Supporting Information for:
Synthesis of Graft Copolymers Based on Selective Living Cationic
Polymerization Using an Acetal Group with a Combination of Lewis
Acids
Hiroaki Shimomoto, Hirotoshi Yoshida, Shokyoku Kanaoka, and Sadahito
Aoshima*
Department of Macromolecular Science, Graduate School of Science, Osaka
University, Toyonaka, Osaka 560-0043, Japan
* aoshima@chem.sci.osaka-u.ac.jp
Table S1. Copolymerization of DMEVE and IBVE with ZnCl2a
DMEVE
time
(mM)
a
conv.
Mn × 10-3
Mw/Mn
(%)
20
40 min
91
15.6
1.11
40
30 min
70
12.5
1.16
80
40 min
63
13.0
1.14
80
2h
87
15.4
1.19
[DMEVE]0 = 20-80 mM, [IBVE]0 = 0.76 M, [IBVE-HCl]0 = 4.0 mM, [ZnCl2]0 = 5.0
mM, [ethyl acetate] = 1.0 M, in toluene at 0 ºC.
Figure S1. 1H NMR spectrum of poly(DMEVE-r-IBVE) obtained with Et1.5AlCl1.5.
Figure S1 shows the spectrum of the polymer obtained with Et1.5AlCl1.5 (Table1, entry
6). The termination reaction was conducted using LiBH4 to produce H-terminated
polymers, since the normal methanol-quenching method produced the terminal acetal
group, which would also initiate cationic polymerization with an appropriate metal
halide as well as pendant acetal groups. The spectrum shows characteristic signals of
the monomers, methyl protons of IBVE (l) at 0.9 ppm, main-chain methylene (a, h)
and methine proton of IBVE (k) at 1.5-1.8 ppm, methine proton of DMEVE (f) at 4.5
ppm, and other methylene or methine protons adjacent with O atom (b,c,d,e,g,i,j) of
IBVE and DMEVE at 3.1-3.6 ppm. The peak intensity ratio of the acetal methine (P) to
the methylene or main-chain methine protons (Q-R/2) of DMEVE was 0.97/13, close
to the calculated values (1/13) assuming that the acetal moieties are intact.
Table S2. Cationic polymerization of IBVE with various metal halides using TME as
an initiatora
a
metal halide
time
conv. (%)
Mn × 10-3
Mw/Mn
ZnCl2
24 h
0
-
-
SnCl4
5 min
85
22.2
1.19
EtAlCl2
24 h
62
45.6
1.32
[IBVE]0 = 0.76 M, [TME]0 = 4.0 mM, [metal halide]0 = 5.0 mM (ZnCl2 and SnCl4)
or 10 mM (EtAlCl2), [ethyl acetate] = 1.0 M, in toluene at 0 ºC.
Figure S2. 1H NMR spectra of (DMEVE8-r-IBVE150)-g-IBVE120 (lower) and the linear
prepolymer (upper).
Figure S3. SEC curves for the synthesis of (A) (DMEVE8-r-IBVE150)-g-MOVE30 and
(B) (DMEVE8-r-MOVE150)-g-IBVE10 {(DMEVE8-r-IBVE150)-g-MOVE30: [DMEVE]0
= 40 mM, [IBVE]0 = 0.76 M, [IBVE-HCl]0 = 4.0 mM, [Et1.5AlCl1.5]0 = 10 mM, [ethyl
acetate] = 1.0 M, in toluene at 0 ºC, conv. = 80% (for the linear polymer), [MOVE]0 =
0.58 M, [acetal units of the prepolymer]0 = 6.0 mM, [TiCl4]0 = 20 mM, [DTBP] = 20
mM, [ethyl acetate] = 1.0 M, in DCM at 0 ºC, conv. = 43% (for the graft polymer);
(DMEVE8-r-MOVE150)-g-IBVE10: [DMEVE]0 = 40 mM, [MOVE]0 = 0.80 M,
[IBVE-HCl]0 = 4.0 mM, [Et1.5AlCl1.5]0 = 10 mM, [ethyl acetate] = 1.0 M, in toluene at
0 ºC, conv. = 77% (for the linear polymer), [IBVE]0 = 0.76 M, [acetal units of the
prepolymer]0 = 6.0 mM, [TiCl4]0 = 20 mM, [DTBP] = 20 mM, [ethyl acetate] = 1.0 M,
in DCM at 0 ºC, conv. = 20% (for the graft polymer); * for the graft copolymer}.
Figure S4. Turbidity measurement of (DMEVE8-r-IBVE150)-g-MOVE30 in water (0.1
wt%, heating rate: 1 ºC/min).