Convenient synthesis of cyclic carbonates from CO2 and epoxides by simple secondary and primary ammonium iodides as metal-free catalysts under mild conditions and its application to synthesis of polymer bearing cyclic carbonate moiety

Article abstract of DOI:10.1002/pola.26492

Hydroiodides of secondary and primary amines effectively catalyzed the reaction of carbon dioxide and epoxides under mild conditions such as ordinary pressure and ambient temperature, to obtain the corresponding five-membered cyclic carbonates in moderate to high yields. Detailed investigation showed that the catalytic activity was highly affected by the counter anions of the ammonium salts; the iodides catalyzed efficiently the carbonate-forming reactions, whereas the bromide and chloride counterparts exhibited almost no catalysis. We also revealed that two important factors on the amine moieties that affected the catalytic reactions. First, the catalytic activity increased with increasing bulkiness of the substituents on the ammonium nitrogen atoms. Second, the catalysis became more efficient as the parent amines become more basic. Dicyclohexylammonium iodide was the best catalyst among the ammonium salts investigated in this study. As an application of this reaction system, we synthesized homo- and copolymers bearing epoxide pendant groups as substrates, which were converted with high efficiency into the corresponding homo- and copolymers bearing cyclic carbonate pendant groups under 1 atm at 45 °C. All polymers were easily purified simply by precipitation in water, and were isolated in high yields (>95%). 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013. Copyright

Full text of DOI:10.1002/pola.26492

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Convenient Synthesis of Cyclic Carbonates from CO2 and Epoxides by
Simple Secondary and Primary Ammonium Iodides as Metal-Free
Catalysts under Mild Conditions and Its Application to Synthesis of
Polymer Bearing Cyclic Carbonate Moiety
Naoto Aoyagi, Yoshio Furusho, Takeshi Endo
Molecular Engineering Institute, Kinki University, Iizuka, Fukuoka 820-8555, Japan
Correspondence to: T. Endo (E-mail: tendo@moleng.fuk.kindai.ac.jp)
Received 1 August 2012; accepted 18 November 2012; published online 18 December 2012
DOI: 10.1002/pola.26492
ABSTRACT: Hydroiodides of secondary and primary amines
effectively catalyzed the reaction of carbon dioxide and epoxides
under mild conditions such as ordinary pressure and ambient
temperature, to obtain the corresponding five-membered cyclic
carbonates in moderate to high yields. Detailed investigation
showed that the catalytic activity was highly affected by the
counter anions of the ammonium salts; the iodides catalyzed
efficiently the carbonate-forming reactions, whereas the bromide
and chloride counterparts exhibited almost no catalysis. We also
revealed that two important factors on the amine moieties that
affected the catalytic reactions. First, the catalytic activity
increased with increasing bulkiness of the substituents on the
ammonium nitrogen atoms. Second, the catalysis became more
efficient as the parent amines become more basic. Dicyclohexy-
lammonium iodide was the best catalyst among the ammonium
salts investigated in this study. As an application of this reaction
system, we synthesized homo- and copolymers bearing epoxide
pendant groups as substrates, which were converted with high
efficiency into the corresponding homo- and copolymers bearing
cyclic carbonate pendant groups under 1 atm at 45 ꢀC. All poly-
mers were easily purified simply by precipitation in water, and
C
V
were isolated in high yields (>95%).
2012 Wiley Periodicals,
Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 1230–1242
KEYWORDS: CO2; cyclic carbonate; catalysts; copolymerization;
heteroatom-containing polymers
INTRODUCTION The increasing concentration of carbon diox-
ide (CO2) in the atmosphere is partly responsible for the cli-
mate changes, while CO2 is also regarded as a cheap, green
C1 resource.1,2 CO2 is an environmentally friendly chemical
reagent and is especially useful as a phosgene substitute.3
One of the most important process is incorporation of CO2
into epoxides to give five-membered cyclic carbonates,4
which are widely used as aprotic polar solvents,5 electro-
lytes,6–8 and lithium ion batteries.9–11 Five-membered cyclic
carbonates are possible to use as starting compounds for
polycarbonate derivatives,12–15 although direct synthesis of
polycarbonates from CO2 and epoxides are reported.16–25
Additionally, polyaddition of bifunctional cyclic carbonates
and a,x-diamines gives poly(hydroxyurethane)s, which have
recently attracted much attention.26–31 For example, poly(hy-
droxyurethane)s can be crosslinked by utilizing their
hydroxyl functionalities to give networked polymers.32 Judi-
cious choice of the crosslinkers can adjust the polarity of the
networked polymers, leading to control over the affinity of
the network polymers toward solvents with different
polarities. The ion gels based on hydroxyurethane-cross-
linked poly(cyclic carbonate methacrylate) have high ionic
conductiviters.33 Several other poly(hydroxyurethane)s are
used as polymer/liquid crystal composite films,34 amphi-
philic antibacterial polymers,35 and dye fixation agent.36
Accordingly, a wide range of CO2 incorporation reactions for
the synthesis of cyclic carbonates have been developed,
including alkali metal salts,37–40 onium salts,41–46 metal com-
plexes,47–58 ionic liquids,59–63 silica-supported catalysts,64–69
polymer catalysts,70–76 chiral catalysts,77–79 and so on.80–85
However, most of these reactions require some pressure
(ꢁ20 atm) and/or high temperature with the exception of
several expensive metal catalysts. We have recently reported
that the LiBr-catalyzed reaction of CO2 and epoxides is
highly accelerated in the presence of N-methyltetrahydropyr-
imidine (MTHP) as a CO2 carrier, and the corresponding
cyclic carbonates are obtained in moderate to high yields
under mild conditions (1 atm, r.t. to 45 ꢀC).86,87 However,
this system requires large amounts of LiBr as well as MTHP
for obtaining the carbonates in reasonable yields.
Additional Supporting Information may be found in the online version of this article.
C
V
2012 Wiley Periodicals, Inc.
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TABLE 1 Effect of anion moiety of catalyst for the synthesis of
cyclic carbonate under ambient conditionsa
Entry
Catalyst
Yield (%)b
1
2
3
a
1aꢂHCl
1aꢂHBr
1aꢂHI
<1
4
CHART 1 Amines used in this study.
85
Additionally, linear88 and cyclic89 amidines are sensitive to
moisture, for example, 1,5-diazabicyclo-[3.4.0]non-5-ene
(DBN) was quantitatively hydrolyzed by using 2 to 25 equiv-
alents of water at room temperature over 12 h.89 Amine
derivatives are inexpensive and more stable than linear and
cyclic amidines, although catalysts of amine salts require
higher pressure and/or higher temperature than amidine-
LiBr catalyst for the synthesis of cyclic carbonates from CO2
and epoxides. During the course of our research on various
ammonium salts, we have found that hydroiodides of sec-
ondary and primary amines efficiently catalyze the cyclic car-
bonate-forming reactions from CO2 and epoxides (Chart 1).
