:0
75:25
50:50
25:75
0:100
5a
5b
5c
5d
87
97
88
95
97
100:0
75:25
50:50
25:75
0:100
13,000 (1.7)
12,000 (1.9)
13,000 (2.3)
12,000 (1.7)
9,700 (1.5)
235
257
39
230
244
228
234
245
257
250
252
60
96
132
162
f
5
4a
3
a
d
e
f
Diethyl ether insoluble fractions.
Determined by TGA.
b
c
1
Determined by H NMR spectroscopy.
Estimated by SEC (eluent 5 DMF 1 1 wt % LiBr, calibrated with polysty-
Determined by DSC analysis.
Same as entry 3 in Table 1.
rene standards).
DSC. The TGA and DSC thermograms are shown in Support-
ing Information Figures S6 and S7.
5 were obtained in good to excellent yields, and the compo-
sition ratios of 5 determined by H NMR analysis were in a
1
good agreement with the feed ratios.
The TG analysis confirmed the lower thermal stabilities of
3
2
polyurethanes 4 than those of polyurethanes 2 : The T
The TG analyses of polyurethanes 5b–5d revealed that their
d5
values of 4 ranged from 233 to 266 8C, whereas those of 2
ranged from 283 to 302 8C.
thermal stabilities were similar to each other and also to
those of 5a (the NPG–HMDI homopolymer) and 4a (a 3-
3
HMDI homopolymer) (Supporting Information Fig. S12). The
thermal degradation started at around 230 8C, and 10% of
the original weights of the polymers were lost by around
In contrast, the DSC analysis of polyurethanes 4 revealed
that their Tg values were higher than those of 2, which
implies that the higher rigidity of the 6–6-6 fused ring sys-
tem, relative to that of the 5–6-5 system, contributed to
enhanced stiffness of the polymer main chain: As shown in
Scheme 3, the central cyclohexane ring in the 5–6-5 fused
ring system is allowed to have two conformations, a thermo-
dynamically favored chair-type one and a less favored boat-
type one. On the other hand, in the 6–6-6 fused ring system,
only the chair-type conformation is permitted for the central
cyclohexane ring, and thus conformational change is much
more inhibited. This conformational restriction for the cyclo-
250 8C.
Supporting Information Figure S13 shows the DSC thermo-
grams of polyurethanes 5. The thermograms confirmed the
glass transitions of the polyurethanes, and the increase in
the relative amount of 3 to NPG resulted in an increase in
the T values. As shown in Figure 1, the T values increased
g g
according to the increase of diol 3-derived units in the poly-
urethanes. As was expected, the incorporation of the confor-
mationally constrained 6–6-6 moieties into the main chain
resulted in efficient suppression of the movement of the
hexane core is the reason for the higher T values of 4 than
g
those of 2.
main chain and increased the T value. The curve shown in
g
Figure 1 represents the dependence of T value on weight
ratio between unit A and unit B, which was predicted by the
g
Ternary Polyaddition System
The high T values of polyurethanes 4, synthesized by poly-
g
addition of diol 3 with diisocyanates, implied the potential
applicability of 3 as a co-monomer that can be added to the
polyadditions of conventional diols with diisocyanates to
increase the T values of the resulting polyurethanes. A ter-
g
nary polyaddition involving NPG, diol 3, and HMDI was per-
formed with varying feed ratios ([NPG] :[3] ) to investigate
0
0
the effect of 3 on the Tg values of the resulting polyur-
ethanes 5 (Scheme 4). The results are summarized in Table
1
13
2
. The H- and C NMR spectra of 5 are shown in Support-
ing Information Figures S8–S11.
First, polyaddition of NPG and HMDI was performed to syn-
thesize the corresponding polyurethane 5a (Entry 1). The Tg
value of the polyurethane was 39 8C.
Then, some of the NPG was replaced with diol 3, and the ter-
nary polyaddition of NPG, diol 3, and HMDI was performed.
The feed ratio, [NPG] :[3] , was varied in the range from
FIGURE 1 Plots of Tg values of polyurethanes 5 versus weight
0
0
g
ratios (unit A:unit B). The curve represents T values predicted
75:25 to 25:75. As a result, the corresponding polyurethanes
by the Fox equation.
