fluoroalkyl acrylates and supporting information for -butyl acrylate … · 2017. 4. 28. · 9 fig....
TRANSCRIPT
1
Supporting Information for
Synthesis of amphiphilic copolymers based on acrylic acid,
fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous-
organic and aqueous media via RAFT polymerization
N. S. Serkhachevaа, O. I. Smirnova, А. V. Tolkacheva,b, N. I. Prokopova, A. V. Plutalovac, E.
V. Chernikovac,*, E.Yu. Kozhunovad, and A. R. Khokhlovd,e
a Moscow Technological University, Institute of Fine Chemical Technologies, Vernadskogo pr.,
86, Moscow, 119571, Russian Federation; b Max-Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476 Potsdam, Germany;
c Faculty of Chemistry, Lomonosov Moscow State University, Leninskie gory 1/3, Moscow,
119991, Russian Federation, Fax: +7 495 9397104, Tel: +7 495 9395406;d Faculty of Physics, Lomonosov Moscow State University, Leninskie gory 1/2, Moscow, 119991,
Russian Federation e Institute of Advanced Energy Related Nanomaterials, University of Ulm, Albert Einstein Allee,
11, D-89081, Ulm, Germany
E-mail: [email protected]
Table of ContentsFig. S1. The instantaneous values of monomer (13) and copolymer (13) composition
(a); dyad composition AAAA (b) and AAAB (c) calculated according to the terminal unit
model using rA = 0.9, rB =0.1 (1), rA = 3.0, rB =0.1 (2), and rA = 10.0, rB =0.1 (3) for
monomer mixture containing 5 mol. % of monomer A. ..........................................................3
Fig. S2. The particle size distribution for 3 wt. % solution of Cop-O2 in DMF (a) and in the
mixture DMF/acrylic acid/OFPA (b); DMF/monomers = 70/30 v/v, acrylic acid/OFPA =
90/10 mole %. ................................................................................................................................4
Fig. S3. 1H NMR (a) and 19F NMR (b) spectra of the copolymer obtained at 76 % monomer
conversion in copolymerization of acrylic acid and 2,2,3,4,4,4-hexafluorobutyl acrylate in
DMF in the presence of BTC and subjected to methylation; acrylic acid/HFBA = 90/10
mole %............................................................................................................................................5
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2017
2
Fig. S4. The SEC curves normalized by the unit area for triblock copolymers synthesized in
DMF (70 wt.%) in the presence of Pol-A; [Pol-A] = 3.010-3 mole/L, [AIBN] = 5.010-4
mole/L, 75oC; molar ratio of butyl acrylate to HFBA 90 : 10 (a) and 85 :15 (b).................6
Fig. S5. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 99 %
monomer conversion in copolymerization of butyl acrylate and 2,2,3,4,4,4-
hexafluorobutyl acrylate in the presence of Pol-A in DMF and subjected to methylation;
[Pol-A] = 3.010-3 mole/L, [AIBN] = 5.010-4 mole/L, DMF/monomers = 70/30 v/v,
[butyl acrylate]/[HFBA] = 90/10 mole %. .................................................................................7
Fig. S6. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 99 %
monomer conversion in emulsion copolymerization of butyl acrylate and 2,2,3,4,4,4-
hexafluorobutyl acrylate in the presence of Pol-A and subjected to methylation; [Pol-A] =
7.710-4 mole/L, [PSK] = 2.610-4 mole/L, monomers : water = 1 : 6 v/v, [butyl
acrylate]/[HFBA] = 90/10 mole %..............................................................................................8
Fig. S7. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 91 %
monomer conversion in dispersion copolymerization of butyl acrylate and 2,2,3,4,4,4-
hexafluorobutyl acrylate in the presence of Pol-A in methanol/water (80/20 v/v) mixture
and subjected to methylation; media/monomers = 7/1 v/v, [butyl acrylate]/[HFBA] =
90/10 mole %; [Pol-A] = 2.210-3 mole/L, [AIBN] = 1.110-3 mole/L. ...............................9
Table S1. Molecular weight characteristics of the copolymers of acrylic acid and 2,2,3,4,4,4-
hexafluorobutyl acrylate (95 : 5 mole %), acrylic acid and 2,2,3,3,4,4,5,5-
octafluoropentyl acrylate (90 : 10 mole %) synthesized in DMF in the presence of
trithiocarbonates. ...........................................................................................................................10
Table S2. Molecular weight characteristics of the “grown” copolymers (mode 2) of butyl
acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate synthesized in DMF in the presence of
trithiocarbonates. ...........................................................................................................................11
Table S3. Molecular weight characteristics of the “grown” copolymers of butyl acrylate and
2,2,3,4,4,4-hexafluorobutyl acrylate, butyl acrylate and 2,2,3,3,4,4,5,5-octafluoropentyl
acrylate (mode 2) synthesized by emulsifier-free emulsion polymerization in the presence of
trithiocarbonates. ...........................................................................................................................12
3
Fig. S1. The instantaneous values of monomer (13) and copolymer (13) composition (a); dyad composition AAAA (b) and AAAB (c) calculated according to the terminal unit model using rA = 0.9, rB =0.1 (1), rA = 3.0, rB =0.1 (2), and rA = 10.0, rB =0.1 (3) for monomer mixture containing 5 mol. % of monomer A.