Herein, we report a novel efficient synthetic method for
mono-, bis-, and polycyclic carbonates from CO2 and epox-
ides by using a catalytic amount of hydroiodides of second-
ary and primary amines under mild conditions such as ordi-
nary pressure and ambient temperature (Scheme 1).
Reaction conditions: 1 mmol of 4a, 0.05 mmol of 1aꢂHX, 0.2 mL of
NMP, 25 ꢀC under 1 atm of CO2 for 24 h.
b
Determined by 1H NMR.
salts (1aꢂHCl, 1aꢂHBr, and 1aꢂHI) were synthesized by
using hydrohalogenic acids in high yields (Experimental sec-
tion), and we found that the reactivity of 4a was strongly
affected by the anions of 1a salts. Although 1aꢂHCl and
1aꢂHBr gave no cyclic carbonate, the use of iodide (1aꢂHI)
resulted in an increased yield of 85% (entries 1–3). The ca-
talysis is thus highly affected by the leaving ability of the
counter anion moiety of the ammonium salt. Therefore, the
leaving of iodide anion at the ring-closure step is most likely
to be the rate-determining step for the reaction. A plausible
mechanism for the catalytic synthesis of carbonates consists
of nucleophilic attack of the halide anion to the epoxy group
followed by carbonate formation with CO2 and subsequent
ring-closing reaction (Scheme 2). The 1H NMR spectrum of
an equimolar mixture of 1aꢂHI and 4a in deuterated N,N-
dimethylformamide (DMF-d7) in the absence of CO2 showed
no change and was identical to the sum spectrum of those of
1aꢂHI and 4a right after the mixing, clearly indicating that
RESULTS AND DISCUSSION
First, we investigated the effect of the counter anions of the
1a salts on the carbonate formation from phenyl glycidyl
ether (4a) and CO2 in 1-methyl-2-pyrrolidone (NMP) at 1
atm and ambient temperature (Table 1). Dicyclohexylamine
SCHEME 1 Synthesis of cyclic carbonates from epoxides and CO2.
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TABLE 2 Effect of cation of catalyst for the synthesis of cyclic
carbonate under ambient conditionsa
Entry
Catalyst
Yield (%)b
1
2
3
4
5
a
1aꢂHI
3aꢂHI
N-Me-3aꢂI
TBAIc
HId
85
28
8
SCHEME 2 A plausible mechanism for catalyzed synthesis of
17
NDe
cyclic carbonates from epoxides and CO2.
Reaction conditions: 1 mmol of 4a, 0.05 mmol of catalyst, 0.2 mL of
the catalytic cycle does not involve the activation of the
epoxide by the secondary ammonium salt moiety of the
catalyst through hydrogen-bonding interaction (Fig. 1). This
absence of the activation of the epoxide by the secondary
ammonium salt can be attributed to the strong hydrogen-
accepting ability of DMF and NMP, of which the donor num-
NMP, 25 ꢀC under 1 atm of CO2 for 24 h.
b
Determined by 1H NMR.
c
0.05 mmol of tetrabutylammonium iodide.
d
0.05 mmol of 55% aqueous hydriodic acid.
e
Not detected.
1
bers are 26.6 and 27.3, respectively.90 The H NMR spectrum
The formation of 6a supports the existence of the alkoxide
generated by the iodide anion in the catalytic cycle, which
undergoes the carbonate-forming reaction in the presence of
CO2. The 1aꢂHI does not catalyze the ring-opening reaction
of 5a with iodide anion, because the 1H NMR spectrum of
5a with 1aꢂHI in DMF-d7 did not show any changes even af-
ter 24 h (Supporting Information Fig. S1). In addition, the
13C NMR signal of CO2 in DMF-d7 (125.1 ppm) did not
gradually changed with time in the absence of CO2 and
showed a new set of signals at 3.45, 3.55, 3.99, 4.03, and
4.08 ppm after 24 h, which were assignable to the methine
and methylene protons of the iodohydrin 6a. The time-aver-
aged signal of the active protons of 6a, 1a, and unreacted
1aꢂHI appeared at ca. 6 ppm as a broad singlet due to their
chemical exchange faster than on the 1H NMR time scale.
1
FIGURE 1 Partial H NMR spectra (400 MHz, 25 ꢀC) of a solution of 4a with 1alHI in DMF-d7.
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TABLE 3 Effect of structure of catalyst for the synthesis of
obtained from strongly basic secondary amines (1a–c: pKa >
10) gave 5a in moderate to high yields, and the results indi-
cate that the reactivity of the carbonate formation was
affected by the size of the alkyl substituents on the ammo-
nium iodides (entries 1–3). The bulkiness of the alkyl sub-
stituents on the secondary ammonium iodide played an im-
portant role in the synthesis of carbonate (5a) under mild
conditions, as indicated by the result that the catalytic
activity increased with increasing bulkiness of the alkyl sub-
stituents, i.e., Cy2 > n-Bu2 > (CH2)5. In contrast, the use of
hydroiodides obtained from moderately basic dibenzylamine
(1d: pKa ¼ 8.8) and weakly basic diphenylamine (1e: pKa ¼
0.8) resulted in almost no reaction under mild conditions
(entries 4, 5), as suggested by the fact that the reaction of
propylene oxide and CO2 with polyaniline hydroiodide
(based on diphenylamine structure) required relatively
severe conditions such as 50 atm and 115 ꢀC.72 As in the
case of secondary ammonium iodides (1a–cꢂHI), hydroio-
dides of strongly basic primary amines (2a–d: pKa ¼ 10–11)
also gave 5a in moderate to high yields (entries 6–9). The
catalytic activity was affected by the bulkiness of the alkyl
substituents on the catalysts, as shown by the result that the
catalytic activity increased with increasing bulkiness of the
alkyl substituents, that is, t-Bu > Cy, i-Pr > n-Bu (entries 6–
9). Ammonium iodide (2eꢂHI, NH4I) gave 5a in a much
lower yield than that obtained by using monoalkylated pri-
mary ammonium iodides (2a–dꢂHI) as carbonate-forming
catalyst (entry 10). The use of hydroiodides of moderately
basic benzylamine (2f: pKa ¼ 9.1) and weakly basic aniline
(2g: pKa ¼ 4.6) resulted in a low yield and almost no reac-
tion, respectively (entries 11, 12). Overall, the primary am-
monium iodides showed moderate to excellent catalytic ac-
tivity comparable to that of the secondary ones. In addition,
bulky alkyl substituents (t-Bu, Cy) and strongly basic amino
group (pKa > 10) endowed the ammonium catalysts with
cyclic carbonate under ambient conditionsa
Entry
Catalyst
Amine (pKa /ꢃ)b
Yield (%)c
1
1aꢂHI
1bꢂHI
1cꢂHI
1dꢂHI
1eꢂHI
2aꢂHI
2bꢂHI
2cꢂHI
2dꢂHI
2eꢂHI
2fꢂHI
2gꢂHI
11.4 6 0.2
11.0 6 0.2
10.5 6 0.1
8.8 6 0.2
0.8 6 0.2
10.7 6 0.3
10.6 6 0.1
10.7 6 0.3
10.7 6 0.1
9.21e
85
54
34
1
NDd
81
67
64
50
13
18
NDd
2
3
4
5
6
7
8
9
10
11
12
a
9.1 6 0.1
4.6 6 0.1
Reaction conditions: 1 mmol of 4a, 0.05 mmol of catalyst, 0.2 mL of
NMP, 25 ꢀC under 1 atm of CO2 for 24 h.
b
The pKa values were obtained from SciFinder.91
Determined by 1H NMR.
c
d
Not detected.
e
Determined in water.92
change either after the addition of 1aꢂHI (Supporting
Information Fig. S2), suggesting that 1aꢂHI does not directly
activate CO2 before formation of 6a.
