Supporting information
Cyclopolymerization of α,ω-Heterodifunctional Monomers Containing Styrene and
Maleimide Moieties
Lei Zou,† Jian’an Liu,‡ Yongming Chen,*† Fu Xi†
1. Experiments and data
Synthesis of S3EG: A mixture of triethylene glycol (33 g, 0.22mol), 4-vinylbenzyl
chloride (3.38 g, 90%, 0.02mol), NaOH (0.8 g, 0.02mol), H2O (0.36 g, 0.02mol) and
2,6-di-tert-butylphenol (0.02eq. to 4-vinylbenzyl chloride) was stirred at 70 ºC for 24 h.
The mixture was diluted with 200mL of water, and extracted with 100mL of
dichloromethane for three times. The dichloromethane extracts were combined, washed
with 100mL of brine for three times, dried over MgSO4, and concentrated. The product
was purified by column chromatography (petrol ether/ethyl acetate, 2/1 (v/v)) as a
viscous liquid (4.0 g, yield 75%). 1H-NMR (400MHz, CDCl3) δ (ppm) 3.62-3.75 (m,
12H), 4.56 (s, 2H), 5.23 (d, 1H, J = 9 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.71 (q, 1H, J1= 9
Hz, J2= 17.6 Hz,), 7.29 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
SEG: 1H-NMR (400MHz, CDCl3) δ (ppm) 3.60 (t, 2H, J = 4.7 Hz), 3.76 (t, 2H, J = 4.7
Hz), 4.56 (s, 2H), 5.25 (d, 1H, J = 10 Hz), 5.75 (d, 1H, J = 17.6 Hz), 6.71 (q, 1H, J1= 10
Hz, J2= 17.6 Hz), 7.30 (d, 2H, J = 8.5 Hz), 7.40 (d, 2H, J = 8.5 Hz).
SEGT: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.43 (s, 3H), 3.65 (t, 2H, J = 4.8 Hz), 4.20 (t,
2H, J = 4.8 Hz), 4.46 (s, 2H), 5.25 (d, 1H, J = 11 Hz), 5.75 (d, 1H, J = 17.6 Hz), 6.71 (q,
1H, J1= 11 Hz, J2= 17.6 Hz), 7.21 (d, 2H, J = 8 Hz), 7.30 (d, 2H, J = 8 Hz), 7.36 (d, 2H, J
= 8.5 Hz), 7.79 (d, 2H, J = 8.5 Hz).
SEGMF: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.83 (s, 2H), 3.62 (t, 2H, J = 5.7 Hz), 3.74
(t, 2H, J = 5.7 Hz), 4.49 (s, 2H), 5.23 (d, 1H, J = 9 Hz), 5.27 (s, 2H), 5.73 (d, 1H, J =
17.6 Hz), 6.50 (s, 2H), 6.70 (q, 1H, J1= 9 Hz, J2= 17.6 Hz,), 7.25 (d, 2H, J = 8.5 Hz), 7.36
(d, 2H, J = 8.5 Hz).
S1
SEGM: 1H-NMR (400MHz, CDCl3) δ (ppm) 3.62 (t, 2H, J = 5.7 Hz), 3.74 (t, 2H, J = 5.7
Hz), 4.52 (s, 2H), 5.23 (s, H, J = 11 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.66 (s, 2H), 6.70 (q,
1H, J1= 11 Hz, J2= 17.6 Hz), 7.28 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
S2EG: 1H-NMR (400MHz, CDCl3) δ (ppm) 3.61 (m, 4H), 3.71 (m, 4H), 4.56 (s, 2H),
5.24 (d, 1H, J = 11 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.71 (q, 1H, J1= 11 Hz, J2= 17.6 Hz),
7.30 (d, 2H, J = 8.5 Hz), 7.39 (d, 2H, J = 8.5 Hz).
S2EGT: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.43 (s, 3H), 3.56 (m, 4H), 3.70 (t, 2H, J =
4.7 Hz), 4.17 (t, 2H, J = 4.7 Hz), 4.51 (s, 2H), 5.24 (d, 1H, J = 11 Hz), 5.74 (d, 1H, J =
17.6 Hz), 6.71 (q, 1H, J1= 11 Hz, J2= 17.6 Hz), 7.26- 7.30 (m, 4H), 7.38 (d, 2H, J = 8.5
Hz), 7.79 (d, 2H, J = 8.5 Hz).