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000
5

JOURNAL OF
POLYMER SCIENCE
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WWW.POLYMERCHEMISTRY.ORG
Fox equation. The T values of the copolymers 5b, 5c, and
14 F. Fenouillot, A. Rousseau, G. Colomines, R. Saint-Loup, J.
P. Pascault, Prog. Polym. Sci. 2010, 35, 578.
g
5d were in good accordance with the predicted ones.
1
5 S. Mu n~ oz-Guerra, C. Lavilla, C. Japu, A. Mart ꢀı nez de
Ilarduya, Green Chem. 2014, 16, 1716.
6 C. Japu, A. Mart ꢀı nez de Ilarduya, A. Alla, M. G. Garc ꢀı a-
CONCLUSIONS
1
A highly rigid diol on a 6–6-6 fused ring system, 3, was syn-
thesized by the reaction of myo-inositol with 2,3-butanedione
and methanol. Its polyaddition with disocyanates gave the
corresponding polyurethanes 4. DSC analyses of 4 revealed
the higher glass transition temperatures of these polymers
relative to those of the previously reported polyurethanes 2
obtained by polyaddition of another myo-inositol-derived
diol bearing a 5–6-5 fused ring system. In addition, 3 was
applicable as a co-monomer in the polyaddition of NPG and
HMDI. By increasing the amount of 3 that replaced some of
ꢀ
~
Martın, J. A. Galbis, S. Munoz-Guerra, Polym. Chem. 2013, 4,
3524.
17 C. Lavilla, A. M. de Ilarduya, A. Alla, M. G. Garc ꢀı a-Mart ꢀı n, J.
A. Galbis, S. Mu n~ oz-Guerra, Macromolecules 2012, 45, 8257.
18 B. Begines, F. Zamora, E. Benito, M. d. G. Garc
ıa-Mart ꢀı n, J.
A. Galbis, J. Polym. Sci. Part A: Polym. Chem. 2012, 50, 4638.
9 J. Wu, P. Eduard, S. Thiyagarajan, L. Jasinska-Walc, A.
Rozanski, C. F. Guerra, B. A. J. Noordover, J. van Haveren, D.
S. van Es, C. E. Koning, Macromolecules 2012, 45, 5069.
ꢀ
1
2
0 A. Saadaoui, R. Medimagh, S. Marque, D. Prim, S. Chatti, H.
Casabianca, M. Said Zina, Des. Monom. Polym. 2016, 20, 221.
1 E. Zakharova, A. Mart ꢀı nez de Ilarduya, S. Le oꢀ n, S. Mu n~ oz-
g
the NPG, the T value of the polyurethane was efficiently
2
increased. These results imply that 3 would be applicable for
Guerra, Des. Monom. Polym. 2016, 20, 157.
the development of various high-T polymers.
g
22 A. Wroblewska, A. Zych, S. Thiyagarajan, D. Dudenko, D.
van Es, M. R. Hansen, C. Koning, R. Duchateau, L. Jasinska-
Walc, Polym. Chem. 2015, 6, 4133.
2
3 L. Jasinska-Walc, D. Dudenko, A. Rozanski, S. Thiyagarajan,
ACKNOWLEDGMENT
P. Sowinski, D. van Es, J. Shu, M. R. Hansen, C. E. Koning,
Macromolecules 2012, 45, 5653.
This work was supported by JSPS KAKENHI Grant Number
JP24550262.
2
4 L. Fertier, M. Ibert, C. Buffe, R. Saint-Loup, C. Joly-Duhamel,
J. J. Robin, O. Giani, Prog. Org. Coat. 2016, 99, 393.
5 J. J. Gallagher, M. A. Hillmyer, T. M. Reineke, ACS Sustain.
Chem. Eng. 2016, 4, 3379.
6 B. Wang, K. Mireles, M. Rock, Y. Li, V. K. Thakur, D. Gao, M.
R. Kessler, Macromol. Chem. Phys. 2016, 217, 871.
7 D. M. Fidalgo, A. A. Kolender, O. Varela, Mater. Today Com-
mun. 2015, 2, e70.