Next, we synthesized N-methyldicyclohexylamine derivatives
(3aꢂHI and N-Me-3aꢂI: Experimental section) to study
effects of cations on the carbonate formation at ordinary
temperatures and pressures. As shown in Table 2, tertiary
ammonium salt (3aꢂHI) gave a much lower yield of 5a than
that obtained by using secondary ammonium salt (1aꢂHI) as
carbonate-forming catalyst (entries 1, 2). Quaternary ammo-
nium salts (N-Me-3aꢂI and tetrabutylammonium iodide
(TBAI)) had even less activity than that of the tertiary am-
monium salt (3aꢂHI) (entries 3, 4). The oxonium cation was
not suitable for the catalyst of the synthesis of carbonate,
because the aqueous hydrogen iodide gave no cyclic carbon-
ate (entry 5). The order of catalytic activity was secondary
>> tertiary > quaternary ammonium iodide, indicating that
the protons on the ammonium nitrogen atoms played an im-
portant role in the synthesis of carbonate (5a) under mild
conditions.
TABLE 4 Effect of solvent for the synthesis of cyclic carbonate
under ambient conditionsa
Entry
Solv.
Yield (%)b
1
2
3
4
5
6
7
a
NMP
85
72
67
62
32
11
<1
DMI
DMAc
DMF
DMSO
THF
Furthermore, we examined various hydroiodides of second-
ary and primary amines (1a–e, 2a–g) in the carbonate for-
mation from 4a and CO2 in NMP at 1 atm and ambient tem-
perature (Table 3). Secondary and primary ammonium
iodides (1b–eꢂHI and 2a–gꢂHI) were synthesized with hydri-
odic acid in high yields (Experimental section). Hydroiodides
Toluene
Reaction conditions: 1 mmol of 4a, 0.05 mmol of 1aꢂHI, 0.2 mL of sol-
vent, 25 ꢀC under 1 atm of CO2 for 24 h.
b
Determined by 1H NMR.
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of 4a at 25 ꢀC (entries 1–5). Glycidyl methacrylate (4f) and
epichlorohydrin (4g) containing electron withdrawing groups
on the carbon atom next to the epoxy group were as reactive
as aryl glycidyl ethers (4b–c), while epoxides bearing hydro-
carbon substituents, such as 1,2-epoxyhexane (4h) and sty-
rene oxide (4i), had much lower reactivity than those of
other epoxides (entries 6-9). The yields of hetero-functional
carbonates (5a–g) increased when the reaction temperature
TABLE 5 Synthesis of various cyclic carbonates by 1alHI
under mild conditionsa
ꢀ
was raised from 25 to 45 C (entries 10–16). Under the mild
Entry
Epoxide
Temperature (ꢀC)
Yield (%)b
ꢀ
conditions (45 C, 1 atm), the hydrocarbon-substituted epox-
ides with low reactivity (4h–i) were converted to the corre-
sponding carbonates (5h–i), which were obtained in more
than 60% yield (entries 17, 18). The scaled-up reaction of
4a (1.50 g, 10 mmol) was carried out under 1 atm CO2 at
45 ꢀC and 5a was isolated in quantitative yield by simple
precipitation from water (entry 19). The reaction of 4f (1.42
g, 10 mmol) under the same conditions gave 5f in a high iso-
lated yield of 93% after purification by partitioning between
ethyl acetate and water (entry 20).
1
4a
4b
4c
4d
4e
4f
25
25
25
25
25
25
25
25
25
45
45
45
45
45
45
45
45
45
45
45
85
68
2
3
60
4
42
5
57
6
69
7
4g
4h
4i
70
8
27
9
20
Furthermore, we applied the 1aꢂHI-catalyzed carbonation
reaction to a bifunctional epoxide and a polymethacrylate
bearing glycidyl pendant group (Scheme 3). The biscarbonate
(5j) was obtained quantitatively in the same manner as that
for the 5a. Poly(glycidyl methacrylate) (4k) was synthesized
by free-radical polymerization of glycidyl methacrylate using
2,20-azobis(isobutyronitrile) (AIBN), and 4k was converted
quantitatively into 5k in a high isolated yield of 92% by sim-
ply precipitation with methanol. The number average molec-
ular weight of 5k (Mn 9070) estimated by size exclusion
chromatography (SEC) was 1.31 times higher than that of 4k
(Mn 12,000), and the change in the molecular weight was in
good agreement with a 1.31-fold increase in the formula
weights of the repeating units (FW for 4k 142 unitꢃ1; FW
for 5k 186 unitꢃ1). In addition, the polydispersity indices of
5k remained the same as that of 4k, indicating that neither
scission of the polymer backbone nor crosslinking of the
polymer did not take place during the carbonation reaction.
The lithium bromide (LiBr)-catalyzed carbonate-forming
reaction of 4k proceeded slowly, and a significant amount of
the epoxy group remained unreacted (carbonate/epoxy ¼
61:39) under the same mild conditions, although LiBr has
been used to synthesize various cyclic carbonates with high
conversion at high temperature conditions.93,94
10
11
12
13
14
15
16
17
18
19c
20
a
4a
4b
4c
4d
4e
4f
97
97
93
90
90
95
4g
4h
4i
4ad
4fd
95
88
84
>99e
93e
Reaction conditions: 1 mmol of epoxide, 0.05 mmol of 1aꢂHI, 0.2 mL
of NMP, 25 or 45 ꢀC under 1 atm of CO2 for 24 h.
b
Determined by 1H NMR.
Reaction time ¼ 48 h.
Scaled up 10 times.
Isolated yields.
c
d
e
efficient catalytic activity under mild conditions, and the di-
cyclohexylamine hydroiodide (1aꢂHI) was the best catalyst
among the ammonium salts investigated here (1a–2gꢂHI).
