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Novel strategies for the synthesis of hydroxylated and carboxylated polystyrenes

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Abstract

Hydroxylated and carboxylated polystyrenes (PHMSt and PCSt, respectively) were synthesized using facile strategies. For this purpose, PSt was synthesized through atom transfer radical polymerization (ATRP) approach and then brominated at the para-position of the aromatic rings to produce PBrSt. The bromination efficiency was calculated to be 37 and 68%, even though there was a degradation of the polymer chains, using 60 or 100 mol% of bromine relative to the PSt, respectively. The brominated polymer was converted into Grignard reagent (PSt-magnesium-Br), and then reacted with anhydrous formaldehyde and solid carbon dioxide (Dry Ice) to afford PHMSt and PCSt, respectively. The chemical structures of all synthesized polymers were characterized using Fourier transform infrared (FTIR) as well as proton nuclear magnetic resonance (1H NMR) spectroscopies. Furthermore, the thermal behavior of the synthesized PHMSt and PCSt were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

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References

  1. Bhandari S, Chandra S (1994) Synthesis and film-forming properties of chlorinated polystyrene. Pigm Resin Technol 23:3–9

    Article  CAS  Google Scholar 

  2. Keskkula H, Turley SG (1978) Polyisoprene modified polystyrene. Polymer 19:797–800

    Article  CAS  Google Scholar 

  3. Jaymand M (2014) Recent progress in the chemical modification of syndiotactic polystyrene. Polym Chem 5:2663–2690

    Article  CAS  Google Scholar 

  4. Jaymand M (2011) Exfoliated syndiotactic polystyrene-graft-poly(methyl methacrylate)/montmorillonite nanocomposite prepared by solvent blending. Polym J 43:901–908

    Article  CAS  Google Scholar 

  5. Adhikari R, Michler GH (2004) Influence of molecular architecture on morphology and micromechanical behavior of styrene/butadiene block copolymer systems. Prog Polym Sci 29:949–986

    Article  CAS  Google Scholar 

  6. Bagheri A, Azdast T, Doniavi A (2013) An experimental study on mechanical properties of friction stir welded ABS sheets. Mater Design 43:402–409

    Article  CAS  Google Scholar 

  7. Hatamzadeh M, Mahyar A, Jaymand M (2012) Chemical modification of polyaniline by N-grafting of polystyrenic chains synthesized via nitroxide-mediated polymerization. J Braz Chem Soc 23:1008–1017

    Article  CAS  Google Scholar 

  8. Jaymand M (2012) Synthesis and characterization of syndiotactic polystyrene-graft-poly(methyl methacrylate) via free radical polymerization. Polym-Plast Technol Eng 51:514–520

    Article  CAS  Google Scholar 

  9. Bevacqua F, Basso A, Gitto R, Bradley M, Chimirri A (2001) Solid-phase friedel–crafts acylation on polystyrene resins-synthesis of antiepiletic 1-aryl-3,5-dihydro-4H-2,3-benzodiazepin-4-ones. Tetrahedron Lett 42:7683–7685

    Article  CAS  Google Scholar 

  10. Nasef MM, Saidi H (2004) Structure of polyethylene-graft-polystyrene sulfonic acid membranes prepared by radiation-induced grafting. Int J Polym Mater Polym Biomater 53:1027–1043

    Article  CAS  Google Scholar 

  11. Ishikawa T, Morino K, Sudo A, Endo T (2010) Incorporation of ketone groups into poly(4-hydroxystyrene)s main chain by radical copolymerization of 4-(tert-butoxy)styrene and 2,2-diphenyl-4-methylene-1,3-dioxolane and their photoscission. J Polym Sci A 48:4344–4350

    Article  CAS  Google Scholar 

  12. Song JS, Chagal L, Winnik MA (2006) Monodisperse micrometer-size carboxyl-functionalized polystyrene particles obtained by two-stage dispersion polymerization. Macromolecules 39:5729–5737

