Meina supporting informationMeina Liu,a Beng Hoon Tan,b Robert P. Burford,a and Andrew B. Lowe*a a...
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1 Supporting Information Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation Meina Liu, a Beng Hoon Tan, b Robert P. Burford, a and Andrew B. Lowe* a a Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, University of New South Wales, Kensington, Sydney, New South Wales 2052, Australia b Institute of Materials Research and Engineering (IMRE), Agency for Science Technology and Research, 3 Research Link, Singapore 117602 Table of Contents 1 Experimental Procedure and Characterization of Compounds and polymers S1-10 2 Copies of 1 H- and 13 C spectra of Compounds and polymers S11-23 3 References S24 Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2013
Transcript of Meina supporting informationMeina Liu,a Beng Hoon Tan,b Robert P. Burford,a and Andrew B. Lowe*a a...
1
Supporting Information
Nucleophilic thiol-Michael chemistry and hyperbranched
(co)polymers: synthesis and ring-opening metathesis
(co)polymerization of novel difunctional exo-7-oxanorbornenes with in
situ inimer formation
Meina Liu,a Beng Hoon Tan,b Robert P. Burford,a and Andrew B. Lowe*a
a Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, University of
New South Wales, Kensington, Sydney, New South Wales 2052, Australia
b Institute of Materials Research and Engineering (IMRE), Agency for Science Technology and Research,
3 Research Link, Singapore 117602
Table of Contents
1 Experimental Procedure and Characterization of Compounds and polymers S1-10
2 Copies of 1H- and 13C spectra of Compounds and polymers S11-23
3 References S24
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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1. Experimental Procedure and Characterization of Compounds and
polymers
Real-time 1H NMR monitoring of thiol-Michael adduct ROMP kinetics
Homopolymerization of M1
Using M1 (32.9 mg, 0.047 mmol) and RuCl2(PCy3)2CHPh (2.9 mg, 0.0035 mmol for a targeted molecular
weight of 10,000). PM1: 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.69-1.75 (m, 4H), 2.43-2.68 (m, 4H),
3.33-3.76 (m, 12H), 4.31-5.05 (m, 8H), 5.84-6.12 (m, 4H), 7.28-7.33 (m, 4H). Mn (NMR) =10,956; Mn
(DMAC GPC) = 23,634; Mw = 33,166, PDI = 1.40; c/t ratio =26.5/73.5.
O
NO O
PM3
O
O
SS O
N
O
O O
n
n
O
O
O
Homopolymerization of M3
Using M3 (28.8 mg, 0.041 mmol) and RuCl2(PCy3)2CHPh (2.7 mg, 0.0032 mmol for a targeted molecular
weight of 10,000). PM3: 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.63-1.93 (m, 4H), 2.60-2.83 (m, 12H),
3.39-3.80 (m, 12H), 4.26-5.04 (m, 8H), 5.81-6.13 (m, 4H). Mn (NMR) = 6329; Mn (DMAC GPC) = 17,316;
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Mw = 26,126, PDI = 1.50; c/t ratio = 30.0/70.0.
Homopolymerization of M4
Using M4 (12.9 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (1.1 mg, 0.0013 mmol for a targeted molecular
weight of 10,000). PM4: 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.28-2.06 (m, 20H), 2.51-2.74 (m, 5H),
3.01-3.37 (m, 5H), 3.79-3.90 (m, 3H), 4.21-5.23 (m, 3H), 5.85-6.12 (m, 2H), 6.35-6.82 (m, 1H), 7.19-7.51
(m, 1H). Mn (NMR) = 17,106; Mn (DMAC GPC) = 10,045; Mw = 13,705, PDI = 1.36; c/t ratio = 33.9/66.1.
Homopolymerization of M5
Using M5 (11.5 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (1.0 mg, 0.0012 mmol for a targeted molecular
weight of 10,000). PM5: 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.68-2.27 (m, 6H), 3.23-3.40 (m, 2H),
4.08-5.08 (m, 5H), 5.77-6.12 (m, 2H), 7.34-7.78 (m, 8H). Mn (NMR) = 9555; Mn (DMAC GPC) = 16,128;
Mw = 25,844, PDI = 1.60; c/t ratio = 27.8/72.2.
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See our previous report1.
See our previous report1.
See our previous report1.
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Copolymerization of M1/M6 (25:75)
Using M1 (8.7 mg, 0.0125 mmol), M6 (27.9 mg, 0.0375 mmol) and RuCl2(PCy3)2CHPh (3.1 mg, 0.0037
mmol for a targeted molecular weight of 10,000).
