Download Supporting Information for: Stereospecific Cationic Polymerization of

Supporting Information for:
Stereospecific Cationic Polymerization of Vinyl Ethers Using Iron(II) Sulfate:
A Stepping Stone to Stereospecific Living Cationic Polymerization
ARIHIRO KANAZAWA, SHOKYOKU KANAOKA, and SADAHITO AOSHIMA*
Department of Macromolecular Science, Graduate School of Science, Osaka University,
Toyonaka, Osaka 560-0043, Japan
Contents:
Experimental Section
Table S1. Cationic polymerization of IBVE using FeSO4
Chart S1. Structures of vinyl ethers examined in the present study.
Figure S1. MWD curves for poly(VE)s obtained using FeSO4
Figure S2. 13C NMR spectra of poly(VE)s obtained using FeSO4 or soluble metal halides
Table S2. Cationic polymerization of IBVE using FeSO4 with various alcohols, protic acids, or
cationogen
Figure S3. MWD curves for poly(IBVE)s obtained using FeSO4 with IBVE–HCl and those before
and after MEK-fractionation
Figure S4. MWD curves for poly(IBVE)s obtained in the monomer addition experiment using
FeSO4 with tBuOH
Figure S5. 1H NMR spectra of poly(IBVE)s with various end structures obtained with the
IBVE–HCl/ZrCl4 initiating system using iBuOH, MeOH, iPrOH, and tBuOH as a quencher, and
those obtained with FeSO4
References
- S1 -
Experimental Section
Materials.
Ethyl vinyl ether (EVE; TCI; >98.0%), isopropyl vinyl ether (IPVE; Wako; 97.0%),
2,3-dihydrofuran (DHF; Aldrich; 99%), 3,4-dihydro-2H-pyran (DHP; Aldrich; 97%), phenyl acetate
(Nacalai Tesque; 98%), and triethyl phosphate (TCI; >98.0%) were distilled twice over calcium
hydride before use. Cyclohexyl vinyl ether (CHVE; TCI; >95.0%), 2-methoxyethyl vinyl ether
(MOVE; Maruzen Petrochemical; 99.9%), 2-ethoxyethyl vinyl ether (EOVE; Maruzen
Petrochemical; 99.9%), methyl 2-propenyl ether (MPE; Aldrich; 97%), and ethylene glycol diethyl
ether (EGE; Aldrich; 98%) were distilled over calcium hydride and then sodium. 1,4-Dioxane
(Wako; >99.5%), tetrahydrofuran (THF; Wako; >99.5%), and diethyl ether (Wako; >99.5%) were
distilled over calcium hydride and then lithium aluminum hydride. Hexane (Wako; >96.0%) was
dried using solvent purification columns (Glass Contour). Benzophenone (TCI; >99.0%) was
recrystallized twice with hexane. For ethylene glycol, which is almost insoluble in toluene, a stock
solution in 1,4-dioxane was prepared from anhydrous ethylene glycol (Wako; 99.5%; H2O <50ppm).
1,1,1,3,3,3-hexafluoro-2-propanol (HFIP; Fluorochem; 99.9%) was distilled over molecular sieve
4A. Ethanesulfonic acid (Aldrich; >95%), trifluoroacetic acid (Nacalai Tesque; 99%), and
2,6-di-isopropylphenol (TCI; >98.0%) were used without further purification.
