Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2014
Electronic Supplementary Information
Sulfonated poly(arylene ether phosphine oxide)s with various distribution and content of pendant sulfonic acid groups synthesized by direct polycondensation Huiying Liao,a Ke Zhang,b Gangsheng Tong,c Guyu Xiaoa* and Deyue Yana a
School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai
Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China. b
School of Materials Science and Engineering, University of Shanghai for Science and Technology, 516 Jungong
Road, Shanghai, 200093, China. c
Instrumental Analysis Center, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
1. Assignment of the NMR spectra of DSPPO The dept135 and 13C NMR spectra of DSPPO are indicated in Fig. S1a. As shown, (a)
2' 3' 1'
F
4'
SO3Na O 5 6 4 1 P F
7
3 12
8 9 10
3' 1'
1
5 11
3
2
11 SO3Na
12 10 9 4
8
2' 2
6 4'
7 dept135
168 156
135 130 125 Chemical shift / ppm
(b)
120
3,12,8 9
10
2'
3'
2
2
2'
5
2' 3' F
1'
O
4'
P
7 8 9
3 12
SO3 Na
1
F
2
11 SO3Na
5 3
3'
8
12 10 9
10
5 6 4
Fig. S1. Dept135, 13C NMR (a) and HMQC (b) spectra of DSPPO
*
Corresponding author. Tel: +86 21 54742664, E-mail:
[email protected]
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Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2014
the signal peaks of the carbon atoms of DSPPO were well assigned. Carbon 1 and 1' displayed a C/F coupling constant of ~256 Hz. Carbon 4, 4' and 7 exhibited a C/P coupling constant of about 100 Hz, which is equivalent to that of the carbon atoms with similar chemical environments.[1] The HMQC spectrum of DSPPO is presented in Fig. S1b. The signals of the odd carbon atoms of DSPPO in the HMQC spectrum was determined as above, so the signal peaks of the hydrogen atoms of DSPPO could be assigned by the HMQC spectrum, which were indicated in Fig. S1b.
2. Assignment of the 1H NMR spectra of polymers The
chemical
structure
of
PEPOF,
msPEPOF-100,
dsPEPOF-100
and
tsPEPOF-130 is displayed in Fig. S2a. The 1H NMR spectrum of PEPOF was assigned in our previous report as indicated in Fig. S2b,[2] which was used to assist the analysis of the
1
H NMR spectra of the three ionomers. msPEPOF-100 is a
homopolymer, its signal peaks in the 1H NMR spectrum could be well assigned (Fig. S2b). On the other hand, as indicated in Figure S2a, the non-sulfonated repetitive unit of tsPEPOF-130 is exactly the repetitive unit of PEPOF. Moreover, tsPEPOF-130 and msPEPOF-100 also possess identical structural moieties, i.e. benzenesulfonate side groups and hexafluoroisopropylidene diphenyl moieties. These hydrogen atoms with similar chemical environments have approximate chemical shift.[3] Therefore, on the basis of the assignment of the 1H NMR spectra of PEPOF and msPEPOF-100, the assignment of the 1H NMR spectrum of tsPEPOF-130 could be determined, which was presented in Fig. S2b. Similarly, the assignment of the 1H NMR spectrum of dsPEPOF-100 was also resolved by the assistance of the 1H NMR spectra of PEPOF, msPEPOF-100 and tsPEPOF-130. Hence, all the 1H NMR spectra of the three ionomers were determined. 2
Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2014
(a) tsPEPOF-130: 1 2 O
6 7
P
CF3
3 4
O n
6 7
1' 2'
CF3
O
O CF3
3 4
n
6 7
6 7
CF3
O 1''
3''
O P
2'' 6'
O m
CF3
SO3Na 6 7
CF3
O
O
1''
CF3
n
SO3Na
5'
P
SO3Na
SO3Na
3' 4'
5 msPEPOF-100: 1' 2' O
CF3
O
O CF3
6' 5'
6' 5'
P
PEPOF: 1 2
2''
3' 4'
NaO3S
5 dsPEPOF-100: 1 2 O
3' 4'
3''
O P
CF3
O
n
SO3Na 6 7
O P
CF3
O
O CF3
3 4
n
5
(b)
1,6
2,3,5 3'' tsPEPOF-130
3''
3',6',4
5'
4'
5'
4'
2',2,3,5 3',6',4
1''
2'' 1',1,6
7
1''
2'' 1',6
dsPEPOF-100
2' msPEPOF-100
7
4'
5'
7 3',6' 1,6
2,3,5 4
7
PEPOF
8.1
7.8 7.5 Chemical shift / ppm
7.2
6.9
Fig. S2. Chemical structures (a) and 1H NMR spectra (b) of PEPOF, msPEPOF-100, dsPEPOF-100 and tsPEPOF-130.
Table S1. Mechanical properties and methanol permeability of membranes. Mechanical properties Membranes
msPEPOF-100 dsPEPOF-100 dsPEPOF-110 dsPEPOF-120 tsPEPOF-100 tsPEPOF-110 tsPEPOF-120 tsPEPOF-130 Nafion 117
Tensile strength (MPa) 40.4 43.3 42.4 44.4 41.3 43.4 46.5 37.8 –
Young’s modulus (GPa) 1.10 1.11 1.13 0.94 1.08 1.13 1.09 0.77 –
Elongation at break (%) 6.2 10 8.2 7.4 6.0 7.0 6.7 9.0 –
Methanol permeability (×10-7 cm2/s) 2.4 2.2 2.7 3.3 1.2 1.4 2.0 2.5 15 3
Electronic Supplementary Material (ESI) for Polymer Chemistry This journal is © The Royal Society of Chemistry 2014
References 1. L. C. Fu, G. Y. Xiao, D. Y. Yan, J. Mater. Chem., 2012, 22, 13714–13722. 2. H. Y. Liao, G. Y. Xiao, D. Y. Yan, Chem. Commun., 2013, 49, 3979–3981. 3. N. Tan, G. Y. Xiao, D. Y. Yan, Chem. Mater., 2010, 22, 1022–1031.
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