Random and Block Styrenic Copolymers Bearing Both
Ammonium and Fluorinated Side-Groups.
David Valade, Frédéric Boschet, Bruno Améduri
Institut Charles Gerhardt, Ingénierie et Architectures Macromoléculaires,
UMR CNRS 5253, Ecole Nationale Supérieure de Chimie de Montpellier,
8 Rue de l'Ecole Normale, 34296 Montpellier, France
SUPPORTING INFORMATION
1
.
kd
Initiator decomposition
A2
2
.
(a)
.
A
Initiation
A
AM
M
.
A
A-I
R-I
kT r
.
AM
Propagation
Pn
Degenerative Transfer
(b)
.
R
kT r
Pn
M
.
.
.
kT r
R-I
(c)
Pn -I
R
(d)
kT r
k
k
M
M
Pn
.
ke
x
Pm-I
Pn -I
x
k
M
M
.
.
ke
kp
Pn
Pm
Pm
.
(e)
P n Pm
Termination
Scheme S1 Mechanism of Iodine Transfer Polymerization
Synthesis of 1H,1H,2H,2H-perfluorooctyl-oxymethylstyrene (FS)
This
synthesis
consists
in
phase
transfer
catalysis
involving
1H,1H,2H,2H-
perfluorooctanol (99.45 g, 0.273 mol) and sodium hydroxide solution (700 mL at 50 %)
introduced in a 2 L three-neck round-bottom flask equipped with a condenser and a
mechanical stirrer. The mixture was stirred for 1 hour prior to the introduction of
dichloromethane (700 mL), and tetrabutyl ammonium hydrogenosulfate (TBAH) (9,15 g,
2
0.027 mol). One hour later, chloromethylstyrene (CMS) (45.1 g, 0.295 mol) was added
dropwise, and the solution turned yellow. The solution was then heated at 40 °C for 20 h,
resulting into a brown mixture.
The solution was extracted several times with a 1M HCl solution, and then with
deionized water. Dichloromethane was then evaporated, and the solution maintained
under vacuum (2.10-2 mbar) at 70 °C for 3 hrs to eliminate traces of dichloromethane and
also unreacted CMS. The product was purified over silica gel with a pentane/chloroform
mixture (70/30). The obtained yellow product was further dried under vacuum, and
analyzed by 1H and 19F NMR spectroscopy (purity 83 % and yield 66 %).
1
H NMR (CDCl3,  (ppm), Figure S1): 2.48 (triplet, 3JH-F = 18 Hz, 3JH-H = 6 Hz, -O-CH2-
CH2-RF); 3.80 (triplet, -O-CH2-CH2-RF); 4.56 (singulet, -C6H4-CH2-O-); 5.30 et 5.81
(doublets, 3JH-H = 12 Hz and 3JH-H = 18 Hz, CH2=CH-C6H4-); 6.75 (doublet of doublets,
CH2=CH-C6H4-); 7.34 and 7.43 (doublets, CH2=CH-C6H4-O-).
19
F NMR (CDCl3,  (ppm)): signals relative to the C6F13- are identical to those of the
alcohol: -81.3 ppm (CF3-C4F8-CF2-CH2-), -113.6 ppm (CF3-C4F8-CF2-CH2-), and –122.1,
-123.1, -123.9, and -126.5 ppm (CF3-C4F8-CF2-CH2-).
3
d d'
e
f
b
a
c
7.5
7.0
g
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
Figure S1. 1H NMR spectrum of 1H,1H,2H,2H-perfluorooctyl-oxymethylstyrene
(FS) recorded in CDCl3.
4
2.5
a
C6F13
f
e
b
CH2 CH
n
I
H2C
CH
h
g
c
g
e
d
h
H2C
H2C
Cl
Cl
e
f
c
7.5
d
7.0
6.5
5.5
5.4
6.0
5.5
b
a
20.0
5.0
4.5
4.0
3.5
3.0
2.5
2.0
Figure S2. 1H NMR spectrum of the intermediate RF-(CMS)n-I (Run #10 in Table 3)
polymer recorded in CDCl3.
5
1.5
a
b
CF3
CF2
c
3
d
a
CF2 CF2 I
a
b
c' d'
CF3
CF2
CF2 CF2
3
CH2 CH
n
I
H 2C
Cl
b + c’
d
c
d'
10.8
-60
30.0
-70
-80
-90
-100
-110
-120
Figure S3. 19F NMR spectrum of the intermediate RF-(CMS)n-I (Run #10 in Table 3)
polymer recorded in CDCl3
6
-130
Figure S4. DSC thermograms of poly(CMS-co-FS) (sample # 3, Table 2) and
poly(CMS)-b-poly(FS) copolymers (sample #17, Table 4).
7