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Supporting Information for

Tertiary Sulfonium as Cationic Functional Group for Hydroxide Exchange Membranes Bingzi Zhang, Shuang Gu, Junhua Wang, Ye Liu, Andrew Herring, Yushan Yan*

1. Experimental methods

Synthesis of diphenyl(3-methyl-4-methoxyphenyl) sulfonium triflate: 16.2 g (80 mmol) diphenyl

sulfoxide and 9.77 g (80 mmol) methylanisole were dissolved in 800 mL dichloromethane. The solution

was cooled to -78 oC in a dry ice-acetone bath and 22.6 g (80 mmol) trifluoromethanesulfonic anhydride

was added dropwise. The mixture was stirred at room temperature for 1 h. After the reaction, the mixture

was washed three times with saturated sodium bicarbonate solution and then with double deionized water

(DDI) water and dried under anhydrous magnesium sulfate for 24 h. The treated solution was

concentrated to 100 mL by a rotary evaporator and added dropwisely into 500 mL ethyl ether to

precipitate (3-methyl-4-methoxyphenyl) sulfonium triflate. The white precipitate was filtered and dried

under vacuum at room temperature for 24 hrs.

Synthesis of diphenyl(3-bromomethyl-4-methoxyphenyl) sulfonium chloride: 4.56 g (10 mmol)

diphenyl(3-methyl-4-methoxyphenyl) sulfonium triflate and 1.78 g (10 mmol) N-bromosuccinimide

(NBS) was dissolved in 100 mL dichloroethane. The solution was heated to 85 oC, followed by addition

of 0.12 g (0.5 mmol) benzoyl peroxide (BPO). The mixture was stirred at room temperature for 24 h.

After the reaction, the mixture was added dropwise into 300 mL ethyl ether to precipitate diphenyl(3-

bromomethyl-4-methoxyphenyl) sulfonium triflate. The precipitate was washed three times with ethyl

ether and dried under vacuum at room temperature for 24 h. Then, diphenyl(3-bromomethyl-4-

methoxyphenyl) sulfonium triflate was dissolved in 1000 mL DDI water, followed by addition of 120 g

IRA-900 anion exchange resin to convert triflate ions to chloride ions. After 48 h, the resin was filtered

and the water was evaporated to give diphenyl(3-bromomethyl-4-methoxyphenyl) sulfonium chloride.

Synthesis of chloromethylated polysulfone (CMPSf): 15 g (33.9 mmol) polysulfone (PSf) was dissolved in 750 mL chloroform. 10.18 g (339 mmol) paraformaldehyde and 36.9 g (339 mmol) trimethylchlorosilane were added into PSf solution, followed by dropwise addition of 1.767 g (6.78 mmol) stannic chloride. The mixture was stirred at 55 oC for 72 h. After the reaction, the mixture was poured into ethanol to precipitate CMPSf. The precipitate was separated by filtration, washed three times with ethanol and dried under vacuum at room temperature for 24 h. The degree of chloromethylation is 128% (1H NMR in Figure S3).

Synthesis of butylaminated polysulfone (PSf-BA): 2.02 g (4 mmol) chloromethylated polysulfone was dissolved in 40 mL 1-methyl-2-pyrrolidinone, followed by addition of 4.69 mL (40 mmol) butyl amine and 3.16 g (8 mmol) cesium carbonate. The mixture was stirred at room temperature for 48 h. After the reaction, the mixture was added dropwise into 400 mL DDI water to precipitate butylaminated polysulfone. The precipitate was washed three times with DDI water, filtered and dried in vacuum at 60

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2012

oC for 4Figure S

SynthesfunctionMeOTAreaction,washed wfunctiona

PreparaThe PSf-followedMeOTA48 h to immerse

MeasurThermogToledo scatteringeneratoimpedanby immeperiod. Tresidual carried ofollowed

2. 1H N

8 h. The con4).

sis of dipnalized polyS chloride w, the solutionwith ethanol alization of M

ation of Mef-MeOTASCld by evaporaSOH membrexchange ch

ed in DDI wa

rement: 1H gravimetric aTGA/DSC1 g (SAXS) p

or. The condnce method aersing the mThen the memKOH, follow

out by dissold by 1H NMR

NMR spect

nversion of c

phenyl(3-meysulfone (PSwere dissolven was added d

three times, MeOTAS cat

OTAS hydrl/N-methylpy

ating the solvrane was obthloride ions

ater for 48 h t

NMR speanalysis (TGthermograv

pattern was oductivity meat room temp

membranes inmbranes werwed by the 1Hlving and keR analysis.

tra

chloromethy

ethyl-4-methSf-MeOTASd in 1 mL Ndropwise intofiltered and dtion was 46%

roxide functyrrolidone (Nvent at 30 oCained by treafor hydroxi

to remove res

ectra were GA) was perf

imetric analobtained on easurements perature1. Then a 1 M KOHre washed thoH NMR analyeping the co

yl group to s

hoxyphenyl) SCl): 0.110 gNMP. The solo ethanol to pdried in vacu

% (1H NMR i

tionalized pNMP) solutioC for 24 h to ating PSf-Meide ions. Thesidual KOH.

measured aformed in nilyzer at a hAnton Paar were carried

e alkaline staH solution atoroughly by ysis. The alk

ompounds in

econdary am

tertiary sg (0.2 mmollution was stprecipitate PSuum at room n Figure S5)

polysulfoneon (10 wt %)

obtain a PSeOTASCl in en the memb

at 400 MHitrogen (flow

heating rate SAXSess w

d out by usability test oft 60 oC or roand immerse

kaline stabilit1 M KOD/D

mine is close

sulfoniuml) PSf-BA atirred at 60 oCSf-MeOTAStemperature

).

