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Alkali-Grafting Proton Exchange Membranes Based on Co-Grafting of α-Methylstyrene and Acrylonitrile into PVDF 2022 Shufeng Li.pdf

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Alkali-Grafting Proton Exchange Membranes Based on Co-Grafting of α-Methylstyrene and Acrylonitrile into PVDF 2022 Shufeng Li.pdf

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polymers
Article
Alkali-GraftingProtonExchangeMembranesBasedon
Co-Graftingof -MethylstyreneandAcrylonitrileintoPVDF
ShufengLi*,XuelinLi,PengfeiFuandYaoZhang
KeyLaboratoryofAdvancedTextileComposites,CollegeofTextileScienceandEngineering,
TiangongUniversity,Tianjin300387,China;******@(.);
******@(.);******@(.)
*Correspondence:******@;Tel.:+86-022-8395-5287
Abstract:Anovelalkali-inducedgraftingpolymerizationwasdesignedtosynthesizeaPFGPAproton
exchangemembranebasedontheco-graftingof -methylstyrene(AMS)andacrylonitrile(AN)into
thepoly(vinylidenedifluoride)(PVDF):by
immersingthePVDFmembranesintoa1MNaOHsolutionandmixingthePVDFpowderswith
16%or20%,AMSwithANcouldbeco-graftedintothePVDFbackbonesintwo
graftingsolvents,THForIPA/,thegraftedmembranesweresulfonatedtoprovidethe
,theNa4SiO4treatmentsshowedagreatergraftingdegree

–50percentgraftingdegreewasobtainedin
eithertheTHForIPA/watersolventaftertheNa4SiO4treatmentandtheTHFresultedinagreater


ofabout40–50percentshowedabetterdimensionalstabilityinmethanol,greaterwateruptake
capabilities,andlowerionexchangecapacitiesandconductivitiesthantheNaflon117membranes.
Citation:Li,S.;Li,X.;Fu,P.;Zhang,%NaSiOtreatmentandTHFasthegraftingsolventexhibiteda
44
Alkali-
MembranesBasedonCo-Graftingof
alkali-graftedPFGPAmembranesinpracticaluse.
-MethylstyreneandAcrylonitrile
,14,2424.
/Keywords:PVDF;alkali-grafting; -methylstyrene;acrylonitrile;protonexchangemembrane
polym14122424
AcademicEditors:AndrzejPuszka
andBeataPodko´
Received:15May2022Recently,protonexchangemembranefuelcells(PEMFCs)haveattractedmoreand
Accepted:10June2022moreattentionasportable,clean,andefflcientelectrochemicalenergyconversionsystems
Published:15June2022duetotheirlowoperationtemperature,longlifetime,andhighpowerdensity[1].The
Publisher’sNote:MDPIstaysneutralprotonexchangemembrane(PEM)isoneofthekeycomponentsofthePEMFCs,which
withregardtojurisdictionalclaimsinprovidethechannelfortheprotontransportation[2].Naflon,aperfluorosulfonicacid
publishedmapsandinstitutionalaffll-polymerwithhighionconductivity,thermal,andmechanicalstability,isthemostsuc-
[3].However,Naflonmembranesexhibitthedrawbacks
ofhighcost,lowperformanceunderthelowrelativehumiditycondition,whichlimits
thecommercialapplicationonalarge-scale[4].Hence,manyeffortshavebeenmadeto
developalternativemembranesassubstitutesforNaflon[5]suchastheorganic/inorganic
Copyright:©[6,7],sulfonatedaromaticpolymers[8],blendedNafloncomposite
LicenseeMDPI,Basel,[9],andfluorinecontainingpolymersbygraftingpolymerization[10].Sul-
Thisarticleisanopenaccessarticlefonatedaromaticpolymersexhibitexcellentwateruptakecapability,ionexchangecapacity,
,
-
Attribution(CCBY)license(https://rinecontainingpolymers[10]includingthefluorinated(PTFE,FEP,andPFA)orpartially
(PVDFandETFE)membranespossessexcellentchemicalandthermalstability,
/).
Polymers2022,14,:///polym14122424:.
Polymers2022,14,24242of16
,howtointroduceionexchangegroupsinto
thefluorinatedpolymericmatrixisthekeytosuccessfullypreparingthefluorinatedPEMs.
RadiationgraftingisaneffectivewaytopreparethePEMsforfuelcells[11–13].The
propertiesofthemembranescanbeeasilycontrolledbymodifyingthegraftingpolymer-
(St)[14],duetoitslowcostandadjustableionexchange
capacitybysulfonation,isanappropriatematerialtoberadiation-graftedintothefluori-
,acrylonitrile(AN),methylacrylonitrile(MAN)[15],and
dimethylaminoethylmethacrylate(DMAEMA)[16]-
tiongraftingisstricttothepolymerizinginstrumentationduetotheuseofhighenergy
-andX-ray,whichisrelativelytoxicandexpensive.
Recently,Qiu[17]proposedanalkali(NaOH)solution-inducedgraftingpolymeriza-
tiontosynthesizethePVDF-g-PSSAmembrane,whichdisplayedahigherconductivity
[18]investi-
gatedthetetrasodiumorthosilicate(Na4SiO4)-inducedgraftingpolymerizationofPVDF


