Electronic Supplementary Material (ESI) for Polymer Chemistry.
This journal is © The Royal Society of Chemistry 2014
Polymerization procedure of diblock copolymer P1-P2(m-141) by catalyst transfer
polymerization.
All reactions were performed in a dry box under Ar atmosphere. To P2(141) THF solution,
the second monomer, 1 treated with iPrMgCl·LiCl complex (1.3 M solution in THF) was
added and stirred at room temperature for 30 h. The reaction was quenched with HCl
aq./methanol. The insoluble material was washed with methanol and collected by suction
filtration. The residue was reprecipitated from chloroform solution into acetone/methanol to
give P1-P2(m-141) as a pale pink solid. Detailed synthetic condition was shown in Table S1.
Table S1. Synthesis condition of P1-P2(m-141).
Monomer Ni(dppe)Cl2 THF Monomer/ Ni(dppe)Cl2 Yield / g (%)
Sample
/ mmol / g (mmol) / ml
2.63
P1-P2(34-141)
5.40
0.0758
300
71
(47)
1.88
P1-P2(44-141)
5.40
0.0606
300
89
(48)
2.44
P1-P2(62-141)
6.48
0.0530
300
122
(48)
Synthesis of diblock copolymer ionomers SP1-P2(m-141).
The neopentyl protected sulfonyl group in P1-P2(m-141) was cleaved with an Nmethylpyrrolidone solution of diethylamine hydrobromide at 120 ºC for 48 h to obtain the
acid form of the copolymer SP1-P2(m-141).
After cooling to room temperature, the
reaction mixture was poured into diethyl ether. The insoluble material was collected by
suction filtration. The product was stirred in 1 M HCl aq for 48 h and in water for 24 h to
give SP1-P2(m-141) as a brown solid.
Sample
SP1-P2(34-141)
Table S2. Synthesis condition of SP1-P2(m-141).
P1-P2 / g
(C2H5)2NH HBr / g NMP / ml Yield /g (%)
(mmol)
2.10
1.88 (12.2)
40.0
1.22 (63)
SP1-P2(44-141)
1.60
1.58 (10.3)
20.0
0.716 (49)
SP1-P2(62-141)
1.90
2.45 (15.9)
20.0
1.47 (88)
(a) H
P2(141)
141
(a) Mn = 34,800、 Mw = 39,100
Mw / Mn = 1.12
(b) H
NSBu34
P1-P2(34-141)
141
(b) Mn = 51,000、 Mw = 61,700
Mw / Mn = 1.21
(c) H
NSBu44
P1-P2(44-141)
141
(c) Mn = 58,700、 Mw = 68,900
Mw / Mn = 1.17
P1-P2(62-141)
(d) H
NSBu62
141
12
14
16
time / min
18
(d) Mn = 67,200、 Mw = 80,500
Mw / Mn = 1.20
Figure S1. GPC profiles of P2(141) and P1-P2(m-141) in THF.
a
d
e
b c
OCH2CH2CH2CH2CH2CH3
f
j
h
g
i
OCH2CH2CH2CH2
Br
C6H13O
141
k
RO3S
j
k
l
m
SO3CH2C(CH3)3
H
62
C4H8O
R = CH2C(CH3)3
a
c, h
f
8.0 7.8 7.6 7.4 7.2 7.0 6.8
2.0
m
e
d
1.5
1.0
THF
0.5
THF
H2O
b
8.0
6.0
l
i
g
4.0
ppm
2.0
0.0
Figure S2. 1H NMR spectrum of P1-P2(62-141) in THF-d8.
o p
g h i
j k l m
d e f
r s t
q
n
OCH
CH
CH
CH
CH
CH
OCH
CH
CH
CH
SO
CH
2
2
2
2
2
3
2
2
2
2
3
2C(CH3)3
b c
b c
a
a
Br
H
141
62
C6H13O
RO3S
C4H8O
R = CH2C(CH3)3
THF
t
r
g
d
j
80
75
70
m
40
35
f
160.0
q
140.0
h
ke
l s
30
o p, a
cn
THF
i
25
20
r
d
b
120.0
100.0
80.0
ppm
60.0
40.0
Figure S3. 13C NMR spectrum of P1-P2(62-141) in THF-d8.
20.0
0.0
d
e
b c
OCH2CH2CH2CH2CH2CH3
a
j
h
g
i
OCH2CH2CH2CH2
f
Br
141
C6H13O
RO3S
C4H8O
c, h
j
8.0 7.8 7.6 7.4 7.2 7.0 6.8
2.0
e
d
1.5
1.0
THF
SO3H+H2O
8.0
6.0
SO3H
H
62
a, f
k
k
0.5
THF
b, g
i
4.0
ppm
2.0
0.0
Figure S4. 1H NMR spectrum of SP1-P2(62-141) in THF-d8.
g h i
j k l m
d e f
n
OCH
CH
CH
CH
CH
CH
OCH
c
2
2
2
2
2
3
2CH2CH2CH2
b
b c
a
a
Br
H
141
62
C6H13O
RO3S
C4H8O
o p
q
THF
g
d
80
75
c
160.0
70
q
140.0
SO3H
THF
h
f
i
e
40
opq
35
30
25
d
b
120.0
20
100.0
80.0
ppm
60.0
40.0
20.0
Figure S5. 13C NMR spectrum of SP1-SP2(62-141) in THF-d8.
0.0
0.5
Absorbance
0.4
0.3
0.2
0.1
0.0
3500
3000
2500
2000
Wavenumber / cm-1
1500
1000
1500
1000
Figure S6. FT-IR spectrum of P1-P2(141-62).
Absorbance
0.3
0.2
0.1
0.0
3500
3000
2500
2000
Wavenumber / cm-1
Figure S7. FT-IR spectrum of SP1-P2(141-62).
Mn = 45,000
Mw = 134,000
Mw/ Mn = 2.97
10
Figure S8.
12
14 16
time / min
18
GPC profile of S-PPBP.
20