Electronic Supplementary Material (ESI) for Chemical Science
This journal is © The Royal Society of Chemistry 2013
Supporting Information for RAFT Dispersion
Polymerization in Non-Polar Solvents:
Facile Production of Block Copolymer Spheres, Worms
and Vesicles in n-Alkanes
Lee A. Fielding*, Matthew Derry, Vincent Ladmiral, Julien Rosselgong, Aurélie M.
Rodrigues, Liam Ratcliffe, Shinji Sugihara and Steven P. Armes*
Figure S1. RAFT polymerization of LMA in toluene at 70°C and 50 wt. % solids using CPDB CTA. The
targeted composition was PLMA38 and the CTA/initiator molar ratio was 5.0. (A) evolution of Mn and Mw/Mn
with monomer conversion, as judged by THF GPC (vs. poly(methyl methacrylate) calibration standards); (B)
Conversion vs. time data calculated from 1H NMR spectra.
S1
Electronic Supplementary Material (ESI) for Chemical Science
This journal is © The Royal Society of Chemistry 2013
Figure S2. Assigned 1H NMR spectra obtained for the PLMA17 macro-CTA (in CD2Cl2) and a PLMA17PBzMA50 diblock copolymer (in CDCl3).
Figure S3. Conversion vs. time curve and corresponding semi-logarithmic plot obtained for the polymerization
of BzMA at 90°C using a PLMA17 macro-CTA under RAFT dispersion polymerization conditions in n-heptane
at 15 wt. % solids. Conditions: target DP for the PBzMA block = 300; macro-CTA/initiator molar ratio = 2.0.
S2
Electronic Supplementary Material (ESI) for Chemical Science
This journal is © The Royal Society of Chemistry 2013
Table S1. Summary of monomer conversions, calculated degrees of polymerization and GPC molecular weights
for PLMA macro-CTAs synthesized by RAFT solution polymerization of LMA in toluene at 70°C using AIBN.
Conditions: [LMA]0 = 50 wt. %, CTA/AIBN molar ratio = 5.0.
Targeted degree of
polymerization
CTA type
PLMA10
PLMA40
PLMA60
PLMA38
PLMA35
PLMA70
CDB
CDB
CDB
CPDB
PETTC
PETTC
NMR
conversion
Mean DP
1
( H NMR)
85
74
73
85
95
74
17
37
47
39
45
75
-1
Mn / g mol
4 900
9 800
12 800
8 900
9 100
13 000
THF GPC
-1
Mw / g mol
5 900
12 000
16 100
9 900
10 300
15 000
Mw/Mn
1.20
1.23
1.26
1.11
1.13
1.16
S3
Electronic Supplementary Material (ESI) for Chemical Science
This journal is © The Royal Society of Chemistry 2013
Table S2. Summary of monomer conversions, particle diameters and molecular weights obtained for PLMA17PBzMAx syntheses conducted by RAFT dispersion polymerization of BzMA in n-heptane at 90°C using T21s
initiator (macro-CTA/initiator molar ratio = 2.0) for at least 18 h at 12.5 to 25.0 % solids.
Solids
12.5
15.0
17.5
20.0
21.2
22.5
23.8
25.0
Target composition
PLMA17-PBzMA200
PLMA17-PBzMA150
PLMA17-PBzMA100
PLMA17-PBzMA75
PLMA17-PBzMA63
PLM17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA25
PLMA17-PBzMA300
PLMA17-PBzMA250
PLMA17-PBzMA200
PLMA17-PBzMA150
PLMA17-PBzMA100
PLMA17-PBzMA75
PLMA17-PBzMA63
PLMA17-PBzMA50
PLMA17-PBzMA25
PLMA17-PBzMA125
PLMA17-PBzMA88
PLMA17-PBzMA75
PLMA17-PBzMA63
PLMA17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA300
PLMA17-PBzMA250
PLMA17-PBzMA200
PLMA17-PBzMA150
PLMA17-PBzMA100
PLMA17-PBzMA75
PLMA17-PBzMA63
PLMA17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA25
PLMA17-PBzMA50
PLMA17-PBzMA175
PLMA17-PBzMA125
PLMA17-PBzMA88
PLMA17-PBzMA63
PLMA17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA25
PLMA17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA25
PLMA17-PBzMA300
PLMA17-PBzMA250
PLMA17-PBzMA200
PLMA17-PBzMA150
PLMA17-PBzMA100
PLMA17-PBzMA75
PLMA17-PBzMA63
PLMA17-PBzMA50
PLMA17-PBzMA38
PLMA17-PBzMA25
BzMA %
conversion
98
97
97
96
98
96
97
91
98
96
96
97
98
98
98
97
96
98
98
98
98
97
99
98
98
98
98
98
99
98
98
97
96
98
99
99
99
99
98
99
95
99
97
97
99
98
99
99
98
99
98
98
98
99
Actual
PBzMA DP
196
146
97
72
62
48
37
23
294
240
192
146
98
74
62
49
24
123
86
74
62
49
38
294
245
196
147
98
74
62
49
37
24
49
173
124
87
62
49
38
24
50
37
24
