Title Phosphoated & sulfoated poly(petafluorostyree) Vladimir Ataasov & Joche Kerres Istitute of Chemical Process Egieerig Uiversity of Stuttgart, Germay & P S 1
utlie Phosphoated poly(petafluorostyree) (PWN2010) Sythesis & Characterizatio Coductivity (EIS) Structure (SAXS) Ahydride formatio (phosphoic acid codesatio) Resistace to radical attack (etos test) Emulsio polymerizatio of petafluorostyree Molecular weight (GPC) Sulfoated poly(petafluorostyree) (sps) Sythesis & Characterizatio Resistace to heat (TGA) ydratio isotherms (water uptake) Coductivity (EIS) 2
Phosphoatio of PS + PS (commercial) Characteristics: P(SiMe 3 ) 3 160-170 C 5-8 hrs - Me 3 Si (bp. 16 C) P SiMe 3 SiMe 3 Water Refluxig 5 mi -2 Me 3 Si or (Me 3 Si) 2 P PWN2010 Yield: 98% phosphoatio above 90 % molecular weight M w = 67 kda (M w (PS) = 59 kda) IEC = 7 mmol g -1 (calc. 7.8 mmol g -1 ) pk a1 = 0.5 (Polystyree-P 3 2 : pk a1 = 1.9) resistace to heat up to 340 C T g above 340 C water soluble powder 3 Ataasov & Kerres Macromolecules 2011, 44, 6416
Coductivity at 1atm water pressure T ( C) Relative humidity σ (S cm -1 ) 160 16,0 150 20,8 140 130 27,6 37,1 P 3 2 PWN2010 120 50,7 110 70,5 100 100 Nafio117 P 3 2 P 3 2 PVPA PmPPA 1000/T (K -1 ) 4. Steiiger Phys. Chem. Chem. Phys., 2007, 9, 1764
SAXS SAXS Itesity (a.u.) d = 2p/q = 23 Å PWN 84% 2010, 84% R N117 Ambiet R q0 = 0,27 Å -1 q0 = 0,27 A-1 d=2p/q=23 A q1 = 0,557 Å -1 q1 = 0,557 1000 0,01 0,1 1 q (Å -1 )
Thermogravimetric aalysis C 3 S S P 3 3 2 3 PαMSSA PSSA PS PWN2010 Weight / wt % Polymer Defuctioal. [ C] Degradatio [ C] PαMSSA 201 381 PSSA 247 382 PS - 402 PWN 2010 340 391 Temperature / C
Phosphoic acid codesatio 31 P solid-state NMR fi110915-gudat-ataasov2_sol.101_001001r Dryig: 50 C, p = 1 mbar, a week bservig: Sigle resoace Reaso: free phosphoic fuctio Coclusio: Iability of PWN2010 to udergo self-codesatio at 50 C Aealig: 250 C, p = 1 atm, 5 hrs bservig: Shoulder i the mai resoace Reaso: formatio of ew phosphorous species Coclusio: PWN2010 formed ahydride at 250 C (cofirmed by TIR) 300 250 200 150 100 50 0-50 -100-150 -200-250 -300
Simulatio of 31 P CP/MAS NMR PVPA Itegratio: acid: ahydride= 58: 42 Ahydride > 90% Experimetal spectrum of PWN aealed at 250 C P acid form differece P P ahydride form A. Kaltbeitzel et al. Solid State Ioics 178 (2007) 469
eto test of PWN2010 W(log M) PWN Weightloss [wt%] PWN after 24, 48 ad 96h eto test PWN before eto test M w / kda PDI Before T - 67 7.4 After 24h T 0 137 3.2 After 48h T 0 106 2.8 After 96h T 2 105 2.8 9 Molecular weight (g mol -1 )
Emulsio polymerizatio of PS Name M calc kda M exp kda M w exp kda PDI PS - 25 105 4.2 1 100 312 716 2.3 Iit.: K 2 S 2 8 M/ 2 = 1/2 M/SDS = 50/1 T = 80 94 C for 1 h Rect. Time: 2 h PS 4 3 1 2 2 100 260 780 3.0 3 100 140 440 3.1 4 30 110 295 2.7 commercial Molecular weight (g mol -1 )
Sulfoatio of PS 24 30 C, 1h + NaS DMAc PS Characteristics: SNa tps 2 2 /C 50 C, 15 hrs S 3 sps sulfoatio 100 % IEC = 3.4 mmol g -1 (calc. 3.9 mmol g -1 ) pk a = - 2 (PSSA: pk a = - 0.5) resistace to heat up to 270 C molecular weight is ukow: sps is partially soluble oly i DMS
19 NMR 19 i DMS.esp B A A C A B A C B PS B SNa tps B A A B S 3 sps -130-135 -140-145 -150-155 -160-165 ppm
Thermogravimetrical aalysis Weight / wt % Polymer Defucioal. [ C] C 3 S 3 S 3 PαMSSA PSSA sps tps PS PWN2010 Degradatio [ C] PαMSSA 201 381 PSSA 247 382 sps 268 351 S 3 S P 3 2 tps 325 478 PS - 402 PWN 2010 340 391 Temperature / C
ydratio isotherms Water cotet (wt%) 30 C sps PWN2010 Nafio 117 λ([ 2 ]/[-P 3 2 or S 3 ]) 30 C sps PWN2010 Nafio 117 R (%) R (%) The absolute higher water uptake of sps ad PWN2010 is due to its higher umber of fuctioal group i compare to Nafio117.
Coductivity at 1atm water pressure Temperature ( C) 160 140 120 100 Coductivity (S cm -1 ) sps S 3 3 S sps 2-220 S 2 S 2 S 3 PWN2010 Nafio117 P 3 2 C C 2 C 2 C y x 2 C 2 C z C 2 C 2 S 3 C 3 M. Schuster et al Macromolecules 2009, 42, 3129. 1000/T (K -1 )
Summary & Coclusios Phosphoated poly(petafluorostyree) with phosphoatio degree above 90% is obtaied The high coductivity (σ = 0.1 S cm -1 at 110 C): Lamellar structurig (SAXS). The reduced formatio of ahydrides ( 31 P MAS NMR) Resistace to radical attack. Poly(petafluorostyree) was obtaied by emulsio polymerizatio Molecular weight (GPC): up to 800 kda Cotrol over molecular weight Sulfoated poly(petafluorostyree) is obtaied with 100% sulfoatio degree. Io coductivity (σ = 50 ms cm -1 at 150 C) is makig this material oe of the best io-coductig polymer. 16
Ackowledgmets Sadrie Lyoard (CEA, Greoble) Dietrich Gudat (Uiversity of Stuttgart) Wolfgag Meyer (MPI-P, Maiz) Klaus-Dieter Kreuer (MPI-K, Stuttgart) Thak you! Bastia Ruffma (IAT, Schweri) Deutsche orschugsgesellschaft (DG) 17