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Polyaniline salt catalyzed synthesis of hyperbranched polyester and its use as dopant in polyaniline salt for coating, fluorescence, and supercapacitor electrode

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Abstract

Synthesis of novel polyaniline salts is an important work for their use in industrial applications. The objective of this work is to use alcohol in the polymerization of aniline instead of hazardous protic acids, which are mostly being used. For this purpose, hyperbranched polyesters (HBPEs) containing many alcohol groups were selected. In the HBPEs, alcohol groups could be increased via preparation of first, second, and third generation of HBPE. HBPEs were synthesized from the reaction of 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) and triethanolamine (TEA) as a nitrogen containing core. This reaction was promoted using polyaniline salt containing high-strength protic acid, trifluoromethanesulfonic acid, as catalyst for the first time. Interestingly, used these HBPEs in the aqueous polymerization of aniline to polyaniline salt containing HBPEs. Properties of these novel polyaniline salts in terms of yield, density, conductivity, solubility, crystalline nature, morphology, and application as electrode in supercapacitor were determined. These polyaniline salts containing dual dopants of H2SO4 and HBPE are stabile up to 210 °C and showed highly ordered semicrystalline nature with nanorods morphology (35 to 60 nm). Yield, density, and conductivity of the PANI-HBPEs salts are independent of the generation of HBPEs. Polyaniline salt containing third-generation hyperbranched polyester sample showed higher specific capacitance(450 F g−1). These polyaniline salts are insoluble in most of the common organic solvents. Polyaniline salts containing HBPEs in organic solvent were synthesized via emulsion polymerization pathway (E-PANI-HBPEs). These polyaniline salts contains three dopants, HBPE, dodecyl hydrogen sulfate (DHS) and H2SO4, were isolated in chloroform solvent, which showed particle size around 85 nm, with fluorescence property, and hydrophilicity. Polyaniline-HBPEs prepared via emulsion polymerization showed higher conductivity than that of the samples prepared via aqueous polymerization pathways.

Synthesis and properties of PANI-HBPE salts

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References

  1. Shirakawa H, Louis EJ, MacDiarmid AG, Chiang CK, Heeger AJ (1977) Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH)x. J Chem Soc Chem Commun 16:578–580

    Article  Google Scholar 

  2. Huang Y, Li J, Chen X, Wang X (2014) Applications of conjugated polymer based composites in waste water purification. RSC Adv 4:62160–62178

    Article  CAS  Google Scholar 

  3. Dutta K, Das S, Rana D, Kundu PP (2015) Enhancements of catalyst distribution and functioning upon utilization of conducting polymers as supporting materials in DMFCs: a review. Polym Rev 55:1–56

    Article  CAS  Google Scholar 

  4. Wang YZ, Epstein AJ (1999) Interface control of light-emitting devices based on pyridine-containing conjugated polymers. Acc Chem Res 32:217–224

    Article  CAS  Google Scholar 

  5. Zhang W, Cheng Y, Yin X, Liu B (2011) Solid-state dye-sensitized solar cells with conjugated polymers as hole-transporting materials. Macromol Chem Phys 212:15–23

    Article  CAS  Google Scholar 

  6. Elkais R, Gvozdenovic M, Jugovic BZ, Grgur BN (2013) The influence of thin benzoate-doped polyaniline coatings on corrosion protection of mild steel in different environments. Prog Org Coat 76:670–676

    Article  CAS  Google Scholar 

  7. Wang K, Wu H, Meng Y, Wei Z (2014) Conducting polymer nanowire arrays for high performance supercapacitors. Small 10:14–31

    Article  CAS  PubMed  Google Scholar 

  8. Mirfakhrai T, Madden JDW, Baughman RH (2007) Polymer artificial muscles. Mater Today 10:30–38

    Article  CAS  Google Scholar 

  9. Novak P, Muller K, Santhanam VSK, Haas O (1997) Electrochemically active polymers for rechargeable batteries. Chem Rev 97:207–282

    Article  CAS  PubMed  Google Scholar 

  10. Dutta K, Kumar P, Das S, Kundu PP (2014) Utilization of conducting polymers in fabricating polymer electrolyte membranes for application in direct methanol fuel cells. Polym Rev 54:1–32

    Article  CAS  Google Scholar 

  11. Nataraj MSK, Tejraj M, Aminabhavi, Sukumar R, Madhusoodana CD (2006) Polyaniline membranes for separation and purification of gases, liquids, and electrolyte solutions. Sep Purif Rev 35:249–283

    Article  CAS  Google Scholar 

  12. Song E, Choi JW (2013) Conducting polyaniline nanowire and its applications in chemiresistive sensing. Nanomaterials 3:498–523