8 A. Sudo, Y. Shirakawa, T. Sakue, J. Polym. Sci. Part A:
Polym. Chem. 2017, 55, 1524.
2
REFERENCES AND NOTES
2
1
S. L. Kristufek, K. T. Wacker, Y.-Y. Timothy Tsao, L. Su, K. L.
Wooley, Nat. Prod. Rep. 2017, 34, 433.
M. J. Sanford, L. Pe n~ a Carrodeguas, N. J. Van Zee, A. W.
Kleij, G. W. Coates, Macromolecules 2016, 49, 6394.
S. Tateyama, S. Masuo, P. Suvannasara, Y. Oka, A. Miyazato,
2
2
2
3
K. Yasaki, T. Teerawatananond, N. Muangsin, S. Zhou, Y.
Kawasaki, L. Zhu, Z. Zhou, N. Takaya, T. Kaneko, Macromole-
cules 2016, 49, 3336.
2
2
9 A. Sudo, S. Sugita, J. Polym. Sci. Part A: Polym. Chem.
016, 54, 3436.
3
2
0 A. Sudo, T. Sano, M. Harada, D. Ishida, ACS Macro Lett.
014, 3, 808.
4
5
6
I. Barbara, A. L. Flourat, F. Allais, Eur. Polym. J. 2015, 62, 236.
K. Satoh, Polym. J. 2015, 47, 527.
3
1 S. Okamoto, S. Onoue, M. Kobayashi, A. Sudo, J. Polym.
B. G. Harvey, A. J. Guenthner, G. R. Yandek, L. R. Cambrea,
Sci. Part A: Polym. Chem. 2014, 52, 3498.
2 A. Sudo, Y. Shibata, A. Miyamoto, J. Polym. Sci. Part A:
Polym. Chem. 2013, 51, 3956.
H. A. Meylemans, L. C. Baldwin, J. T. Reams, Polymer 2014,
3
5
7
8
9
5, 5073.
K. Yao, C. Tang, Macromolecules 2013, 46, 1689.
G. Q. Chen, M. K. Patel, Chem. Rev. 2012, 112, 2082.
C. Z uꢀ n~ iga, M. S. Larrechi, G. Lligadas, J. C. Ronda, M. Gali aꢁ ,
33 R. Valluru, W. Van den Ende, Plant Sci. 2011, 181, 387.
34 R. H. Michell, Nat. Rev. Mol. Cell. Biol. 2008, 9, 151.
35 K. M. Sureshan, M. S. Shashidhar, T. Praveen, T. Das,
V. C aꢀ diz, J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 1219.
Chem. Rev. 2003, 103, 4477.
6 T. Suzuki, S. T. Suzuki, I. Yamada, Y. Koashi, K. Yamada, N.
Chida, J. Org. Chem. 2002, 67, 2874.
10 G. M. Miyake, Y. Zhang, E. Y. X. Chen, Macromolecules
010, 43, 4902.
3
2
1
1 A. F. Sousa, J. F. J. Coelho, A. J. D. Silvestre, Polymer 2016,
37 A. E. Koumbis, C. D. Duarte, C. Nicolau, J. M. Lehn, Chem.
Med. Chem. 2011, 6, 169.
98, 129.
12 S. Chatti, S. M. Weidner, A. Fildier, H. R. Kricheldorf, J.
38 S. V. Ley, D. K. Baeschlin, D. J. Dixon, A. C. Foster, S. J.
Polym. Sci. Part A: Polym. Chem. 2013, 51, 2464.
3 J. Wu, P. Eduard, L. Jasinska-Walc, A. Rozanski, B. A. J.
Noordover, D. S. van Es, C. E. Koning, Macromolecules 2013,
6, 384.
Ince, H. W. M. Priepke, D. J. Reynolds, Chem. Rev. 2001, 101,
53.
1
39 J.-L. Montchamp, F. Tian, M. E. Hart, J. W. Frost, J. Org.
Chem. 1996, 61, 3897.
4
6
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000