    Article  CAS  Google Scholar 

  13. Nakahama S, Hirao A (1990) Protection and polymerization of functional monomers: Anionic living polymerization of protected monomers. Prog Polym Sci 15:299–335

    Article  CAS  Google Scholar 

  14. Schüll C, Frey H (2012) Controlled synthesis of linear polymers with highly branched side chains by “hypergrafting”: poly(4-hydroxy styrene)-graft-hyperbranched polyglycerol. ACS Macro Lett 1:461–464

    Article  Google Scholar 

  15. Barclay GG, Hawker CJ, Ito H, Orellana A, Malenfant PRL, Sinta RF (1998) The “living” free radical synthesis of poly(4-hydroxystyrene): physical properties and dissolution behavior. Macromolecules 31:1024–1031

    Article  CAS  Google Scholar 

  16. Sweat DP, Kim M, Schmitt AK, Perroni DV, Fry CG, Mahanthappa MK, Gopalan P (2014) Phase behavior of poly(4-hydroxystyrene-block-styrene) synthesized by living anionic polymerization of an acetal protected monomer. Macromolecules 47:6302–6310

    Article  CAS  Google Scholar 

  17. Deokar S, Ghadage RS, Rajan CR, Ponrathnam S (2004) Facile synthesis of poly(4-hydroxy styrene) from polystyrene. J Appl Polym Sci 91:3192–3201

    Article  CAS  Google Scholar 

  18. Nasrullah JM, Raja S, Vijayakumaran K, Dhamodharan R (2000) A practical route for the preparation of poly(4-hydroxystyrene), a useful photoresist material. J Polym Sci A 38:453–461

    Article  CAS  Google Scholar 

  19. Cho H, Kim J, Patil P, Kim JY, Kim T (2007) Synthesis of succinylated poly(4-hydroxystyrene) and its application for negative-tone photoresist. J Appl Polym Sci 103:3560–3566

    Article  CAS  Google Scholar 

  20. Stepanek M, Hajduova J, Prochazka K (2012) Association of poly(4-hydroxystyrene)-block-poly(ethylene oxide) in aqueous solutions: block copolymer nanoparticles with intermixed blocks. Langmuir 28:307–313

    Article  CAS  Google Scholar 

  21. Kim J, Zhou H, Nguyen ST, Torkelson JM (2006) Synthesis and application of styrene/4-hydroxystyrene gradient copolymers made by controlled radical polymerization: compatibilization of immiscible polymer blends via hydrogen-bonding effects. Polymer 47:5799–5809

    Article  CAS  Google Scholar 

  22. Noro A, Matsushita Y, Lodge TP (2009) Gelation mechanism of thermoreversible supramacromolecular ion gels via hydrogen bonding. Macromolecules 42:5802–5810

    Article  CAS  Google Scholar 

  23. Epoxy resins or polyisocyanates reacted with derivatized novolak polyhydroxystyrene. Du Pont Electronic Polymers L.P., US patent, 1977, NO US7566752

  24. Lu SY, Hamerton I (2002) Recent developments in the chemistry of halogen-free flame retardant polymers. Prog Polym Sci 27:1661–1712

    Article  CAS  Google Scholar 

  25. Mountrichas G, Pispas S (2006) Synthesis and pH responsive self-assembly of new double hydrophilic block copolymers. Macromolecules 39:4767–4774

    Article  CAS  Google Scholar 

  26. Kawaguchi H (2000) Functional polymer microspheres. Prog Polym Sci 25:1171–1210

    Article  CAS  Google Scholar 

  27. Du M, Guo B, Lei Y, Liu M, Jia D (2008) Carboxylated butadiene–styrene rubber/halloysite nanotube nanocomposites: interfacial interaction and performance. Polymer 49:4871–4876

    Article  CAS  Google Scholar 

  28. Lee SG, Ha JW (2016) Synthesis of highly carboxylated monodisperse polystyrene microspheres by dispersion polymerization in fluorinated alcohol. Macromol Res 24:675–683