Next, the carbonate formation of 4a with CO2 was carried
out in various solvents using 1aꢂHI (Table 4). Cyclic carbon-
ate (5a) was obtained in moderate to high yields in aprotic
polar amide solvents such as NMP, 1,3-dimethyl-2-imidazoli-
dinone (DMI), N,N-dimethylacetamide (DMAc), and DMF
(entries 1-4). In contrast, aprotic polar sulfoxide solvent
such as dimethylsulfoxide (DMSO) gave 5a in low yield
(entry 5), and the yield of 5a remarkably decreased in tetra-
hydrofuran (THF) and toluene (entries 6, 7).
Finally, we investigated the isolation procedure using water
as an environmentally friendly solvent, employing homo- and
copolymers bearing cyclic carbonate moieties (4k–n)
obtained with 1aꢂHI-catalyzed reaction (Table 6). Epoxy-con-
taining polymers (4l–n) were synthesized by a method simi-
lar to that for 4k (Experimental section). The carbonated
polymer (5k) was isolated via precipitation in water, and its
yield was slightly higher than that obtained through the pre-
cipitation in methanol (entry 1). As with reaction of 4k, the
epoxy-containing homo- and copolymers (4l–n) were also
converted quantitatively into 5l–n (>99%) under 1 atm at
45 ꢀC with an increase in the number average molecular
weight, which were in good agreement with the increases in
the formula weights (entries 2–4). Moreover, the carbonated
Then, we examined the carbonate-forming reactions of other
epoxides with 1aꢂHI at 25 or 45 ꢀC (Table 5). Various gly-
cidyl ethers, such as 4-chlorophenyl glycidyl ether (4b), 4-
methoxyphenyl glycidyl ether (4c), n-butyl glycidyl ether
(4d), and allyl glycidyl ether (4e), gave the corresponding
carbonates (5b–e) in lower yields than that for the reaction
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SCHEME 3 Synthesis of bifunctional cyclic carbonate (5j) and polymethacrylate bearing cyclic carbonate pendant group (5k).
polymers (5l–n) were isolated quantitatively by the precipi-
tation method using water in spite of the fact that the poly-
mers employed here had low molecular weights with an Mn
of about 3000 to 6000. Thus, water was quite effective in
the removal of 1aꢂHI and NMP from reaction mixture, while
efficiently precipitating the carbonated polymers (5k–n).
mine (>98.0%), isopropylamine (>99.0%), butylamine
(>98.0%), ammonium iodide (>99.5%), hydrochloric acid
(35.0–37.0%), phenyl glycidyl ether (>98.0%), epichlorohy-
drin (>99.0%), butyl glycidyl ether (>97.0%), 1,2-epoxyhex-
ane (>96.0%), styrene oxide (>98.0%), 2,20-azobis(isobutyr-
onitrile) (>98.0%), dry 1-methyl-2-pyrrolidone (>97.0%),
dry dichloromethane (>99.0%), toluene (>99.5%) were
obtained from Wako Pure Chemical Industries. Hydrobromic
acid (47.0–49.0%), hydriodic acid (55.0–58.0%), methyl
iodide (>99.5%), 1,4-dioxane (>99.5%) were obtained from
Kanto Chemical. Aniline (ꢄ99.5%), 4-chlorophenyl glycidyl
ether (99%), 4-methoxyphenyl glycidyl ether (99%), glycidyl
methacrylate (ꢄ97%) were obtained from Aldrich Chemical.
Bisphenol A diglycidyl ether was obtained from Nippon Steel
Chemical; 4-vinylbenzyl glycidyl ether was obtained from
AGC Seimi Chemical. All vinyl monomers (glycidyl
EXPERIMENTAL
Materials
CO2 (>99.99%) was obtained from Fukuho Teisan. Dicyclo-
hexylamine (>99.0%), dibutylamine (>99.0%), piperidine
(>99.0%),
diphenylamine
(>99.0%),
tert-butylamine
(>98.0%), benzylamine (>99.0%), N-methyldicyclohexyl-
amine (>98.0%), allyl glycidyl ether (>99.0%), methyl meth-
acrylate (>99.8%), styrene (>99.0%) were obtained from
Tokyo Kasei Kogyo. Dibenzylamine (>97.0%), cyclohexyla-
TABLE 6 Synthesis of polymers bearing cyclic carbonate pendant groups by 1alHI under mild conditions and purified by watera,a
Mn (Mw/Mn)d
Incorporation
of CO2 (%)c
Entry
Epoxide (x:y)
Yield (%)b
Epoxide: 4k–n
Carbonate: 5k–n
1
2
3
4
a
4k (1:0)
4l (1:1)
4m (1:0)
4n (1:1)
95
>99
98
>99
>99
>99
>99
c
9,070 (2.42)
3,000 (2.54)
4,640 (1.88)
4,260 (1.79)
11,500 (2.52)
3,520 (2.61)
6,140 (1.93)
5,020 (1.86)
>99
Reaction conditions: 1 mmol of epoxide, 0.05 mmol of 1alHI, 0.2 mL
Determined by 1H NMR.
Estimated by SEC (DMF containing 10 mM LiBr, polystyrene
d
of NMP, 45 ꢀC under 1 atm of CO2 for 24 h.
b
Isolated yield after precipitation in water.
standard).
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methacrylate, methyl methacrylate, 4-vinylbenzyl glycidyl
ether and styrene) were washed with 10% aqueous sodium
hydroxide solution, extracted with toluene, and dried with
anhydrous Na2SO4 before use. 2,20-Azobis(isobutyronitrile)
was recrystallized from methanol. All other reagents were
used as received without further purification.
1.91-2.01 (m, 4H, NCH2CH2), 3.04 (t, 4H, J ¼ 8.0 Hz,
NCH2CH2), 8.26 (brs, 2H, NH2). 13C NMR (CDCl3, d, ppm):
13.3 (CH3), 20.0 (CH2CH3), 27.4 (NCH2CH2), 47.6
(NCH2CH2).
Piperidine Hydroiodide (1cꢂHI). Ninety-eight percent yield
as a pale yellow solid.97 1H NMR (CDCl3, d, ppm): 1.74 (quin,
2H, J ¼ 6.0 Hz, NCH2CH2CH2), 2.00 (quin, 4H, J ¼ 6.0 Hz,
NCH2CH2CH2CH2), 3.21-3.33 (m, 4H, CH2NCH2), 8.33 (brs,
2H, NH2). 13C NMR (CDCl3, d, ppm): 21.9 (NCH2CH2CH2),
22.1 (NCH2CH2CH2CH2), 44.6 (CH2NCH2).