(PSf-MeOT) was pouredf-MeOTASC1 M KOH abrane was w

Hz on an w rate: 20 mof 10 oC/m

with a PANasing an ex-sf TAS based oom temperaed in DDI wty test of the D2O solution

to 100% (1H

(MeOTAS) and 0.227g (C for 24 hrs

SCl. The precfor 24 h. Th

TASOH) basd onto a flat gCl membraneat room tempwashed thoro

AV400 spemL/min) withmin. Small-analytical PW3situ four-eleHEMs was

ature for a cater for 48 hmodel comp

n at 60 oC fo

H NMR in

chloride (0.4 mmol) . After the

cipitate was e degree of

sed HEM: glass sheet, e. The PSf-perature for oughly and

ectrometer. h a Mettler ngle X-ray 3830 X-ray ctrode AC carried out ertain time

h to remove pounds was or 10 days,


Figure S1(CDCl3) a

Figure S2chloroform

Figure S3solvent ancalculated

Where, Aring) in th

1. 1H NMR spas solvent and

2. 1H NMR spm (CDCl3) as s

3. 1H NMR spnd tetramethyld from the follo

A9 and A7 are ine spectrum of

ectrum of diptetramethylsil

ectrum of dipsolvent and te

ectrum of chllsilane (TMS) owing equation

ntegral area off CMPSf.

phenyl(3-methane (TMS) as

phenyl(3-bromtramethylsilan

loromethylateas internal stan:

DC

f 9 (proton in −

hyl-4-methoxys internal stand

momethyl-4-mne (TMS) as in

ed polysulfonandard. The de

9

7

210

AC

A

−CH2Cl) and 7

xyphenyl) sulfdard.

methoxyphenyternal standar

ne (CMPSf). Degree of chloro

00%

7 (proton adjac

fonium triflate

yl) sulfoniumrd.

Deuterated chloomethylation (

cent to −SO2−

e. Deuterated

m triflate. Deut

oroform (CDC(DC) of CMPS

group in the a

chloroform

terated

Cl3) as f was

aromatic


Figure S4and tetramthe conve

Figure S5dimethyl sunconvertcalculated

4. 1H NMR spmethylsilane (Tersion of chloro

5. 1H NMR spsulfoxide (DMSted butylamined from the follo

ectrum of buTMS) as internomethyl group

ectrum of MeSO) as solvene group (as showing equation

utylaminated pnal standard. T

p to butyl amin

eoTAS chloridnt and tetramethown in Figuren:

4DS

polysulfone (PThe disappeare is close to 1

de functionalithylsilane (TM

e S4). The deg

(12 )

2 11

DCA

DC

(PSf-BA). Deurance of the ch00%.

ized polysulfoMS) as internal gree of function

1

2 100%

AA

terated chlorohemical shift 4

one (PSf-MeOstandard. H9’-

nalization of M

oform (CDCl3) 4.44 ppm indic

OTASCl). Deu-13’ are assigne

MeOTAS cation

as solvent cates that

terated ed to the n (DS) was


3. SAXS diffraction pattern

Firgure S6. SAXS pattern of PSf-MeOTASCl with an IEC of 0.69 mmol g-1.

4. Stability tests

100 200 300 400 500 600 700 8000

20

40

60

80

100

(a)

Wei

gh

t / %

Tem perature / oC

PSf PSf-BA PSf-MeOTASOH

100 200 300 400 500 600 700 800

-2.0

-1.5

-1.0

-0.5

0.0

(b)

Wei

gh

t lo

ss r

ate

/ (%

oC

1)

Temperature / oC

PSf PSf-BA PSf-MeOTASOH

Figure S7. Thermal gravimetric analysis (TGA) curves (a) and derivative thermal gravimetric (DTG) curves (b) of the pristine PSf (black line), butylaminated PSf (PSf-BA) (blue line) and PSf-MeOTSOH (red line). Test conditions: nitrogen atmosphere with 20 mL min−1 of flow rate, and 10 oC min−1 of heating rate.


Figure S8. 1H NMR spectra of PSf-MeOTAS polymer subjected to alkaline degradation test for different time. (a) 0 day or before test, (b) 1 day, (c) 5 days, and (d) 10 days. Deuterated dimethyl sulfoxide (DMSO-d6) as solvent and tetramethylsilane (TMS) as internal standard. Test conditions: 1 M KOD/D2O for test solution and 60 oC for test temperature.

Scheme S1. Chemical structures of two model compounds: MeOTAS (a) and MeO-free TAS (b).

(a) (b)

3SC l SCl


Figure S9. 1H NMR spectra of MeOTAS cation compound. (a) before alkaline degradation test, and (b) after degradation test. Deuterated water (D2O) as solvent and tetramethylsilane (TMS) as internal standard. Test conditions: 1 M KOD/D2O for test solution, 60 oC for test temperature, and 10 days for test time period.

Figure S10. 1H NMR spectra of MeO-free TAS cation compound. (a) before alkaline degradation test, and (b) after alkaline degradation test. Deuterated water (D2O) as solvent and tetramethylsilane (TMS) as internal standard. Test conditions: 1 M KOD/D2O for test solution, 60 oC for test temperature, and 10 days for test time period.


1. S. Gu, R. Cai, T. Luo, Z. W. Chen, M. W. Sun, Y. Liu, G. H. He and Y. S. Yan, Angew. Chem., Int. Ed., 2009, 48, 6499‐6502.


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