    Article  CAS  Google Scholar 

  29. Menshikova AY, Evseeva TG, Skurkis YO, Tennikova TB, Ivanchev SS (2005) Monodisperse carboxylated polystyrene particles: synthesis, electrokinetic and adsorptive properties. Polymer 46:1417–1425

    Article  CAS  Google Scholar 

  30. Atici OG, Akar A, Rahimian R (2001) Modification of poly(maleic anhydride-co-styrene) with hydroxyl containing compounds. Turk J Chem 25:259–266

    CAS  Google Scholar 

  31. Jaymand M, Hatamzadeh M, Omidi Y (2015) Modification of polythiophene by the incorporation of processable polymeric chains: recent progress in synthesis and applications. Prog Polym Sci 47:26–69

    Article  CAS  Google Scholar 

  32. Matyjaszewski K, Tsarevsky NV (2014) Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc 136:6513–6533

    Article  CAS  Google Scholar 

  33. Nicolas J, Guillaneuf Y, Lefay C, Bertin D, Gigmes D, Charleux B (2013) Nitroxide-mediated polymerization. Prog Polym Sci 38:63–235

    Article  CAS  Google Scholar 

  34. Jaymand M (2013) Recent progress in chemical modification of polyaniline. Prog Polym Sci 38:1287–1306

    Article  CAS  Google Scholar 

  35. Jaymand M (2011) Synthesis and characterization of novel type poly (4-chloromethylstyrene-grft-4-vinylpyridine)/TiO2 nanocomposite via nitroxide-mediated radical polymerization. Polymer 52:4760–4769

    Article  CAS  Google Scholar 

  36. Massoumi B, Mousavi-Hamamlu SV, Ghamkhari A, Jaymand M (2017) A novel strategy for synthesis of polystyrene/Fe3O4 nanocomposite: RAFT polymerization, functionalization, and coordination techniques. Polym-Plast Technol Eng 56:873–882

    Article  CAS  Google Scholar 

  37. Jaymand M (2011) Synthesis and characterization of well-defined poly (4-chloromethylstyrene-g-4-vinylpyridine)/TiO2 nanocomposite via ATRP technique. J Polym Res 18:1617–1624

    Article  CAS  Google Scholar 

  38. Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4428

    Article  CAS  Google Scholar 

  39. Wang JS, Matyjaszewski K (1995) Controlled/“living” radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process. Macromolecules 28:7901–7910

    Article  CAS  Google Scholar 

  40. Shin J, Chang Y, Nguyen TLT, Noh SK, Bae C (2010) Hydrophilic functionalization of syndiotactic polystyrene via a combination of electrophilic bromination and suzuki–miyaura reaction. J Polym Sci A 48:4335–4343

    Article  CAS  Google Scholar 

  41. Massoumi B, Abbasi F, Jaymand M (2016) Chemical and electrochemical grafting of polythiophene onto polystyrene synthesized via ‘living’ anionic polymerization. New J Chem 40:2233–2242

    Article  CAS  Google Scholar 

  42. Cooper GD, Finkbeiner HL (1962) Titanium-catalyzed rearrangement and olefin-exchange of Grignard reagents. J Org Chem 27:1493–1497

    Article  Google Scholar 

  43. Noller CR, Adams WR (1926) The preparation and use of aldehyde esters formed by ozonation of the methyl esters of various unsaturated acids. J Am Chem Soc 48:1074–1080

    Article  CAS  Google Scholar 

  44. Hatamzadeh M, Jaymand M (2014) Synthesis and characterization of polystyrene-graft-polythiophene via a combination of atom transfer radical polymerization and Grignard reaction. RSC Adv 4:16792–16802

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Authors earnestly acknowledge the support from Tabriz University of Medical Sciences and Azarbaijan Shahid Madani University.

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Correspondence to Mehdi Jaymand.

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Mohammad-Rezaei, R., Massoumi, B., Abbasian, M. et al. Novel strategies for the synthesis of hydroxylated and carboxylated polystyrenes. J Polym Res 25, 93 (2018). https://doi.org/10.1007/s10965-018-1490-x

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