Characterizations
1H (400 MHz) and 13C (100 MHz) nuclear magnetic reso-
nance (NMR) spectroscopy measurements were performed
on a JEOL ECS-400/SS instrument using tetramethylsilane as
an internal standard at ambient temperatures. Number aver-
age molecular weight (Mn) and polydispersity index (Mw/
Mn) were estimated by size exclusion chromatography (SEC)
using a TOSOH HLC-8220 GPC instrument equipped with
three consecutive polystyrene gel columns [TSK-gels (particle
size, exclusion limit); super AW4000 (6 lm, >4 ꢅ 105),
super AW3000 (4 lm, >6 ꢅ 104), and super AW2500 (4
lm, >2 ꢅ 103), 15 cm each] and a guard column [TSK-guard
column Super AW-H, 3.5 cm] with DMF containing 0.01M
LiBr as an eluent at a flow rate 0.5 mL/min at 40 ꢀC after
calibration with polystyrene standards.
Dibenzylamine Hydroiodide (1dꢂHI). Hundred percent
yield as a white solid.98 1H NMR (CDCl3, d, ppm): 4,23 (s,
4H, CH2N), 7.41-7.54 (m, 10H, ArH), 9.20 (brs, 2H, NH2). 13C
NMR (CDCl3, d, ppm): 50.1 (CH2N), 128.7 (Ar), 129.0 (Ar),
130.0 (Ar), 131.8 (Ar).
Diphenylamine Hydroiodide (1eꢂHI). Ninety-eight percent
yield as a pale yellow solid.99 1H NMR (DMSO-d6, d, ppm):
6.27 (brs, 2H, NH2), 6.81 (t, 2H, J ¼ 8.0 Hz, ArH), 7.07 (d,
4H, J ¼ 8.0 Hz, ArH), 7.22 (t, 4H, J ¼ 8.0 Hz, ArH). 13C NMR
(DMSO-d6, d, ppm): 116.7 (Ar), 119.6 (Ar), 129.1 (Ar),
143.4 (Ar).
Synthesis
t-Butylamine Hydroiodide (2aꢂHI). Hundred percent yield
as a white solid.100 1H NMR (DMSO-d6, d, ppm): 1.27 (s, 9H,
C(CH3)3), 7.78 (brs, 3H, NH3). 13C NMR (DMSO-d6, d, ppm):
27.1 (C(CH3)3), 51.2 (C(CH3)3).
Synthesis of Ammonium Iodides (1a-eꢂHI, 2a-gꢂHI, and
3aꢂHI)
Cyclohexylamine Hydroiodide (2bꢂHI). Hundred percent
yield as a white solid.101 1H NMR (DMSO-d6, d, ppm): 1.02-
1.15 (m, 1H, CH2), 1.18-1.33 (m, 4H, CH2), 1.54-1.63 (m, 1H,
CH2), 1.66-1.77 (m, 2H, CH2), 1.83-1.91 (m, 2H, CH2), 2.93-
3.04 (m, 1H, NCH), 7.69 (brs, 3H, NH3). 13C NMR (DMSO-d6,
d, ppm): 23.7 (CH2), 24.5 (CH2), 30.3 (CH2), 49.3 (NCH).
Isopropylamine Hydroiodide (2cꢂHI). Ninety-nine percent
yield as a pale yellow solid.102 1H NMR (CDCl3, d, ppm): 1.57
(d, 6H, J ¼ 6.4 Hz, CH(CH3)2), 3.86 (quin, 1H, J ¼ 6.4 Hz,
CH(CH3)2), 7.16 (brs, 3H, NH3). 13C NMR (CDCl3, d, ppm):
21.1 (CH(CH3)2), 45.9 (CH(CH3)2).
A solution of 55% aqueous hydriodic acid (1 mL, ca. 7.3 mmol)
was added dropwise for 1 min to the mixture of amine (4
mmol) in dioxane (8 mL) at room temperature. After the
mixture was stirred at room temperature for 12 h, the mixture
was evaporated in vacuo. The residue was washed with ether,
and the precipitate was dried in vacuo for 4 h at 60 ꢀC (1eꢂHI
and 2gꢂHI were dried at 40 ꢀC) to give corresponding
ammonium hydroiodide.
Butylamine Hydroiodide (2dꢂHI). Ninety-three percent
yield as a pale yellow solid.103 1H NMR (DMSO-d6, d, ppm):
0.89 (t, 3H, J ¼ 7.2 Hz, CH3), 1.33 (sext, 2H, J ¼ 7.2 Hz,
CH2CH3), 1.52 (quin, 2H, J ¼ 7.2 Hz, NCH2CH2), 2.81 (t, 2H, J
¼ 7.2 Hz, NCH2CH2), 7.65 (brs, 3H, NH3). 13C NMR (DMSO-
d6, d, ppm): 13.5 (CH3), 19.0 (CH2CH3), 28.9 (NCH2CH2), 38.5
(NCH2CH2).
Benzylamine Hydroiodide (2fꢂHI). Hundred percent yield
as a white solid.104 1H NMR (DMSO-d6, d, ppm): 4,07 (s, 2H,
CH2N), 7.36-7.51 (m, 5H, ArH), 8.14 (brs, 3H, NH3). 13C NMR
(DMSO-d6, d, ppm): 42.3 (CH2N), 128.5 (Ar), 128.6 (Ar),
128.9 (Ar), 133.9 (Ar).
Dicyclohexylamine Hydroiodide (1aꢂHI). Hundred per-
cent yield as a white solid.95 1H NMR (DMSO-d6, d, ppm):
1.03-1.16 (m, 2H, CH2), 1.18-1.36 (m, 8H, CH2), 1.57-1.66
(m, 2H, CH2), 1.72-1.81 (m, 4H, CH2), 1.94-2.05 (m, 4H,
CH2), 3.07-3.21 (m, 2H, NCH), 8.09 (brs, 2H, NH2). 13C NMR
(DMSO-d6, d, ppm): 23.8 (CH2), 24.8 (CH2), 28.9 (CH2), 52.2
(NCH).
Aniline Hydroiodide (2gꢂHI). Hundred percent yield as a
white solid.105 1H NMR (DMSO-d6, d, ppm): 7.38 (d, 2H, J
¼ 7.2 Hz, ArH), 7.44 (t, 1H, J ¼ 7.2 Hz, ArH), 7.54 (t,
1H, J ¼ 7.2 Hz, ArH) , 9.76 (brs, 2H, NH2). 13C NMR
(DMSO-d6, d, ppm): 123.1 (Ar), 128.2 (Ar), 129.9 (Ar),
131.6 (Ar).
Dibutylamine Hydroiodide (1bꢂHI). Ninety-six percent
yield as a yellow solid.96 1H NMR (CDCl3, d, ppm): 0.97 (t,
6H, J ¼ 7.2 Hz, CH3), 1.45 (sext, 4H, J ¼ 7.2 Hz, CH2CH3),
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N-Methyldicyclohexylamine Hydroiodide (3aꢂHI). Ninety-
eight percent yield as a brown solid. 1H NMR (CDCl3, d,
ppm): 1.16–1.41 (m, 6H, CH2), 1.67-1.79 (m, 6H, CH2), 1.90–
2.00 (m, 4H, CH2), 2.04-2.12 (m, 2H, CH2), 2.42–2.50 (m, 2H,
CH2), 2.71 (d, 3H, J ¼ 5.6 Hz, CH3), 3.34-3.44 (m, 2H, NCH),
9.25 (brs, 1H, NH). 13C NMR (CDCl3, d, ppm): 24.7 (CH2),
25.0 (CH2), 25.1 (CH2), 26.7 (CH2), 28.5 (CH2), 32.8 (CH3),
62.7 (NCH).