0 20 40 60
0,1
0,2
0,3
fA
1', 2'
3'
2
3FA
Conversion, %
1
(a)
0,02
0,04
0,06
0,08
0,10
0 20 40 60
0,1
0,2
0,3
0,4
3
2
Conversion, %
AAAB (b)
1
0 20 40 60
0.04
0.08
0.12
1
2
3
Conversion, %
AAAA (c)
4
Fig. S2. The particle size distribution for 3 wt. % solution of Cop-O2 in DMF (a) and in the mixture DMF/acrylic acid/OFPA (b); DMF/monomers = 70/30 v/v, acrylic acid/OFPA = 90/10 mole %.
(a)
(b)
5
Fig. S3. 1H NMR (a) and 19F NMR (b) spectra of the copolymer obtained at 76 % monomer conversion in copolymerization of acrylic acid and 2,2,3,4,4,4-hexafluorobutyl acrylate in DMF in the presence of BTC and subjected to methylation; acrylic acid/HFBA = 90/10 mole %.
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
-50
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
Inte
nsity
16.7
0
1.46
0.65
1.00
3.52
4.55
5.93
6.02
7.13
7.23
O
O
S S
S O
O
CH3CH3
O
O
O
O
F
FF
FF
F
F
FF
F
FF
n p k z1
2 3
45
1-35
4
6
6
-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60f1 (ppm)
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
Inte
nsity
-214
.49
-119
.51
-117
.02
-73.
45
32
1
O
O
S S
S O
O
CH3CH3
O
O
O
O
F2F F
F3
F2
F3
n p k z
1
2
3
(a)
(b)
6
Fig. S4. The SEC curves normalized by the unit area for triblock copolymers synthesized in DMF (70 wt.%) in the presence of Pol-A; [Pol-A] = 3.010-3 mole/L, [AIBN] = 5.010-4 mole/L, 75oC; molar ratio of butyl acrylate to HFBA 90 : 10 (a) and 85 :15 (b).
103 104 105
P1
Conversion
M
(a)
103 104 105
P1
Conversion
M
(b)
7
Fig. S5. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 99 % monomer conversion in copolymerization of butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate in the presence of Pol-A in DMF and subjected to methylation; [Pol-A] = 3.010-3 mole/L, [AIBN] = 5.010-4 mole/L, DMF/monomers = 70/30 v/v, [butyl acrylate]/[HFBA] = 90/10 mole %.
(a)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
-50
0
50
100
150
200
250
300
350
400
450
500
550
107.2
8
15.5
6
72.8
8
8.60
4.22
1.00
0.91
3.62
4.01
4.43
5.18
7.26
O
O
S
O
O
CH3
S
S
O
O
CH3
O
O
CH3CH3
O
O
O
O
F
FF
FF
F
F
FF
F
FF
1 2
3
45
6
8
7
1-3 8 7
5
4
6
(b)
-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60f1 (ppm)
-20
0
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
-213
.01
-120
.36
-115
.85
-74.
11
23
1
O
O
S
O
O
CH3
S
S
O
O
CH3
O
O
CH3CH3
O
O
O
O
F2F
F3
F2F
F31
2
3
8
Fig. S6. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 99 % monomer conversion in emulsion copolymerization of butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate in the presence of Pol-A and subjected to methylation; [Pol-A] = 7.710-4 mole/L, [PSK] = 2.610-4 mole/L, monomers : water = 1 : 6 v/v, [butyl acrylate]/[HFBA] = 90/10 mole %.