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Kelly FM, Meunier L, Cochrane C, Koncar V (2013) Polyaniline: application as solid state electrochromic in a flexible textile. Displays 34:1–7

    Article  CAS  Google Scholar 

  14. Gordana CM (2013) Recent advances in polyaniline research: polymerisation mechanisms, structural aspects, properties and applications. Synth Met 177:1–47

    Article  CAS  Google Scholar 

  15. Peng D, Zhi L, Zhenzhen C, Jiao Z, Chao W, Xinhua X (2016) Rapid synthesis of hierarchical nanostructured polyaniline hydrogel for high power density energy storage application and three-dimensional multilayers printing. J Mater Sci 51:4274–4282

    Article  CAS  Google Scholar 

  16. Guo F, Liu Q, Hongyu M (2016) Flexible and cross-linked polyaniline nets as promising supercapacitor electrodes. Mater Lett 163:115–117

    Article  CAS  Google Scholar 

  17. Apparao T, Arukula R, Narayan R, Rao CRK, Raju KVSN (2015) Energy storage and surface protection properties of dianiline co-polymers. RSC Adv 5:106523–106535

    Article  CAS  Google Scholar 

  18. Ravi B, Rajender B, Palaniappan S (2016) Improving the electrochemical performance by sulfonation of polyaniline-graphene-silica composite for high performance supercapacitor. Int J Polym Mater 65:835–840

    Article  CAS  Google Scholar 

  19. Park YR, Doh JH, Shin K, Seo YS, Kim YS, Kim SY, Choi WK, Hong YJ (2015) Solution-processed quantum dot light-emitting diodes with PANI: PSS hole-transport interlayers. Org Electron 19:131–139

    Article  CAS  Google Scholar 

  20. Kulkarni MV, Kasiviswanath A, Khanna PK (2006) Synthesis and characterization of conducting polyaniline doped with polymeric acids. J Macromol Sci Pure Appl Chem 43:759–771

    Article  CAS  Google Scholar 

  21. Ramesh G, Palaniappan S (2015) A novel process of alcohol promoted polymerization of aniline to form a nanofibrous, fluorescent and highly crystalline polyaniline salt. New J Chem 39:8545–8551

    Article  CAS  Google Scholar 

  22. Gao C, Yan D (2004) Hyperbranched polymers: from synthesis to applications. Prog Polym Sci 29:183–275

    Article  CAS  Google Scholar 

  23. Flory PJ (1952) Molecular size distribution in three dimensional polymers. VI. Branched polymers containing A—R—Bf-1 type units. J Am Chem Soc 74:2718–2723

    Article  CAS  Google Scholar 

  24. Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca

    Google Scholar 

  25. Hsieh TT, Tiu C, Simon GP (2001) Melt rheology of aliphatic hyperbranched polyesters with various molecular weights. Polymer 42:1931–1939

    Article  CAS  Google Scholar 

  26. Ikladious NE, Mansour SH, Rozik NN, Dirnberger K, Eisenbach CD (2008) New aliphatic hyperbranched polyester polyols based on 1,3,5-tris(2-hydroxyethyl) cyanuric acid as a core. J Polym Sci A: Polym Chem 46:5568–5579

    Article  CAS  Google Scholar 

  27. Jena KK, Raju KVSN, Prathab B, Aminabhavi TM (2007) Hyperbranched polyesters: synthesis, characterization, and molecular simulations. J Phys Chem B 111:8801–8811

    Article  CAS  PubMed  Google Scholar 

  28. Malmstrom E, Johansson M, Hult A (1995) Hyperbranched aliphatic polyesters. Macromolecules 28:1698–1703

    Article  Google Scholar 

  29. Magnusson H, Malmstrom E, Hult A (2000) Structure buildup in hyperbranched polymers from 2,2-Bis(hydroxymethyl)propionicAcid. Macromolecules 33:3099–3104

    Article  CAS  Google Scholar 

  30. Goswami A, Singh AK (2004) Hyperbranched polyester having nitrogen core: synthesis and applications as metal ion extractant. React Funct Polym 61:255–263

    Article  CAS  Google Scholar 

  31. Palaniappan S, Rajender B (2010) A novel polyaniline-silver nitrate-p-toluenesulfonic acid salt as recyclable catalyst in the stereoselective synthesis of β-amino ketones: “one- pot” synthesis in water medium. Adv Synth Catal 352:2507–2514

    Article  CAS  Google Scholar 

  32. Hansen AS, Du L, Kjaergaard HJ (2014) The effect of fluorine substitution in alcohol–amine complexes. Phys Chem Chem Phys 16:22882–22891

