Abstract
Poly(vinylphosphonic acid) (PVPA) was synthesized by free radical polymerization of vinylphosphonic acid (VPA) in different solvents. Bromotrichloromethane as a chain transfer agent (CTA) was used in some experiments to control molecular weight of the PVPA. The effects of solvent type and initiator and CTA concentrations on the microstructure, molecular weight and stereoregularity of the resulting PVPA was extensively investigated by FTIR, 1HNMR, 31PNMR and elemental analysis. Polymers with a number-average molecular weight (Mn) in the range of 1550 to 42,190 gmol−1 were prepared. High molecular weight PVPA with Mn of 42,190 gmol−1 was obtained from aqueous solution polymerization of VPA with initiator/monomer molar ratio of 0.16/100 at 80°C. Molecular weight decreased with increasing the concentration of initiator and CTA. 1HNMR spectra were used to investigate tetrad sequences for the methylene protons of PVPA, from which stereochemical information of the polymer chain was obtained. Tetrad sequences were also calculated by Bernoullian probabilities. Moreover, the percent of head-to-head and tail-to-tail irregularities of the resulting PVPA were obtained to be in the range of 16.6–58% depending on the reaction conditions. The PVPA synthesized in acetic anhydride as a solvent had highest amount of the irregularities due to the high reaction rate, which does not allow controlling the structure. Furthermore, due to the importance of PVPA in the proton exchange membranes (PEMs), the effects of molecular weight and temperature on the acidity and titration behavior of PVPA polyelectrolyte were investigated. It was found that molecular weight has no significant effect on the acidity and dissociation of protons at operational conditions of degree of dissociation lower than 0.5. It was also found that by increasing the temperature, pH values were decreased, meaning that dissociation of protons and consequently the proton conductivity of PVPA membranes can be affected by temperature. Titration behavior of PVPA also showed that the PVPA has a behavior similar to a monoprotic acid.
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References
Tan J, Gemeinhart RA, Ma M, Saltzman WM (2005) Biomaterials 26:3663–3671
Millaruelo M, Steinert V, Komber H, Klopsch R, Voit B (2008) Macromol Chem Phys 209:366–374
Jiang DD, Yao Q, McKinney MA, Wilkie CA (1999) Polym Degrad Stab 63:423–434
Iumamoglu T, Yagci Y (2001) Turk J Chem 25:1–9
Park CH, Nam SY, Lee YM (1999) J Appl Polym Sci 74:83–89
Sahoo SK, Nagarajan R, Roy S, Samuelson LA, Kumar J, Cholli AL (2004) Macromolecules 37:4130–4138
Aslan A, Golcuk K, Bozkurt A (2012) J Polym Res 19:22
Ellis J, Anstice M, Wilson AD (1991) Clin Mater 7:341–346
Adusei GO, Deb S, Nicholson JW (2005) Dent Mater 21:491–497
Hector LG, Opalka SM, Nitowski GA, Wieserman L, Siegel DJ, Yu H, Adams JB (2001) Surf Sci 494:1–20
David G, Boutevin B, Seabrook S, Destarac M, Woodward G, Otter G (2007) Macromol Chem Phys 208:635–642
Sen U, Acar O, Celik S, Bozkurt A, Ata A, Tokumasu T, Miyamoto A (2013) J Polym Res 20:217
Schuster M, Rager T, Noda A, Kreuer KD, Maier J (2005) Fuel Cells 3:355–365
Acar O, Sen U, Bozkurt A, Ata A (2009) Int J Hydrog Energy 34:2724–2730
Aslan A, Celik S, Bozkurt A (2009) Solid State Ionics 180:1240–1245
Jiang F, Kaltbeitzel A, Zhang J, Meyer WH (2014) Int J Hydrog Energy 39:11157–11164
Sinirlioglu D, Mufftuoglu AE, Bozkurt A (2015) J Polym Res 22:154
David G, Boyer C, Tayouo R, Seabrook S, Ameduri B, Boutevin B, Woodward G, Destarac M (2008) Macromol Chem Phys 209:75–83
Kim YK, Gu L, Bryan TE, Kim JR, Chen L, Liu Y, Yoon JC, Breschi L, Pashley DH, Tay FR (2010) Biomaterials 31:6618–6627
Komber H, Steinert V, Voit B (2008) Macromolecules 41:2119–2125
Bingol B, Meyer WH, Wagner M, Wegner G (2006) Macromol Rapid Commun 27:1719–1724
Blidi I, Geagea R, Coutelier O, Mazieres S, Violleau F, Destarac M (2012) Polym Chem 3:609–612
Levin YA, Romanov VG, Ivanov BY (1975) Polym Sci USSR (Vysokomol Soyed) 17:880–886
Kosolapoff GM (1952) J Am Chem Soc 74:3427–3428
Kosolapoff GM (1948) J Am Chem Soc 70:1971–1972
Jin S, Gonsalves KE (1998) Macromolecules 31:1010–1015
Pike RM, Cohen RA (1960) J Polym Sci 44:531–538
Farrokhi M, Abdollahi M (2016) J Polym Res 23:122
Laguecir A, Ulrich S, Labille J, Fatin-Rouge N, Stoll S, Buffle J (2006) Eur Polym J 42:1135–1144
Sutheimer SH, Ferraco MJ, Cabaniss SE (1995) Anal Chim Acta 304:187–194
Sakurai M, Imai T, Yamashita F, Nakamura K, Komatsu T, Nakagawa T (1993) Polym J 25:1247–1255
Arnold A, Overbeek JTG (1950) J Phys Chem 69:192–206
Nagarajan R, Tripathy S, Kumar J (2000) Macromolecules 33:9542–9547
Durmus Z, Kavas H, Sozeri H, Toprak MS, Aslan A, Baykal A (2012) J Supercond Nov Magn 25:1185–1193
Kavlak S, Guner A, Rzayev ZMO (2012) J Appl Polym Sci 125:3617–3629
Kowalewski VJ, Kowalewski DG (1960) J Chem Phys 32:1272–1273
Koenig JL (1980) Chemical microstructure of polymer chains. Wiley Interscience Publ, NY
Strandberg C, Rosenauer C, Wegner G (2010) Macromol Rapid Commun 31:374–379
Katchalsky A, Shavit N, Eisenberg H (1954) J Polym Sci 13:69–84
Ullner M, Jonsson B, Widmark PO (1994) J Chem Phys 100:3365–3366
Reed CE, Reed WF (1992) J Chem Phys 96:1609–1620
Katchalsky A (1951) J Polym Sci 7:393–412
Katchalsky A, Gillis J (1949) Recl Trav Chim Pay-B 68:879–897
Lappan U, Geibler U, Oelmann M, Schwarz S (2012) Colloid Polym Sci 290:1665–1670
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Taherkhani, Z., Abdollahi, M. & Sharif, A. Synthesis and microstructural characterization of low to high molecular weight poly(vinylphosphonic acid)s: effect of molecular weight and temperature on acidity and polyelectrolyte behavior. J Polym Res 24, 132 (2017). https://doi.org/10.1007/s10965-017-1287-3
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DOI: https://doi.org/10.1007/s10965-017-1287-3