Copolymerization of M1/M6 (50:50)
Using M1 (17.4 mg, 0.025 mmol), M6 (18.6 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (3.0 mg, 0.0036
mmol for a targeted molecular weight of 10,000).
Copolymerization of M1/M6 (75:25)
Using M1 (26.1 mg, 0.0375 mmol), M6 (9.3 mg, 0.0125 mmol) and RuCl2(PCy3)2CHPh (2.96 mg, 0.0035
mmol for a targeted molecular weight of 10,000).
STAT P(M1+M6): 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.58-1.91 (m, 12H), 2.44-2.81 (m, 22H),
3.42-3.45 (m, 7H), 4.28-5.11 (m, 13H), 5.83-6.75 (m, 6H), 7.26-7.51 (m, 4H). Mn (NMR) = 9162; c/t ratio
= 28.0/72.0.
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O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S
NO O
n
O
O
S
STAT P(M3+M7)
O
O
R=CH3
CH3Si
OSi
O
Si
O
SiO
O Si
O
SiO
O SiO
O
O
O
RR
R
R
R
R
R
OSi O Si
O SiO
O
SiOSi
O
O
SiO
OSi O
O
R
R
R
R
R
R
R
Copolymerization of M3/M7 (25:75)
Using M3 (8.85 mg, 0.0125 mmol), M7 (43.3 mg, 0.0375 mmol) and RuCl2(PCy3)2CHPh (4.36 mg,
0.0052 mmol for a targeted molecular weight of 10,000).
Copolymerization of M3/M7 (50:50)
Using M3 (17.7 mg, 0.025 mmol), M7 (28.8 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (3.9 mg, 0.0047
mmol for a targeted molecular weight of 10,000).
Copolymerization of M3/M7 (75:25)
Using M3 (26.6 mg, 0.0375 mmol), M7 (14.42 mg, 0.0125 mmol) and RuCl2(PCy3)2CHPh (3.43 mg,
0.0041 mmol for a targeted molecular weight of 10,000).
STAT P(M3+M7): 1H NMR (300 MHz, CD2Cl2, ppm): δ = 0.62-2.01 (m, 50H), 2.61-2.86 (m, 18H),
3.40-3.80 (m, 22H), 4.11-5.15 (m, 12 H), 5.89-6.48 (m, 6H), 7.31-7.50 (m, 1H). Mn (NMR) = 11,673; c/t
ratio = 30.6/69.4.
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O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S
NO O
n
O
O
S
STAT P(M1+M4)
(C10H20) N
(C10H20) N
Copolymerization of M1/M4 (50:50)
Using M1 (17.4 mg, 0.025 mmol), M4 (12.9 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (2.5 mg, 0.0030
mmol for a targeted molecular weight of 10,000).
STAT P(M1+M4): 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.28-1.85 (m, 32H), 2.46-2.72 (m, 12H),
3.30-3.77 (m, 12H), 4.20-5.06 (m, 12H), 5.82-6.12 (m, 6H), 7.28-7.51 (m, 4H). Mn (NMR) = 12,381; Mn
(DMAC GPC) = 26,200; Mw = 63,500, PDI = 2.42; c/t ratio = 24.6/75.4.
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Copolymerization of M3/M5 (50:50)
Using M3 (17.7 mg, 0.025 mmol), M5 (11.5 mg, 0.025 mmol) and RuCl2(PCy3)2CHPh (2.4 mg, 0.0029
mmol for a targeted molecular weight of 10,000).
STAT P(M3+M5): 1H NMR (300 MHz, CD2Cl2, ppm): δ = 1.28-2.82 (m, 22H), 3.78-3.79 (m, 16H),
4.29-5.07 (m, 11H), 5.84-6.14 (m, 6H), 7.38-7.76 (m, 8H). Mn (NMR) = 29,379; Mn (DMAC GPC) =
28,100, Mw = 73,950, PDI = 2.63; c/t ratio = 28.8/71.2.
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Determination of ROMP kinetics via an aliquot approach
ROMP kinetics via an aliquot approach of M1/M6 (25:75)
Using M1 (0.087 g, 0.125 mmol), M6 (0.279 g, 0.375 mmol) and RuCl2(PCy3)2CHPh (30.6 mg, 0.037
mmol for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 15, 20,
25, 30, 35, 40, 50, 65 and 90 min, with intervals based on prior kinetic experiments).