contentofNaOHorNa4SiO4,theprotonconductivityofthePVDF-g-PSSAmembranes
weregraduallyincreased.
Styrene,oritssulfonatedderivatives,isthemostcommonlyutilizedradiationgrafting
,themainshortcomingofpolystyrenederiva-
tivesisthatthebenzylicC–Hbondiseasilybrokentoformbenzylradicals,resultingina
subsequentchainscissionby -fragmentation[19,20].Usingfluorinatedmonomers(., ,
, -trifluorostyrene(TFS)),TFSpossesses
lowgraftingkinetics[21]andsulfonationdegree[22],leadingtoatoolongreactiontime
-sulfonatedmonomers(.,sulfonyl
fluoridecontainingTFSderivatives[21])canimprovethegraftingkinetics,buttheyare
tooexpensivetobeutilizedonalarge--substitutedstyrenicmonomerssuchas
p-methylstyreneorp-tert-butylstyrenehavealsobeenstudiedasalternativemonomers
inordertoincreasethechemicalstability[23].Theoretically, -methylstyrene(AMS),a
-substitutedstyrenicderivativethatiscommerciallyavailable,isthemostchemically
stable,andthepolymerizedAMSshowedsuperiorstabilitytopolystyreneunderoxidized
conditions[24].However,thehomopolymerizationofAMSisdifflcultduetothelow
sterichindranceofthe -methylgroupandlowceilingtemperature[25].GraftingofAMS
withothermonomerssuchasANormethacrylonitrile(MAN)[26–28]couldenhancethe
,fewstudieshavebeenfoundonthealkaligrafted
PVDFwithAMSanditsco-monomers.
Inthispaper,alkali-inducedgraftingprotonexchangemembraneswithco-grafting
PVDFwith -
contentsofthealkalisandsolventsonthegraftingpolymerizationwereinvestigatedand
theobtainedPVDF-basedprotonexchangemembranes(PFGPA)werecharacterizedin
termsofthemorphology,liquiduptakecapability,swelling,ionexchangecapacity(IEC),
conductivity,
dimensionalstabilityandlowswellinginmethanol,indicatingapotentialapplication
,easeofpreparation,andrelativeenvironmental-
friendliness,thealkaligraftingpolymerizationisattractiveandexhibitsanewapproachto
synthesizingPFGPAmembranes.