(a)
(b)
9
Fig. S7. 1H NMR (a) and 19F NMR (b) spectra of the triblock copolymer obtained at 91 % monomer conversion in dispersion copolymerization of butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate in the presence of Pol-A in methanol/water (80/20 v/v) mixture and subjected to methylation; media/monomers = 7/1 v/v, [butyl acrylate]/[HFBA] = 90/10 mole %; [Pol-A] = 2.210-3 mole/L, [AIBN] = 1.110-3 mole/L.
(a)
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
42.8
2
16.5
2
28.2
5
3.22
1.73
1.00
0.89
3.62
3.99
4.42
5.15
7.24
1-38 7
5
4
6
1
2 3
4
5
6
8
7
O
O
S
O
O
CH3
S
S
O
O
CH3
O
O
CH3CH3
O
O
O
O
F
FF
FF
F
F
FF
F
FF
n m p k l z
(b)
-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60f1 (ppm)
-213
.01
-120
.43
-115
.84
-74.
09
32
1
1
2
3
O
O
S
O
O
CH3
S
S
O
O
CH3
O
O
CH3CH3
O
O
O
O
F2F F
F3
F2
F3
n m p k l z
10
Table S1. Molecular weight characteristics of the copolymers of acrylic acid and 2,2,3,4,4,4-hexafluorobutyl acrylate (95 : 5 mole %), acrylic acid and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (90 : 10 mole %) synthesized in DMF in the presence of trithiocarbonates.
RAFT agent Monomer Conversion, % Mn, kDa Mntheor, kDa Mw/Mn
BTC
510-2
mole/L
HFBA 18.3
41.2
72.7
96.6
2.1
3.2
4.4
4.9
1.7
3.4
5.7
7.5
1.23
1.33
1.36
1.38
Cop-H5
310-3
mole/L
HFBA 0
5.3
12.4
42.2
77.2
5.8
16.5
27.5
45.7
50.5
4.0
8.7
12.7
29.2
48.5
1.40
1.55
1.58
1.59
1.71
BTC
610-3
mole/L
OFPA 0.3
12.4
51.6
77.5
86.7
93.9
9.6
11.1
25.2
29.9
32.1
33.8
1.0
9.7
39.4
59.0
66.0
71.4
1.43
1.40
1.42
1.40
1.40
1.47
Cop-O2
610-3
mole/L
OFPA 0
0.6
71.7
91.3
4.8
32.0
61.1
68.7
4.3
5.0
29.0
35.5
1.20
1.22
1.58
1.59
Note: In the case of Cop-H5 and Cop-O2, the molecular weight characteristics of the “grown” copolymers (mode 2) are given.
11
Table S2. Molecular weight characteristics of the “grown” copolymers (mode 2) of butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate synthesized in DMF in the presence of trithiocarbonates.
RAFT agent HFBA, mole % Conversion, % Mn, kDa Mw/Mn
BTC 10 15.3
36.0
64.6
96.9
10.6
19.6
33.1
46.9
1.52
1.48
1.56
1.43
Pol-A 20 4.1
43.7
63.5
94.1
11.9
47.3
56.4
58.1
1.27
1.48
1.32
1.36
Cop-H5 20 10.9
48.4
65.8
93.2
56.5
56.8
60.3
60.4
1.35
1.45
1.44
1.45
12
Table S3. Molecular weight characteristics of the “grown” copolymers of butyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate, butyl acrylate and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (mode 2) synthesized by emulsifier-free emulsion polymerization in the presence of trithiocarbonates.
RAFT agent Monomer, mole % Conversion, % Mn, kDa Mw/Mn
Pol-A HFBA, 10 3.2
19.9
44.4
780.0
950.0
1030.0
1.44
1.60
1.58
Cop-H5 HFBA, 10 7.4
19.9
47.9
1190.0
1340.0
1300.0
1.34
1.37
1.44
Cop-O2 OFPA, 20 1.1
19.6
57.1
85.4
93.8
7.3
40.5
61.7
77.4
93.0
1.12
1.13
1.32
1.47
1.72
Cop-O10 OFPA, 20 32.6
64.9
84.5
28.3
42.9
50.6
1.20
1.67
1.91