(m, 2H, CH2), 1.44-1.77 (m, 10H, CH2), 1.97-2.05 (m, 4H, CH2),
2.22-2.30 (m, 4H, CH2), 3.09 (s, 6H, CH3), 3.63-3.71 (m, 2H,
NCH). 13C NMR (CDCl3, d, ppm): 24.6 (CH2), 25.2 (CH2), 26.4
(CH2), 44.8 (CH3), 70.6 (NCH).
General Procedure of Five-Membered Cyclic Carbonates
(5a–i)
The epoxide (1 mmol) was added to a mixture of catalyst
(0.05 mmol) in solvent (0.2 mL). The atmosphere inside
the flask was replaced with CO2 (balloon, ca. 1 atm), and
the reaction mixture was stirred for 24 h at 25 or 45 ꢀC.
After reaction, the product yields were determined by 1H
NMR.
Synthesis of Dicyclohexylamine Hydrochloride (1aꢂHCl)
and Hydrobromide (1aꢂHBr)
Synthesis of (Phenoxymethyl)ethylenecarbonate (5a)
A solution of 35% aqueous hydrochloric acid (1 mL, ca. 12
mmol) or 47% aqueous hydrobromic acid (1 mL, ca. 8.8
mmol) was added dropwise for 1 min to the mixture of
dicyclohexylamine (725 mg, 4 mmol) in dioxane (8 mL) at
room temperature. After the mixture was stirred at room
temperature for 12 h, the mixture was evaporated in vacuo.
The residue was washed with ether, and the precipitate
was dried in vacuo for 4 h at 60 ꢀC to give 1aꢂHCl or
1aꢂHBr.
Dicyclohexylamine Hydrochloride (1aꢂHCl). Ninety-eight
percent yield as a white solid.106 1H NMR (CD3OD, d, ppm):
1.16–1.45 (m, 10H, CH2), 1.68-1.76 (m, 2H, CH2), 1.81-1.92
(m, 4H, CH2), 2.04-2.15 (m, 4H, CH2), 3.15–3.24 (m, 2H,
NCH). 13C NMR (CD3OD, d, ppm): 25.5 (CH2), 26.1 (CH2),
30.5 (CH2), 54.5 (NCH).
Phenyl glycidyl ether (1.50 g, 10 mmol) was added to a
solution of dicyclohexylamine hydroiodide (155 mg, 0.5
mmol) in NMP (2 mL). The atmosphere inside the flask was
replaced with CO2 (balloon, ca. 1 atm), and the reaction
mixture was stirred at 45 ꢀC. The reaction progress was
1
monitored by H NMR (24 h, 90%; 48 h, >99%). After 48 h,
the mixture was cooled to rt, and was precipitated into the
water (40 mL). The precipitate was washed with water and
ꢀ
dried at 40 C in vacuo to give 5a (1.93 g, >99%) as a pale
gray powder.38
1H NMR (DMSO-d6, d, ppm): 4.19 (dd, 1H, J ¼ 11.2, 4.8
Hz, PhOCH2), 4.28 (dd, 1H, J ¼ 11.2, 2.8 Hz, PhOCH2),
4.40 (dd, 1H, J ¼ 8.4, 6.0 Hz, OCHCH2O), 4.64 (dd, 1H, J
¼ 8.4, 8.4 Hz, OCHCH2O), 5.12-5.19 (m, 1H, OCHCH2O),
6.94-7.01 (m, 3H, ArH), 7.28-7.35 (m, 2H, ArH). 13C NMR
(DMSO-d6, d, ppm): 66.0 (OCHCH2O), 67.4 (OCHCH2O),
74.8 (PhOCH2), 114.6 (Ar), 121.2 (Ar), 129.6 (Ar), 154.9
(Ar), 157.9 (C¼¼O).
Dicyclohexylamine Hydrobromide (1aꢂHBr).
Hundred percent yield as
a
white solid.107 1H NMR
(DMSO-d6, 80 ꢀC, d, ppm): 1.04–1.18 (m, 2H, CH2), 1.21-
1.47 (m, 8H, CH2), 1.57-1.66 (m, 2H, CH2), 1.72-1.81 (m,
4H, CH2), 1.99–2.08 (m, 4H, CH2), 3.06-3.18 (m, 2H,
NCH), 8.32 (brs, 2H, NH2). 13C NMR (DMSO-d6, 80 ꢀC, d,
ppm): 23.5 (CH2), 24.4 (CH2), 28.4 (CH2), 51.9 (NCH),
52.8 (NCH).
Synthesis of (2-Oxo-1,3-dioxolane-4-yl)methyl
methacrylate (5f)
Synthesis of N,N-Dimethyldicyclohexylamine Iodide
(N-Me-3aꢂI)
Glycidyl methacrylate (1.42 g, 10 mmol) was added to a
solution of dicyclohexylamine hydroiodide (155 mg, 0.5
mmol) in NMP (2 mL). The atmosphere inside the flask was
replaced with CO2 (balloon, ca. 1 atm), and the reaction
mixture was stirred at 45 ꢀC. The reaction progress was
A solution of methyl iodide (1.14 g, 8 mol) was added
dropwise for 1 min to the mixture of N-methyldicyclohex-
ylamine (781 mg, 4 mmol) in anhydrous dichloromethane (8
mL) at room temperature. After the mixture was stirred at
room temperature for 12 h, the mixture was evaporated in
vacuo. The residue was washed with ether, and the precipitate
1
monitored by H NMR (24 h, >99%). After 24 h, the mixture
was cooled to rt and was diluted with water (10 mL). The
mixture was extracted with ethyl acetate (20 mL ꢅ 3). The
combined organic layers were dried (Na2SO4), filtered,
ꢀ
was dried in vacuo for 4 h at 60 C to give N-Me-3aꢂI (1.36 g,
100%) as a white solid.108 1H NMR (CDCl3, d, ppm): 1.16-1.29
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and evaporated in vacuo to give 5f (1.74 g, 93%) as a
1H NMR (CDCl3, d, ppm): 0.84–1.37 (m, 3H, CH3), 1.44–2.17
(m, 2H, ACH2CCH3A), 2.64 (brs, 1H, OCHCH2O), 2.85 (brs,
1H, OCHCH2O), 3.24 (brs, 1H, OCHCH2O), 3.72–3.89 (m, 1H,
CO2CH2), 4.24–4.38 (m, 1H, CO2CH2). 13C NMR (CDCl3, d,
ppm): 18.1, 18.8, 44.6, 44.8, 45.1, 45.7, 53.8, 54.1, 65.6, 65.9,
yellow oil.109
1H NMR (CDCl3, d, ppm): 1.96 (t, 3H, J ¼ 1.6 Hz, CH3), 4.34
(dd, 1H, J ¼ 12.4, 4.0 Hz, OCHCH2O), 4.37 (dd, 1H, J ¼ 8.8,
5.6 Hz, CO2CH2), 4.45 (dd, 1H, J ¼ 8.4, 2.8 Hz, OCHCH2O),
4.61 (dd, 1H, J ¼ 8.8, 8.8 Hz, CO2CH2), 4.99-5.04 (m, 1H,
OCHCH2O), 5.68 (quin, 1H, J ¼ 1.6 Hz, C¼¼CHH), 6.16-6.17
(m, 1H, C¼¼CHH). 13C NMR (CDCl3, d, ppm): 18.1 (CH3), 63.4
(OCHCH2O), 66.0 (OCHCH2O), 73.8 (CO2CH2), 127.3 (C¼¼CH2),
135.0 (C¼¼CH2), 154.5 (CO3), 166.6 (CO2).