297
245
198
149
98
74
62
49
37
25
GPC
Mn
Mw/Mn
51 600
1.18
43 800
1.15
25 600
1.29
19 400
1.30
18 400
1.39
14 800
1.32
13 400
1.34
9 800
1.25
57 100
1.18
50 600
1.24
50 300
1.18
49 300
1.20
38 800
1.14
23 200
1.30
18 600
1.40
20 600
1.32
10 600
1.41
30 800
1.47
22 500
1.34
19 500
1.41
19 000
1.37
15 500
1.35
13 600
1.28
71 500
1.35
64 700
1.26
59 700
1.22
47 300
1.25
28 600
1.29
22 800
1.32
18 100
1.36
14 000
1.35
13 300
1.33
10 300
1.32
13 700
1.30
48 100
1.17
29 400
1.33
23 700
1.58
17 400
1.42
15 000
1.31
12 900
1.38
10 500
1.29
13 300
1.32
12 700
1.31
10 500
1.30
62 700
1.34
54 500
1.18
46 400
1.17
39 700
1.15
28 800
1.16
26 400
1.15
15 900
1.34
15 800
1.37
12 200
1.27
10 400
1.30
DLS
diameter
162
158
153
131
91
98
30
27
182
171
173
164
161
105
107
205
48
166
179
168
390
44
62
188
217
191
179
153
476
216
136
29
26
53
192
196
178
680
52
122
21
68
27
21
220
217
216
201
200
749
223
85
31
32
PDI
0.038
0.031
0.055
0.060
0.067
0.378
0.020
0.051
0.050
0.032
0.051
0.040
0.045
0.056
0.066
0.325
0.278
0.032
0.091
0.243
0.604
0.084
0.134
0.015
0.176
0.099
0.042
0.075
0.460
0.307
0.224
0.017
0.003
0.128
0.023
0.100
0.133
0.501
0.140
0.355
0.041
0.134
0.015
0.034
0.097
0.093
0.150
0.078
0.122
0.704
0.362
0.139
0.186
0.046
TEM
morphology
Vesicles
Vesicles
Vesicles
Vesicles and worms
Vesicles and worms
Worms and spheres
Spheres
Spheres
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles and worms
Vesicles and worms
Vesicles and worms
Spheres
Vesicles
Vesicles
Vesicles and worms
Worms
Worms and spheres
Worms and spheres
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles and worms
Worms
Worms
Spheres
Spheres
Worms
Vesicles
Vesicles
Vesicles
Worms
Worms and spheres
Worms and spheres
Spheres
Worms and spheres
Spheres
Spheres
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles
Vesicles and worms
Worms
Worms
Spheres
Spheres
S4
Electronic Supplementary Material (ESI) for Chemical Science
This journal is © The Royal Society of Chemistry 2013
Table S3. Summary of monomer conversions, particle diameters and molecular weights obtained for PLMA17PBzMAx syntheses conducted by RAFT dispersion polymerization of BzMA in n-heptane at 90°C using T21s
initiator (macro-CTA/initiator molar ratio = 5.0) for at least 18 h at 15.0 to 17.5 % solids.
Solids
15.0
17.5
Target composition
BzMA %
conversion
Actual
PBzMA DP
PLMA17-PBzMA175
97
PLMA17-PBzMA125
GPC
DLS
Mn
Mw/Mn
diameter
PDI
TEM
morphology
170
33 500
1.33
176
0.032
Vesicles
97
121
27 800
1.27
180
0.060
Vesicles
PLMA17-PBzMA75
93
70
20 600
1.33
191
0.134
Vesicles
PLMA17-PBzMA35
94
33
11 700
1.22
27
0.025
Spheres
PLMA17-PBzMA175
96
168
45 100
1.33
179
0.020
Vesicles
PLMA17-PBzMA25
89
22
9 300
1.20
21
0.032
Spheres
Table S4. Summary of monomer conversions, particle diameters and molecular weights obtained for PLMAxPBzMAy syntheses conducted by RAFT dispersion polymerization in n-heptane at 90°C using T21s initiator
(macro-CTA/initiator molar ratio = 2.0) for at least 18 h at 15 % solids.
Target composition
BzMA %
conversion
Actual
PBzMA DP
PLMA37-PBzMA900
97
PLMA37-PBzMA700
GPC
DLS
Mn
Mw/Mn
diameter
PDI
TEM
morphology
873
181 500
1.69
139
0.041
Spheres
98
686
170 100
1.51
117
0.008
Spheres
PLMA37-PBzMA500
93
465
79 300
1.72
88
0.014
Spheres
PLMA37-PBzMA300
98
294
65 300
1.61
70
0.016
Spheres
PLMA37-PBzMA100
97
97
29 700
1.34
41
0.008
Spheres
PLMA39-PBzMA300
97
291
70 800
1.16
63
0.007
Spheres
PLMA39-PBzMA150
96
144
43 100
1.48
49
0.024
Spheres
PLMA45-PBzMA300
97
291
42 200
1.34
61
0.018
Spheres
PLMA45-PBzMA150
97
146
25 800
1.28
43
0.018
Spheres
PLMA47-PBzMA900
98
882
192 300
1.76
119
0.026
Spheres
PLMA47-PBzMA700
97
679
202 900
1.63
108
0.025
Spheres
PLMA47-PBzMA300
98
294
99 000
1.37
70
0.018
Spheres
PLMA47-PBzMA100
98
98
32 700
1.52
45
0.011
Spheres
PLMA75-PBzMA300
98
294
38 400
1.61
53
0.037
Spheres
S5