    Article  CAS  Google Scholar 

  33. Meixiang W (1989) The influence of polymerization method and temperature on the absorption spectra and morphology of polyaniline. Synth Met 31:51–59

    Article  Google Scholar 

  34. Xia Y, Wiesinger JM, Macdiarmid AG, Arthur JE (1995) Camphorsulfonic acid fully doped polyaniline emeraldine salt: conformations in different solvents studied by an ultraviolet/visible/near-infrared spectroscopic method. Chem Mater 7:443–445

    Article  CAS  Google Scholar 

  35. Panel ML, Fangle Z, Dazhang Z, Hui D, Yaokang L, Liangchun L, Lihua G (2018) Ultramicroporous carbon nanoparticles derived from metal–organic framework nanoparticles for high-performance supercapacitor. Mater Chem Phys 211:234–241

    Article  CAS  Google Scholar 

  36. Panel LM, Dazhang Z, Yunhui Z, Mingxian L, Hui D, Wei X, Quanjing Z, Liangchun L, Yaokang L, Lihua G (2017) Design of carbon materials with ultramicro-, supermicro- and mesopores using solvent- and self-template strategy for supercapacitors. Micropor Mesopor Mater 253:1–9

    Article  CAS  Google Scholar 

  37. Panel MXL, Ling YC, Dazhang Z, Hui D, Wei X, Zijie X, Lihua G, Long WC (2016) Zinc tartrate oriented hydrothermal synthesis of microporous carbons for high performance supercapacitor electrodes. Chin Chem Lett 27:399–404

    Article  CAS  Google Scholar 

  38. Rahul RS, Christine Y, Jing T, Toshiaki T, Yusuke I, Naoya K, Yusuke Y (2016) A high-performance supercapacitor cell based on ZIF-8-derived nanoporous carbon using an organic electrolyte. Chem Commun 52:4764–4767

    Article  Google Scholar 

  39. Rahul RS, Shao HH, Kevin CWW, Yusuke Y (2014) Large-scale synthesis of reduced graphene oxides with uniformly coated polyaniline for supercapacitor applications. Chem Sus Chem 7:1551–1556

    Article  CAS  Google Scholar 

  40. Jing T, Yusuke Y (2016) Carbon materials: MOF morphologies in control. Nat Chem 8:638

    Article  CAS  Google Scholar 

  41. Huihua L, Juan S, Linlin W, Xiaomiao F, Ruiqing L, Wenjin Z, Zhendong H, Yanwen M, Lianhui W (2017) Flexible all-solid-state supercapacitors based on polyaniline orderly nanotubes array. Nanoscale 9:193–200

    Article  CAS  Google Scholar 

  42. Xiaomiao F, Ningna C, Jinhua Z, Yi L, Zhendong H, Lei Z, Yanwen M, Lianhui W, Xiaohong Y (2015) Facile synthesis of shape-controlled graphene–polyaniline composites for high performance supercapacitor electrode materials. New J Chem 39:2261–2268

    Article  CAS  Google Scholar 

  43. Xiaomiao F, Jinhua Z, Linlin W, Yi L, Zhendong H, Shufen C, Yanwen M, Lianhui W, Xiaohong Y (2015) Synthesis of shape-controlled NiO–graphene nanocomposites with enhanced supercapacitive properties. New J Chem 39:4026–4034

    Article  CAS  Google Scholar 

  44. Umashankar M, Palaniappan S (2015) Improved electrochemical performances of polyaniline by graphitized mesoporus carbon: hybrid electrode for supercapacitor. J Appl Polym Sci 132:42540

    Google Scholar 

  45. Rizwan U, Salma B, Anwarul HAS, Khurshid A, Fadi A (2016) Synthesis and characterization of polyaniline doped with polyvinyl alcohol by inverse emulsion polymerization. Synth Met 222:162–169

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Acknowledgements

We thank to CSIR, New Delhi under the TAPSUN program (NWP-0056) for funding. We are thankful to Dr.S.Chandrasekhar, Director, and Dr.T.Shekharam, Head, PFM Division,CSIR-IICT for their support and encouragement.SNK thanks UGC, India, for financial Support.

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Correspondence to Palaniappan Srinivasan.

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Karri, S.N., Male, U. & Srinivasan, P. Polyaniline salt catalyzed synthesis of hyperbranched polyester and its use as dopant in polyaniline salt for coating, fluorescence, and supercapacitor electrode. Ionics 25, 191–202 (2019). https://doi.org/10.1007/s11581-018-2583-6

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