S2EGMF: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.77 (s, 2H), 3.56-3.71 (m, 8H), 4.51 (s,
2H), 5.22 (s, 2H), 5.23 (d, 1H, J = 11 Hz), 5.73 (d, 1H, J = 17.6 Hz), 6.47 (s, 2H), 6.71 (q,
1H, J1= 11 Hz, J2= 17.6 Hz,), 7.29 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
S2EGM: 1H-NMR (400MHz, CDCl3) δ (ppm) 3.56-3.75 (m, 8H), 4.52 (s, 2H), 5.23 (s, H,
J = 11 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.66 (s, 2H), 6.71 (q, 1H, J1= 11 Hz, J2= 17.6 Hz),
7.28 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
Synthesis of S6EGT and S7EGT: A mixture of PEG (Mn=300, 120 g, 0.4mol),
4-vinylbenzyl chloride (16.9 g, 90%, 0.1mol), NaOH (4.0 g, 0.1mol), H2O (1.8 g, 0.1mol)
and 2,6-di-tert-butylphenol (0.02eq. to 4-vinylbenzyl chloride) was stirred at 70 ºC for 24
h. The mixture was diluted with 1000mL of water, and extracted with 500mL of
dichloromethane for three times. The dichloromethane extracts were combined and
washed with 500mL of brine for three times, dried over MgSO4, and concentrated. The
residue was obtained as a viscous liquid. Then, the residue and Et3N (15.1 g, 0.15 mol)
were dissolved in a 500 mL round-bottomed flask containing 100 mL of THF. A solution
of tosyl chloride (28.5 g, 0.15 mol) in 50 mL of THF was added over 1 h with stirring.
The mixture was stirred at room temperature for 24 h. Then, H2O (10 mL) was added and
the mixture was stirred for another 4 h. The mixture was diluted with 1000mL of water,
S2
and extracted with 500mL of dichloromethane for three times. The dichloromethane
extracts were combined and washed with 500mL of brine for three times, dried over
MgSO4, and concentrated. The residue was subjected to column chromatography (petrol
ether/acetone, 4/1 (v/v)) to obtain S6EGT and S7EGT as viscous liquids.
S6EGT: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.44 (s, 3H), 3.60-3.70 (m, 22H), 4.15 (t,
2H, J = 4.8 Hz), 4.55 (s, 2H), 5.23 (d, 1H, J = 9 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.71 (q,
1H, J1= 9 Hz, J2= 17.6 Hz), 7.29-7.39 (m, 6H), 7.79 (d, 2H, J = 8.5 Hz).
S6EGMF: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.84 (s, 2H), 3.58-3.70 (m, 24H), 4.55 (s,
2H), 5.23 (d, 1H, J = 11 Hz), 5.25 (s, 2H), 5.73 (d, 1H, J = 17.6 Hz), 6.50 (s, 2H), 6.71 (q,
1H, J1= 11 Hz, J2= 17.6 Hz), 7.29 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
S6EGM: 1H-NMR (400MHz, CD3CN) δ (ppm) 3.46-3.62 (m, 24H), 4.50 (s, 2H), 5.24 (s,
1H, J = 11 Hz), 5.79 (d, 1H, J = 17.6 Hz), 6.75 (s, 2H), 6.75 (q, 1H, J1= 11 Hz, J2= 17.6
Hz), 7.30 (d, 2H, J = 8.4 Hz), 7.43 (d, 2H, J = 8.4 Hz).
13
C-NMR (400MHz, CDCl3) δ
(ppm) 37.24, 67.91, 69.57, 70.18, 70.72, 73.02, 113.88, 126.33, 128.05, 134.29, 136.69,
137.04, 138.10, 170.76. HRMS (EI) m/z calculated for C25H35NO8 [M+] 477.2363, found
477.2368.
S7EGT: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.44 (s, 3H), 3.60-3.70 (m, 26H), 4.15 (t,
2H, J = 4.8 Hz), 4.55 (s, 2H), 5.23 (d, 1H, J = 11 Hz), 5.74 (d, 1H, J = 17.6 Hz), 6.71 (q,
1H, J1= 11 Hz, J2= 17.6 Hz), 7.29-7.39 (m, 6H), 7.79 (d, 2H, J = 8.4 Hz).
S7EGMF: 1H-NMR (400MHz, CDCl3) δ (ppm) 2.85 (s, 2H), 3.59-3.70 (m, 28H), 4.55 (s,
2H), 5.23 (d, 1H, J = 10 Hz), 5.25 (s, 2H), 5.73 (d, 1H, J = 17.6 Hz), 6.50 (s, 2H), 6.71 (q,
1H, J1= 10 Hz, J2= 17.6 Hz), 7.29 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz).
