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: chernikova_elena@mail.ru

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