ROMP kinetics via an aliquot approach of M1/M6 (50:50)
Using M1 (0.17 g, 0.25 mmol), M6 (0.185 g, 0.25 mmol) and RuCl2(PCy3)2CHPh (29.7 mg, 0.035 mmol
for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 20, 30, 40,
60, 80, 100, 120, 150, 180 and 200 min, with intervals based on prior kinetic experiments).
ROMP kinetics via an aliquot approach of M1/M6 (75:25)
Using M1 (0.26 g, 0.375 mmol), M6 (0.093 g, 0.125 mmol) and RuCl2(PCy3)2CHPh (29.5 mg, 0.035
mmol for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 20, 30,
40, 60, 80, 100, 120, 150, 180 and 200 min, with intervals based on prior kinetic experiments).
ROMP kinetics via an aliquot approach of M3/M7 (25:75)
Using M3 (0.089 g, 0.125 mmol), M7 (0.433 g, 0.375 mmol) and RuCl2(PCy3)2CHPh (43 mg, 0.051 mmol
for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 15, 20, 25,
30, 35, 40, 50, 67 and 90 min, with intervals based on prior kinetic experiments).
ROMP kinetics via an aliquot approach of M3/M7 (50:50)
Using M3 (0.177 g, 0.25 mmol), M7 (0.288 g, 0.25 mmol) and RuCl2(PCy3)2CHPh (38.9 mg, 0.046 mmol
for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 20, 30, 40,
60, 80, 100, 130, 150, 180 and 200 min, with intervals based on prior kinetic experiments).
ROMP kinetics via an aliquot approach of M3/M7 (75:25)
Using M3 (0.266 g, 0.375 mmol), M7 (0.144 g, 0.125 mmol) and RuCl2(PCy3)2CHPh (34.3 mg, 0.041
mmol for a targeted molecular weight of 10,000). Aliquots were withdrawn periodically (at 2, 5, 10, 20, 30,
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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40, 60, 80, 100, 120, 150, 180 and 200 min, with intervals based on prior kinetic experiments).
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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2. Copies of 1H- and 13C spectra
10 9 8 7 6 5 4 3 2 1 0 ppm
2.406
2.412
2.436
2.456
2.536
2.558
2.580
2.586
2.778
3.611
3.638
3.656
3.674
4.132
4.150
4.167
5.144
5.149
5.152
6.426
6.430
6.433
7.171
3.9
1
3.9
0
3.9
9
7.9
8
3.9
6
3.8
7
3.9
0
4.0
0
ON
O
OO
O
SSO
ON
O
OO
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
25.68
33.88
35.47
37.33
47.17
60.42
76.57
77.00
77.42
80.56
128.82
136.17
136.58
171.19
175.81
ON
O
OO
O
SSO
ON
O
OO
M1
M1
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
2.489
2.514
2.539
2.658
2.697
2.720
2.745
2.849
3.676
3.694
3.712
4.172
4.191
4.208
5.194
5.197
5.200
6.490
6.494
6.497
4.0
61
1.9
44.
04
4.0
4
4.0
1
3.9
9
4.0
0
NO
O
O
O
SSO
ON
O
O
S
O O
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
26.18
31.53
31.57
34.23
37.20
47.02
60.32
76.57
77.00
77.42
80.44
136.09
170.90
175.58
NO
O
O
O
SSO
ON
O
O
S
O O
M2
M2
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
2.479
2.483
2.505
2.529
2.531
2.620
2.643
2.665
2.690
2.692
2.715
2.738
2.741
2.812
3.544
3.549
3.571
3.594
3.667
3.684
3.703
4.162
4.181
4.197
5.184
5.187
5.191
6.452
6.455
6.459
4.0
18
.00
4.0
3
7.9
84
.09
4.0
2
4.0
1
4.0
0
N
O
OO
O
O S O
O
N
O
O
O
O
O
S
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
26.97
31.30
34.59
37.60
47.36
60.68
70.17
70.79
76.58
77.01
77.45
80.82
136.42
171.43
175.89
N
O
OO
O
O S O
O
N
O
O
O
O
O
S
M3
M3
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
1.183
1.265
1.294
1.429
1.478
1.527
1.640
1.664
1.709
2.389
2.414
2.438
2.468
2.489
2.617
2.640
2.668
2.766
3.638
3.654
3.673