S7EGM: 1H-NMR (400MHz, CD3CN) δ (ppm) 3.49-3.62 (m, 28H), 4.50 (s, 2H), 5.24 (s,
1H, J = 11 Hz), 5.79 (d, 1H, J = 17.6 Hz), 6.75 (s, 2H), 6.75 (q, 1H, J1= 11 Hz, J2= 17.6
Hz), 7.30 (d, 2H, J = 8.0 Hz), 7.43 (d, 2H, J = 8.0 Hz).
S3
2. Table and figures
3608
*
4182=301.1×13 + 272×2 + 23
2703
3910
*
3004
*
*
301
*
4500
5000
3910
*
*
▼
1000
◆
4000
*
3608
3500
301
4513
3306
3881
3580
*
*
◆
◆
4483
*
4182
4212
2401
2401=301.1*7+272+23
*
▼
1500
▼
2000
▼
2500
▼
◆
3000
Mass (m/z)
◆*
◆
3500
4000
4500
5000
Figure S1. MALDI-TOF mass spectrum of resultant polymer of polymerization of
S2EGM in low concentration (0.01 M).
e
d
a
O
O
c
N
O
O
O
O
O
b
K+
O
S6EGM+2eq.KPF6
a
S6EGM+1eq.KPF6
8
d
7
c
e1
6
b
H2O
CH3CN
e2
5
4
Chemical shift (ppm)
3
2
Figure S2. 1H-NMR spectra of S6EGM with 1eq. KPF6 and S6EGM with 2eq. KPF6 in
CD3CN.
S4
n
O
N
O
c
b
O
O
a
O
O
O
a
O
b
c
8
7
6
5
4
3
2
1
0
Chemical shift (ppm)
Figure S3. 1H-NMR spectrum in CDCl3 of resultant polymer of S6EGM in low
concentration (0.02 M).
a
b
c
O
n
d
N
O
f
e
O
O
O
O
g
O
O
g
f
e
d
c
b
180
160
140
120
100
80
60
a
40
20
0
Chemical shift (ppm)
Figure S4.
13
C-NMR spectrum in CDCl3 of resultant polymer of S6EGM in low
concentration (0.02 M).
S5
4114
*
*
4114=
3636
4591
*
153 + 477.5×8 + 119 + 23
S
477
Na+
n
O
S
N
O
5069
*
O
O
O
*
3157
O
2000
2500
▼
▼
5546
▼
▼
*
▼
3000
O
*
153
*
O
3500
4000
4500
5000
5500
6000
6500
Mass (m/z)
Figure S5. MALDI-TOF mass spectrum of resultant polymer of S6EGM in low
concentration (0.02 M).
*
*
4591
3636
4114
*
4114=
153 + 477.5×8 + 119 + 23
*
5069
S
3157
*
n
O
S
N
Na+
477
5546
*
O
O
O
O
O
O
*
3157
6024
*
▼
O
▼
▼
*
6501
153
▼
▼
▼
▼
1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500
Mass (m/z)
Figure S6. MALDI-TOF mass spectrum of resultant polymer of polymerization of
S6EGM in the presence of KPF6 in high concentration (0.1 M).
S6
Table S1. Results of the polymerization of S7EGM in CH3CN under different
conditions
Entry
Monomer
Conversion Mn b
Feed Ratio
Mw/Mn b
Concentration (Monomer/CDB/AIBN) (NMR) a
1
0.02 M
15/1/0.2
76%
2590
1.29
2
0.05 M
15/1/0.2
~80% c
4280
>2
3
0.05 M+K+
15/1/0.2
81%
2570
1.29
4
0.1 M+K+
15/1/0.2
~50% c
2640
1.61
a
Calculated according to the integral areas of resonance of -CH2O- attached to the styrene moieties in
NMR spectrum. This signal was not overlapped by other signals. b Determined by SEC. c There was
minor error in the conversion of monomer calculated by NMR because of signals of unconsumed
terminals in branched structure.
0.02M
0.05M
+
0.05M+K
+
0.1M+K
16
18
20
monomer
22
24
26
28
30
32
Elution time (min)
Figure S7. SEC profiles of polymerization of S7EGM under different conditions.
S7
e
b
a
S7EGM+2KPF6
c
d
e1
O
H2O
Od
CH3CN
e2
N
a
O
O
c
K+
O
O
O
O
O
b
S7EGM+KPF6
d
a
S7EGM
8
d
7
O
c
e1
b
e2
6
5
a
4
3
e
O
N
O
b
n
c
2
Chemical shift (ppm)
Figure S8. 1H-NMR spectra of (A) S7EGM, (B) S7EGM with 1eq. KPF6 and (C) S7EGM
with 2eq. KPF6 in CD3CN.
S8