Phosphonated & sulfonated poly(pentafluorostyrene)

Transkript

1 Title Phosphoated & sulfoated poly(petafluorostyree) Vladimir Ataasov & Joche Kerres Istitute of Chemical Process Egieerig Uiversity of Stuttgart, Germay & P S 1

2 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

3 Phosphoatio of PS + PS (commercial) Characteristics: P(SiMe 3 ) 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

4 Coductivity at 1atm water pressure T ( C) Relative humidity σ (S cm -1 ) , , ,6 37,1 P 3 2 PWN , , Nafio117 P 3 2 P 3 2 PVPA PmPPA 1000/T (K -1 ) 4. Steiiger Phys. Chem. Chem. Phys., 2007, 9, 1764

5 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, ,01 0,1 1 q (Å -1 )

6 Thermogravimetric aalysis C 3 S S P PαMSSA PSSA PS PWN2010 Weight / wt % Polymer Defuctioal. [ C] Degradatio [ C] PαMSSA PSSA PS PWN Temperature / C

7 Phosphoic acid codesatio 31 P solid-state NMR fi 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)

8 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

9 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 After 24h T After 48h T After 96h T Molecular weight (g mol -1 )

10 Emulsio polymerizatio of PS Name M calc kda M exp kda M w exp kda PDI PS Iit.: K 2 S 2 8 M/ 2 = 1/2 M/SDS = 50/1 T = C for 1 h Rect. Time: 2 h PS commercial Molecular weight (g mol -1 )

11 Sulfoatio of PS 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

12 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 ppm

13 Thermogravimetrical aalysis Weight / wt % Polymer Defucioal. [ C] C 3 S 3 S 3 PαMSSA PSSA sps tps PS PWN2010 Degradatio [ C] PαMSSA PSSA sps S 3 S P 3 2 tps PS PWN Temperature / C

14 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.

15 Coductivity at 1atm water pressure Temperature ( C) Coductivity (S cm -1 ) sps S 3 3 S sps 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, /T (K -1 )

16 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

17 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