128.2, 129.0, 176.1, 176.4, 176.9, 177.3. GPC (DMF): Mn
9070 (Mw/Mn ¼ 2.42).
¼
Synthesis of Poly(glycidyl methacrylate-co-methyl
methacrylate) (4l)
Synthesis of 2,2-Bis[4-(1,3-dioxolane-2-one-4-ylmethoxy)-
phenyl]propane (5j)
Copolymer 4l was prepared by the same procedure as 4k,
except using glycidyl methacrylate (2.84 g, 20 mmol) and
methyl methacrylate (2.00 g, 20 mmol). After purification, 4l
(4.74 g, 98%) was obtained as a white powder.111
1H NMR (CDCl3, d, ppm): 0.84–1.35 (m, 6H, CH3, CH3), 1.36–
2.26 (m, 4H, ACH2CCH3A, ACH2CCH3A), 2.64 (brs, 1H, OCH-
CH2O), 2.85 (brs, 1H, OCHCH2O), 3.23 (brs, 1H, OCHCH2O),
3.60 (brs, 3H, CO2CH3), 3.73–3.89 (m, 1H, CO2CH2), 4.23–
4.47 (m, 1H, CO2CH2). 13C NMR (CDCl3, d, ppm): 16.5, 18.6,
18.8, 23.4, 30.2, 30.3, 44.6, 44.8, 45.0, 48.8, 48.9, 51.8, 54.3,
65.5, 65.8, 176.2, 176.8, 177.0, 177.3, 177.7, 178.0. GPC
(DMF): Mn ¼ 3,000 (Mw/Mn ¼ 2.54).
Bisphenol A diglycidyl ether (3.40 g, 10 mmol) was added to a
solution of dicyclohexylamine hydroiodide (309 mg, 1 mmol, 5
mol% based on the epoxy group) in NMP (4 mL). The atmosphere
inside the flask was replaced with CO2 (balloon, ca. 1 atm), and the
mixture was stirred at 45 ꢀC. The reaction progress was
monitored by 1H NMR (24 h, 97%; 48 h, >99%). After 48 h, the
mixture was cooled to rt, and was precipitated into the water (80
mL). The precipitate was washed with water and dried at 80 ꢀC in
vacuo to give 5j (4.26 g, >99%) as a white powder.110
Synthesis of Poly(4-vinylbenzyl glycidyl ether) (4m)
1H NMR (DMSO-d6, d, ppm): 1.58 (s, 6H, C(CH3)2), 4.16 (dd,
2H, J ¼ 11.0, 4.8 Hz, 2(ArOCH2)), 4.24 (dd, 2H, J ¼ 11.0, 2.4
Hz, 2(ArOCH2)), 4.38 (dd, 2H, J ¼ 8.0, 6.0 Hz, 2(OCHCH2O)),
4.62 (dd, 2H, J ¼ 8.4, 8.4 Hz, 2(OCHCH2O)), 5.11-5.17 (m,
2H, 2(OCHCH2O)), 6.85 (d, 4H, J ¼ 8.4 Hz, ArH), 7.12 (d, 4H,
J ¼ 8.8 Hz, ArH). 13C NMR (DMSO-d6, d, ppm): 30.7
(C(CH3)2), 41.2 (C(CH3)2), 66.0 (OCHCH2O), 67.4 (OCHCH2O),
74.8 (PhOCH2), 114.0 (Ar), 127.5 (Ar), 143.3 (Ar), 154.8
(Ar), 155.7 (C¼¼O).
The mixture of 4-vinylbenzyl glycidyl ehter (7.61 g, 40 mmol),
AIBN (328 mg, 2 mmol), and toluene (40 mL) was degassed by
three freeze-evacuate-thaw cycles, and was stirred at 80 ꢀC.
After 24 h, the mixture was evaporated, residue was dissolved
in THF, and was precipitated into the methanol (200 mL). The
suspension was stirred for a further 30 min. The precipitate
was washed with methanol and dried at 40 ꢀC in vacuo to give
4m (6.15 g, 81%) as a colorless syrup.112
Synthesis of Poly(glycidyl methacrylate) (4k)
The mixture of glycidyl methacrylate (5.69 g, 40 mmol), AIBN
(328 mg, 2 mmol), and toluene (40 mL) was degassed by three
freeze-evacuate-thaw cycles, and was stirred at 70 ꢀC. After 12
h, the mixture was cooled to rt, and was precipitated into the
methanol (200 mL). The suspension was stirred for a further 30
min. The precipitate was washed with methanol and dried at 40
ꢀC in vacuo to give 4k (5.79 g, 97%) as a white powder.111
1H NMR (CDCl3, d, ppm): 0.78–1.37 (m, 3H, CH3), 1.44–2.24
(m, 3H, CH2CH), 2.59 (brs, 1H, OCHCH2O), 2.78 (brs, 1H,
OCHCH2O), 3.17 (brs, 1H, OCHCH2O), 3.41 (brs, 1H, ArCH2-
OCH2), 3.74 (brs, 1H, ArCH2OCH2), 4.31–4.77 (m, 2H, ArCH2),
6.16-7.45 (m, 4H, ArH). 13C NMR (DMSO-d6, d, ppm): 40.0,
40.3, 44.2, 50.8, 70.8, 73.1, 127.4, 127.5, 135.1, 144.5. GPC
(DMF): Mn ¼ 4,640 (Mw/Mn ¼ 1.88).