3.747
3.766
3.794
4.138
4.154
4.171
5.142
5.145
5.148
6.012
6.019
6.026
6.406
6.408
6.411
6.542
6.548
6.555
14
.00
2.0
72
.08
4.0
62
.07
2.0
6
2.0
02
.04
2.0
4
2.0
3
1.9
7
2.1
22
.00
O
N
O
OO
O
SN
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
26.31
26.40
28.49
28.86
29.10
29.18
31.23
31.67
34.36
37.42
47.19
49.25
60.42
76.60
77.04
77.44
80.62
107.46
120.17
136.21
171.35
175.71
O
N
O
OO
O
SN
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10 9 8 7 6 5 4 3 2 1 0 ppm
2.105
2.113
2.136
2.158
2.191
2.213
2.223
2.237
2.245
2.800
3.662
3.679
3.697
4.130
4.148
4.167
4.889
5.210
6.497
7.334
7.363
7.381
7.402
7.427
7.688
7.710
7.740
4.0
3
2.0
7
2.0
6
2.0
6
0.9
8
2.0
0
2.0
6
4.0
1
4.0
0O
N
O
OO
O
S
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
22.67
34.35
37.46
47.24
48.68
60.44
76.59
77.04
77.50
80.68
119.77
125.30
127.44
127.95
136.36
140.41
144.39
171.22
175.72
O
N
O
OO
O
S
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
2.230
2.288
2.318
2.345
2.377
2.404
2.481
2.505
2.529
2.645
2.662
2.673
2.698
2.722
2.744
2.792
3.668
3.687
3.704
4.171
4.189
4.208
5.168
5.171
5.174
6.430
6.433
6.436
1.9
8
2.0
23
.90
2.0
2
2.0
2
2.0
3
1.9
7
2.0
0
O
N
O
OO
O
S
FF
F F
FF
F F
FF
FF
FFF
FF
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
22.48
26.54
31.50
31.79
32.08
34.24
37.64
47.36
60.79
76.56
77.00
77.43
80.83
108.50
110.70
111.24
115.15
117.46
118.92
120.84
136.43
171.21
175.92
O
N
O
OO
O
S
FF
F F
FF
F F
FF
FF
FFF
FF
M6
M6
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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-200-180-160-140-120-100-80-60-40-200 ppm
-126.53
-126.50
-126.44
-126.40
-126.37
-123.55
-123.51
-123.00
-122.21
-122.17
-122.15
-121.94
-114.59
-114.54
-114.49
-81.24
-81.21
-81.18
-81.17
-81.16
2.0
14.
07
6.0
8
2.0
5
3.0
0
O
N
O
OO
O
S
FF
F F
FF
F F
FF
FF
FFF
FF
M6
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
0.660
0.666
0.876
0.897
1.551
1.577
1.603
1.625
1.656
1.720
1.737
1.764
1.785
1.805
1.832
1.859
2.426
2.452
2.477
2.501
2.621
2.644
2.669
2.796
3.665
3.682
3.701
4.160
4.178
4.196
5.177
5.180
5.183
6.436
6.439
6.442
13
.96
2.2
84
2.3
8
2.0
17
.05
4.0
62
.08
2.0
8
2.0
0
2.0
3
1.9
8
1.9
8
O
N
O
OO
O
OSi O
Si
O
Si
OSi
OSi
O
SiR
RR
R
R
O Si OR
OOSi
O OR
S
R=CH3
CH3
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
11.53
22.38
22.87
23.75
25.61
26.31
34.48
34.75
37.69
47.41
60.64
76.57
77.00
77.43
80.81
136.44
171.49
175.87
O
N
O
OO
O
OSi O
Si
O
Si
OSi
OSi
O
SiR
RR
R
R
O Si OR
OOSi
O OR
S
R=CH3
CH3
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
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10 9 8 7 6 5 4 3 2 1 0 ppm
1.932
1.958
1.975
2.012
2.539
2.565
2.590
2.705
2.845
2.878
2.926
3.661
3.724
4.046
4.097
4.133
4.199
4.495
4.528
4.904
4.935
4.967
4.979
5.010
5.044
5.132
5.163
5.184
5.189
5.195
6.475
6.478
6.480
12
.03
2.0
2
4.0
1
3.0
1
4.0
1
1.0
2
2.0
1
2.9
8
2.0
0
OAcO
AcO
OAc
OAc
O
N
O
OO
O
S
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.20
20.33
24.74
34.89
37.30
47.16
60.51
61.77
67.94
69.37
73.35
75.35
76.57
77.00
77.42
80.57
83.31
136.23
168.98
169.03
169.67
170.23
170.89
175.78
OAcO
AcO
OAc
OAc
O
N
O
OO
O
S
M8
M8
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PM1
10 9 8 7 6 5 4 3 2 1 0 ppm
1.687
1.748
2.429
2.539
2.574
2.658
2.675
3.325
3.391
3.756
4.313
4.529
5.046
5.843
6.121
7.280
7.331
4.05
7.01
11.