- S2 -
Table S1. Cationic polymerization of IBVE using FeSO4a
entry solvent
additive
temp (ºC) time (h) conv. (%) Mn × 10-3 b Mw × 10-3 b
Mw/Mnb
MEK-insol. (%)c
1
toluene
–
0
9
39
11.7
286
24.5
15
2d
toluene
–
0
27
29
9.0
292
32.5
13
3e
toluene
–
0
9
65
11.1
318
28.8
15
4
toluene
–
–30
46
26
12.0
314
26.2
11
5
toluene
–
30
3
85
10.9
196
18.0
16
6
toluene
–
60
0.6
89
4.2
15.6
10
7
hexane
–
0
9.6
52
10.7
23.5
17
8
DCM
–
0
4
53
9.2
71.2
7.74
6
9
DCE
–
0
4
68
16.6
56.7
3.42
~0
64.8
251
10
toluene
DTBP 5.0 mM
0
28
29
7.3
291
39.7
15
11
toluene
DTBP 20 mM
0
28
20
9.1
337
37.0
19
12
toluene
nBu4NCl 0.1 mM
0
8.7
1
–
–
–
–
13
toluene
ethyl acetate 1.0 M
0
9
26
5.9
170
28.8
10
14f
toluene
phenyl acetate 1.0 M
0
7
67
9.9
147
14.9
7
15
toluene
diethyl ether 1.0 M
0
8
75
8.5
111
13.0
13
16
toluene
1,4-dioxane 1.0 M
0
8
37
8.1
92.3
11.5
6
17
toluene
THF 1.0 M
0
28
17
4.1
67.7
16.4
13
18f
toluene
EGE 1.0 M
0
10
34
6.9
104
15.0
12
19f
toluene
benzophenone 1.0 M
0
4
79
10.2
153
15.0
6
20f
toluene
triethyl phosphate 1.0 M
0
8.7
0
–
–
–
–
a
[IBVE]0 = 0.76 M, [FeSO4]0 = 2.6 mol% to IBVE, [heptane] = 5 vol% (DCM: dichloromethane, DCE:
1,2-dichloroethane).
b
By GPC (polystyrene calibration).
c
Ratios of the MEK-insoluble fractions.
d
[FeSO4]0 = 0.7 mol% to IBVE.
e
[FeSO4]0 = 6.5 mol% to IBVE.
f
The reaction solutions were stirred overnight before initiation.
- S3 -
Chart S1. Structures of vinyl ethers examined in the present study.
- S4 -
Figure S1. MWD curves for poly(VE)s obtained using FeSO4 {[FeSO4]0 = 2.6 mol% to IBVE,
[heptane] = 5 vol% (except for B and D), in toluene at 0 ºC}.
- S5 -
Figure S2. 13C NMR spectra of poly(VE)s obtained using FeSO4 (upper spectra) or soluble metal
halides (lower ones) {in CDCl3 at 30 ºC, 125 MHz [100 MHz for poly(IPVE) and poly(CHVE)
obtained using Et1.5AlCl1.5]; see references 17, S1–S3 for the assignments; the peaks in the spectra
of poly(CHVE) have not been suitably assigned; conditions for the polymerization using metal
halides (see Figure S1 for those using FeSO4): (A) [EVE]0 = 0.73 M, [IBVE–HCl]0 = 4.0 mM,
[ZrCl4]0 = 5.0 mM, [ethyl acetate] = 1.0 M, in toluene at 0 ºC, (B) [IPVE] 0 = 0.80 M,
[IBVE–AcOH]0 = 4.0 mM, [Et1.5AlCl1.5]0 = 10 mM, [ethyl acetate] = 1.0 M, in toluene at 0 ºC, (C)
[CHVE]0 = 0.80 M, [IBVE–AcOH]0 = 4.0 mM, [Et1.5AlCl1.5]0 = 10 mM, [ethyl acetate] = 1.0 M, in
toluene at 0 ºC, (D) [MOVE]0 = 1.0 M, [MOVE–AcOH]0 = 10 mM, [Et1.5AlCl1.5]0 = 20 mM,
[1,4-dioxane] = 1.2 M, in toluene at 0 ºC, (E) [EOVE]0 = 0.75 M, [IBVE–AcOH]0 = 4.0 mM,
[Et1.5AlCl1.5]0 = 20 mM, [ethyl acetate] = 1.0 M, in toluene at 0 ºC, (F) [MPE]0 = 0.84 M,
[IBVE–AcOH]0 = 4.0 mM, [Et1.5AlCl1.5]0 = 20 mM, [ethyl acetate] = 1.0 M, in toluene at –78 ºC}.