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Synthesis of Poly(4-vinylbenzyl glycidyl ether-co-styrene)
(4n)
5.08 (brs, OCHCH2O in carbonate unit). 13C NMR (DMSO-d6,
d, ppm): 16.6, 18.0, 18.3, 29.0, 30.1, 43.8, 44.1, 44.5, 48.5,
52.9, 53.1, 64.6, 65.7, 65.8, 66.2, 73.9, 154.7, 175.8, 176.3,
176.6. GPC (DMF): Mn ¼ 11,100 (Mw/Mn ¼ 2.49).
By using dicyclohexylamine hydroiodide as a catalyst (5 mol %),
completed reaction mixture (24 h) was added dropwise to the
water (15 mL). The precipitate was washed with water and dried
at 50 ꢀC in vacuo to give 5k (177 mg, 95%) as a white powder.
1H NMR (DMSO-d6, d, ppm): 0.67–1.39 (m, 3H, CH3), 1.40-
2.18 (m, 2H, ACH2CCH3A), 3.98–4.46 (m, 3H, OCHCH2O,
CO2CHH), 4.63 (brs, 1H, CO2CHH), 5.09 (brs, 1H, OCHCH2O).
13C NMR (DMSO-d6, d, ppm): 16.6, 18.1, 44.1, 44.5, 52.9,
64.5, 66.2, 73.9, 154.7, 175.5, 176.2, 176.5. GPC (DMF): Mn
¼ 11,500 (Mw/Mn ¼ 2.52).
Copolymer 4n was prepared by the same procedure as 4m,
except using 4-vinylbenzyl glycidyl ether (3.80 g, 20 mmol)
and styrene (2.08 g, 20 mmol). After purification, 4n (3.75 g,
64%) as a white powder.112
Synthesis of Poly(1,3-dioxolane-2-one-4-ylmethyl
methacrylate-co-methyl methacrylate) (5l)
1H NMR (CDCl3, d, ppm): 0.72-2.22 (m, 6H, CH3), 1.44–2.24
(m, 6H, CH2CH, CH2CH), 2.59 (brs, 1H, OCHCH2O), 2.78 (brs,
1H, OCHCH2O), 3.17 (brs, 1H, OCHCH2O), 3.40 (brs, 1H,
ArCH2OCH2), 3.72 (brs, 1H, ArCH2OCH2), 4.26-4.77 (m, 2H,
ArCH2), 6.19–7.49 (m, 9H, ArH). 13C NMR (DMSO-d6, d,
ppm): 40.2, 44.2, 50.8, 70.7, 125.7, 127.5, 127.8, 128.3,
135.0, 145.0. GPC (DMF): Mn ¼ 4,260 (Mw/Mn ¼ 1.79).
Synthesis of Poly(1,3-dioxolane-2-one-4-ylmethyl
methacrylate) (5k)
Dicyclohexylamine hydroiodide (16 mg, 0.05 mmol) was
added to a solution of poly(glycidyl methacrylate-co-methyl
methacrylate) (242 mg, 1 mmol) in NMP (0.2 mL). The
atmosphere inside the flask was replaced bꢀy CO2 (balloon, ca.
1 atm), and the mixture was stirred at 45 C. After 24 h, the
mixture was added dropwise to the water (15 mL). The
precipitate was washed with water and dried at 50 ꢀC in vacuo
to give 5l (286 mg, >99%) as a white powder.94
Dicyclohexylamine hydroiodide (16 mg, 0.05 mmol) was added
to a solution of poly(glycidyl methacrylate) (142 mg, 1 mmol) in
NMP (0.2 mL). The atmosphere inside the flask was replacedꢀby
CO2 (balloon, ca. 1 atm), and the mixture was stirred at 45 C.
After 24 h, the mixture was cooled to rt, and was diluted with the
methanol (15 mL). The suspension was sonicated for a further
60 min. The precipitate was washed with methanol and dried at
40 ꢀC in vacuo to give 5k (171 mg, 92%) as a white solid.94
1H NMR (DMSO-d6, d, ppm): 0.58–1.39 (m, 6H, CH3, CH3),
1.41-2.14 (m, 4H, ACH2CCH3A, ACH2CCH3A), 3.43–3.68 (m,
3H, CO2CH3), 3.95–4.46 (m, 3H, OCHCH2O, CO2CHH), 4.63
(brs, 1H, CO2CHH), 5.08 (brs, 1H, OCHCH2O). 13C NMR
(DMSO-d6, d, ppm): 16.3, 17.9, 18.5, 43.9, 44.1, 44.5, 51.7,
53.5, 64.7, 66.2, 73.8, 154.7, 175.5, 176.4, 177.1. GPC (DMF):
Mn ¼ 3,520 (Mw/Mn ¼ 2.61).
1H NMR (DMSO-d6, d, ppm): 0.67-1.36 (m, 3H, CH3), 1.37–
2.20 (m, 2H, ꢃCH2CCH3-), 4.01–4.46 (m, 3H, OCHCH2O,
CO2CHH), 4.63 (brs, 1H, CO2CHH), 5.09 (brs, 1H, OCHCH2O).
13C NMR (DMSO-d6, d, ppm): 16.3, 16.6, 17.9, 18.3, 23.9,
44.1, 44.5, 53.1, 64.6, 66.2, 73.9, 154.7, 175.5, 176.3, 176.4.
GPC (DMF): Mn ¼ 12,000 (Mw/Mn ¼ 2.41).
Synthesis of Poly[4-((4-vinylbenzyloxy)methyl)-1,3-dioxo-
lane-2-one] (5m)
By using LiBr as a catalyst (5 mol %), 5k was isolated (157
mg, 93%) as the white solid mixture of carbonate and epoxy
group (61:39).94
1H NMR (DMSO-d6, d, ppm): 0.61–1.40 (m, CH3 in carbonate
unit, CH3 in epoxy unit), 1.41–2.14 (m, ꢃCH2CCH3ꢃ in car-
bonate unit, ꢃCH2CCH3ꢃ in epoxy unit), 2.67 (brs, OCHCH2O
in epoxy unit), 2.81 (brs, OCHCH2O in epoxy unit), 3.22 (brs,
OCHCH2O in epoxy unit), 3.69–3.84 (m, CO2CH2 in epoxy
unit), 3.85–4.48 (m, OCHCH2O, CO2CHH in carbonate unit,
CO2CH2 in epoxy unit), 4.62 (brs, CO2CHH in carbonate unit),
Cyclic carbonate-bearing polymer 5m was prepared by the
same procedure as 5l, except using poly(4-vinylbenzyl
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REFERENCES AND NOTES
glycidyl ether) (190 mg, 1 mmol). After purification, 5m
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1H NMR (DMSO-d6, d, ppm): 0.79–2.17 (m, 3H, CH2CH),
3.58–3.77 (m, 2H, ArCH2OCH2), 4.22–4.63 (m, 4H, OCHCH2O,
ArCH2), 4.93 (brs, 1H, OCHCH2O), 6.21–7.30 (m, 4H, ArH).
13C NMR (DMSO-d6, d, ppm): 26.9, 31.3, 66.1, 69.1, 72.2,
72.3, 75.4, 127.1, 135.0, 144.1, 155.0. GPC (DMF): Mn
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