Kynar®polyvinylidenefluoride(PVDF)resinsforbatteries(Mw=400,000~600,000)
werepurchasedfromArkema,-methylstyrene(AMS)waspurchasedfrom
FutianChemicalCom.,Zhaoqing,(AN),N-methylpyrrolidone(NMP),
dibenzoylperoxide(BPO),tetrasodiumorthosilicate(Na4SiO4),1,2-dichloroethane,tetrahy-
drofuran(THF),isopropanol(IPA),hydrogenperoxide,andmethanolwerepurchasedfrom:.
CH
3
HCC
2
CH
HC
2
PVDFbackbone
PVDF
NaSiO
44
powder
CH
C
3
H
Alkali-treatedBPO
PVDFAMS
CH
casting
3
NMP
H
graftedcomponents
C
CHCCH
AN
22
Alkali-treated
PVDF
PVDFN
PVDFn
powder
membrane
C
CHCCH
22
Solvent
casting
R
NMPn
NaOH
C
Polymers2022,14,xFORPEERREVIEW3of17
Polymers2022,14,24243of16
(NMP),dibenzoylperoxide(BPO),tetrasodiumorthosilicate(Na4SiO4),1,2-dichloro-
ethane,tetrahydrofuran(THF),isopropanol(IPA),hydrogenperoxide,andmethanol
werepurchasedfromGuangfuFineChemicalCom.,GuangfuFineChemicalCom.,Tianjin,,
.
N

,,Sulfonation
NaOHandNaNaOHandNa4SiO4SiO4,wereusedtotreatthe4,.
R:-CN,-CONH,-COOH
SOH
2
3
PFGPAmembrane
.
.
NaOHtreatmentprocess:CertainamountsofPVDFpowdersandNMPsolutionwere
mixed,stirredfor2h,:CertainamountsofPVDFpowdersandNMPsolution
weremixed,stirredfor2hweredriedundervacuumat60,-,theywereimmersedintoa50mL
(TBAB)being°,theywereimmersedintoa50
addedat60
(TBAB)be-
toneutral.
ingaddedat60°
Na4SiO4treatmentprocess:CertainamountsofPVDFpowdersweredissolvedin
.%deionizedwater,thentheNaSiOpowderswereadded.
44
Themixturewasstirredfor2h,pouredontotheglassplateanddriedundervacuumtoNa4SiO4treatmentprocess:CertainamountsofPVDFpowdersweredissolvedin
NMPsolutioncontaining3wt.%deionizedwater,thentheNaaffordtheNa4SiO4-treatedPVDFmembranes,expressedas“”.
Themixturewasstirredfor2h,pouredontotheglassplateanddriedundervacuumtoBeforegrafting,thealkali-treatedPVDFmembraneswereswelledin1,2-dichloromethane
,IPA/water(I/W)orTHF,4SiO4-treatedPVDFmembranes,expressedas“PVDF_Na4SiO4percent”.
forgraftingpolymerizationwithANandAMSastheBeforegrafting,thealkali-treatedPVDFmembraneswereswelledin1,2co-monomersandBPOasthe-dichloro-

,IPA/water(I/W)or
PVDF-g-P(AMS-AN)werewashedwithacetoneand1,2-dichloromethanethreetimes,2h
THF,forgraftingpolymerizationwithANandAMSastheco-monomersandBPOasthe
each,toremovetheresiduereactantsonthesurfaceanddriedundervacuumat60Cfor
°
(GD)ofthePVDF-g-P(AMS-AN)wascalculatedaccordingto
PVDFEquation(1).-g-P(AMS-AN)werewashedwithacetoneand1,2-dichloromethanethreetimes,2
heach,toremovetheresiduereactantsonthesurfaceanddriedundm1m0ervacuumat60°C
GD=100%(1)
(GD)ofthePVDFm0-g-P(AMS-AN)wascalculatedaccording
toEquation(1).
1−0
𝐺=100%(1)
0
:.
Polymers2022,14,24244of16
whereGDisthegraftingdegree;m0andm1arethemassesofthePVDFmembranesbefore
andafterthegraftingpolymerization,respectively.
Afterward,thegraftedPVDFmembraneswereswelledin1,2-dichloromethanefor
,theyweresulfonatedinamixtureofchlorosulfonicacid/1,2-dichloromethane
(5:100,v:v)atroomtemperaturefor2h[26]
membraneswerewashedwithdeionizedwatertoneutralanddriedund