- S6 -
Figure S2. (continued)
- S7 -
Table S2. Cationic polymerization of IBVE using FeSO4 with various alcohols, protic acids, or
cationogena
entry
alcohol, protic acid, or cationogen
time
conv.
Mn × 10-3 b
Mw ×
MEK-insol.
Mw/Mnb
1
MeOH 20 mM
(h)
8
(%)
64
9.8
10-3 b
134
2
MeOH 100 mM
8.5
3
–
–
–
–
3
iPrOH 20 mM
8
44
9.1
200
22.1
13
4
iPrOH 100 mM
8
56
7.6
168
22.1
15
5
tBuOH 20 mM
6
81
9.0
155
17.2
14
6
tBuOH 100 mM
8
68
5.6
13.5
13
7
8
HFIP 20 mM
2,6-di-isopropylphenol 20 mM
8
8
41
43
12.7
7.7
177
210
13.9
27.3
11
13
9
ethylene glycol 20 mM
6
0
–
–
–
–
10
ethanesulfonic acid 20 mM
1
80
5.8
158
27.5
9
11d
trifluoroacetic acid 20 mM
6
76
9.2
115
12.5
12e
IBVE–HCl 4.0 mM
8
27
a
5.7 (2.1)
75.8
f
124
c
(%)13
13.7
21.9 (1.28)
10
f
6
[IBVE]0 = 0.76 M, [FeSO4]0 = 2.6 mol% to IBVE, [alcohol, acid, or cationogen]0 = 4.0, 20 or 100 mM,
[heptane] = 5 vol%, in toluene at 0 ºC.
b
By GPC (polystyrene calibration).
c
Ratios of the MEK-insoluble fractions.
d
The reaction solutions were stirred overnight before initiation.
e
[FeSO4]0 = 0.7 mol% to IBVE, [ethyl acetate] = 1.0 M; see Figure S3 for the MWD curves.
f
Values in the parentheses are for a sharp peak.
- S8 -
Figure S3. MWD curves for (A) poly(IBVE)s obtained using FeSO4 with IBVE–HCl and (B) those
before and after MEK-fractionation ([IBVE]0 = 0.76 M, [IBVE–HCl]0 = 4.0 mM, [FeSO4]0 = 0.7
mol% to IBVE, [ethyl acetate] = 1.0 M, [heptane] = 5 vol%, in toluene at 0 ºC).
- S9 -
Figure S4. MWD curves for poly(IBVE)s obtained in the monomer addition experiment using
FeSO4 with tBuOH ([IBVE]0 = [IBVE]added = 0.76 M, [FeSO4]0 = 2.6 mol% to IBVE, [tBuOH]0 =
100 mM, [heptane] = 5 vol%, in toluene at 0 ºC).
- S10 -
Figure S5. 1H NMR spectra of poly(IBVE)s with various end structures obtained with the
IBVE–HCl/ZrCl4 initiating system using (A) iBuOH, (B) MeOH, (C) iPrOH, and (D) tBuOH as a
quencher, and (E)–(H) those obtained with FeSO4 {in CDCl3 at 30 ºC, 500 MHz; polymerization
conditions for A–D (see Table S2 for E–H): [IBVE]0 = 0.76 M, [IBVE–HCl]0 = 10 mM, [ZrCl4]0 =
5.0 mM, [ethyl acetate] = 1.0 M, in toluene at 0 ºC}.
- S11 -
References
(S1)
(a) Takaku, R. Master’s Thesis, Osaka University, 2007. (b) Yonezumi, M.; Takaku, R.;
Kanaoka, S.; Aoshima, S. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 2202–2211.
(S2)
Matsuzaki, K.; Okuzono, S.; Kanai, T. J. Polym. Sci. Polym. Chem. Ed. 1979, 17,
3447–3458.
(S3)
Hatada, K.; Kitayama, T.; Matsuo, N.; Yuki, H. Polym. J. 1983, 15, 719–725.
- S12 -