99
7.99
3.95
4.00
0.29
ON
O
O
O
O
SSO N
O
O
O
O
nn
PM1
PM3
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.631
1.789
1.934
2.605
2.723
2.828
3.394
3.644
3.802
4.262
4.539
5.038
5.815
6.130
4.1
8
12
.08
11
.99
8.2
9
4.0
0
O
NO O
PM3
O
O
SS O
N
O
O O
n
n
O
O
O
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21
PM4
10 9 8 7 6 5 4 3 2 1 0 ppm
1.284
1.585
2.061
2.514
2.736
3.011
3.353
3.788
3.895
4.207
4.257
4.502
4.629
5.014
5.232
5.377
5.854
6.117
6.348
6.553
6.671
6.816
7.188
7.320
7.506
20.
22
5.03
5.07
3.07
3.03
2.00
0.99
1.01
O
n
NO O
OO
S(C10H20)
N PM4
PM5
10 9 8 7 6 5 4 3 2 1 0 ppm
1.680
1.823
1.881
2.082
2.268
3.230
3.402
4.077
4.192
4.952
5.082
5.771
6.115
7.335
7.694
7.780
6.0
2
2.1
0
5.0
5
2.0
0
7.9
9
O
n
NO O
OO
S
PM5
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
22
STAT P(M1+M6)
10 9 8 7 6 5 4 3 2 1 0 ppm
1.579
1.694
1.909
2.440
2.641
2.814
3.417
4.278
4.493
5.053
5.110
5.828
6.158
6.388
6.747
7.264
7.508
12.
00
22.
03
7.0
9
13.
07
6.0
0
3.7
9
O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S(C8F17)
NO O
n
O
O
S(C8F17)
BLOCK (M1+M6)
STAT P(M3+M7)
10 9 8 7 6 5 4 3 2 1 0 ppm
0.618
0.994
1.263
1.895
2.002
2.607
2.728
2.862
3.400
3.615
3.803
4.112
4.287
5.026
5.147
5.886
6.128
6.477
7.310
7.498
50
.11
18
.09
21
.97
12
.06
6.0
0
1.0
5
O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S
NO O
n
O
O
S
BLOCK (M3+M7)
O
O
R=CH3
CH3
Si
OSi
O
Si
O
SiO
O Si
O
SiO
O SiO
O Si
O
O
RR
R
R
R
R
R
O
Si O Si
O SiO
O
SiOSi
O
O
SiO
O
Si OO
R
R
R
R
R
R
R
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23
STAT P(M1+M4)
10 9 8 7 6 5 4 3 2 1 0 ppm
1.282
1.524
1.851
2.464
2.720
3.304
3.446
3.774
4.201
4.258
4.528
5.055
5.824
6.066
6.123
7.277
7.505
32.
06
11.
99
11.
66
11.
36
6.0
0
3.9
5
O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S
NO O
n
O
O
S
BLOCK (M1+M4)
(C10H20) N
(C10H20) N
STAT P(M3+M5)
10 9 8 7 6 5 4 3 2 1 0 ppm
1.282
1.723
2.150
2.706
2.820
3.375
3.631
3.788
4.286
4.528
5.069
5.838
6.138
7.377
7.704
7.761
22
.59
16
.52
11
.32
6.0
0
8.1
9
O
NO O
O
O
S
S
O
NO O
O O
m
m
O
O
n
NO O
O
O
S
NO O
n
O
O
S
BLOCK (M3+M5)
O
O
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24
PM1, [Ru]:M1, 1:20
3456
Chemical shift (ppm)
300 s
386 s
473 s
560 s
1078 s
2723 s
4540 s
C=C bond in monomer
trans and cisC=C bonds in
polymer
PM1, [Ru]:M1, 1:40
3456
Chemical Shift (, ppm)
300 s
820 s
1511 s
3241 s
8868 s
17436 s
3. References
[1] Liu, M.; van Hensbergen, J.; Burford, R. P.; Lowe, A. B. Polym. Chem. 2012, 3, 1647.
Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013
