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Synthesis and characterization of polyvinyl alcohol-g-polystyrene copolymers via MADIX polymerization technique

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Abstract

In polymer structure design, branching can occur randomly or by reactions designed to target specific architectures. This microstructural property affects many physical properties such as polydispersity, molecular weight and polymer chain size. A new reversible addition-fragmentation chain transfer/macromolecular design through interchange of xanthates (RAFT/MADIX) agents with polyvinyl alcohol was performed. In the process, polyvinyl alcohol (PVA), potassium hydroxide, carbon disulfide and derivatives of benzoylchloride were employed, and thus, three new graft chain transfer agents (g-CTA) were synthesized. PVA-g-PS graft copolymers were obtained using MADIX agents by changing various factors including initiator, amount of monomer and reaction time. While the linear increase in molecular weight with monomer consumption was observed, the polymerization reaction was kinetically detected to be the first order. Significant progress has been made in controlling the molecular weight distribution of the polymer by RAFT polymerization. The synthesized graft copolymers were characterized using FTIR, 1H NMR, 13C NMR, GPC and DSC techniques. Also, the three new graft chain transfer agents were characterized by elemental analysis and the existence of xanthate -S-(C = S) O-PVA was confirmed. The synthesis of the copolymer with the MADIX agent, which has an almost infinite number of design possibilities, was successfully achieved. As a result, well-defined statistical PVA-g-PS copolymers having a narrow molecular weight distribution (PDI 1.23–1.47) were obtained.

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References

  1. Mustaqeem M, Saleh TA, ur Rehman A, Farooq Warsi M, Mehmood A, Sharif A, Akther S (2020) Synthesis of Zn0.8Co0.1Ni0.1Fe2O4 polyvinyl alcohol nanocomposites via ultrasound-assisted emulsion liquid phase. Arab J Chem 13:3246–3254

    Article  CAS  Google Scholar 

  2. Sayed MM, Mousa HM, El-Aassar MR, El-Deeb NM, Ghazaly NM, Dewidar MM, Abdal-hay A (2019) Enhancing mechanical and biodegradation properties of polyvinyl alcohol/silk fibroin nanofibers composite patches for Cardiac tissue engineering. Mater Lett 255:126510

    Article  CAS  Google Scholar 

  3. Kobayashi M, Toguchida J, Oka M (2003) Preliminary study of polyvinyl alcohol-hydrogel (PVA-H) artificial meniscus. Biomaterials 24:639–647

    Article  CAS  Google Scholar 

  4. Zhang J, Liu T, Liu Z, Wang Q (2019) Facile fabrication of tough photocrosslinked polyvinyl alcohol hydrogels with cellulose nanofibrils reinforcement. Polymer 173:103–109

    Article  CAS  Google Scholar 

  5. Rac V, Lević S, Balanč B, Olalde Graells B, Bijelić G (2019) PVA Cryogel as model hydrogel for iontophoretic transdermal drug delivery investigations:comparison with PAA/PVA and PAA/PVP interpenetrating networks. Colloid Surf B 180:441–448

    Article  CAS  Google Scholar 

  6. Pundir CS, Sandeep Singh B, Narang J (2010) Construction of an amperometric triglyceride biosensor using PVA membrane bound enzymes. Clin Biochem 43:467–472

    Article  CAS  Google Scholar 

  7. Sanaeifar N, Rabiee M, Abdolrahim M, Tahriri M, Vashaee D, Tayebi L (2017) A novel electrochemical biosensor based on Fe3O4 nanoparticles-polyvinyl alcohol composite for sensitive detection of glucose. Anal Biochem 519:19–26

    Article  CAS  Google Scholar 

  8. Ma’Radzi AH, Sugihara S, Toida T, Maeda Y, (2014) Synthesis of polyvinyl alcohol stereoblock copolymer via the combination of living cationic polymerization and RAFT/MADIX polymerization using xanthate with vinyl ether moiety. Polymer 55:5332–5345

    Article  Google Scholar 

  9. Segura T, Menes-Arzate M, León F, Ortega A, Burillo G, Peralta RD (2016) Synthesis of narrow molecular weight distribution polyvinyl acetate by gamma-rays initiated RAFT/MADIX miniemulsion polymerization. Polymer 102:183–191

    Article  CAS  Google Scholar 

  10. Göktaş M (2019) Synthesis and characterization of various block copolymers using PMMA-Br macroinitiator. Chem Zvesti 73:2329–2339

    Google Scholar 

  11. Koyilapu R, Singha S, Kutcherlapati SNR, Jana T (2020) Grafting of vinylimidazolium-type poly(ionic liquid) on silica nanoparticle through RAFT polymerization for constructing nanocomposite based PEM. Polymer 195:122458

    Article  CAS  Google Scholar 

  12. Mishra S, Rawal A, Nebhani L (2020) Imprinting the location of an in-built RAFT agent and selective grafting of polymer chains inside or outside the pores of mesoporous silica nanoparticles. Micropor Mesopor Mater 294:109898

    Article  CAS  Google Scholar 

  13. Chmielarz P, Park S, Sobkowiak A, Matyjaszewski K (2016) Synthesis of β-cyclodextrin-based star polymers via a simplified electrochemically mediated ATRP. Polymer 88:36–42

    Article  CAS  Google Scholar 

  14. Glaied O, Dubé M, Chabot B, Daneault C (2009) Synthesis of cationic polymer-grafted cellulose by aqueous ATRP. J Colloid Interface Sci 333:145–151

    Article  CAS  Google Scholar 

  15. Guo H, Li X, Wang JL, Jin XH, Lin XF (2010) Acidic ionic liquid [NMP]H2PO4 as dual solvent-catalyst for synthesis of β-alkoxyketones by the oxa-Michael addition reactions. Tetrahedron 66:8300–8303

    Article  CAS  Google Scholar 

  16. Ishigaki Y, Mori H (2018) Synthesis of poly(chloroprene)-based block copolymers by RAFT-mediated emulsion polymerization. Polymer 140:198–207

    Article  CAS  Google Scholar 

  17. Tang BK, Li J, Ren Q, Wang CY (2019) Synthesis of poly(sodium styrene sulfonate)-b-poly(butyl acrylate) block copolymers via RAFT emulsifier-free emulsion polymerization and their application in PEDOT aqueous dispersions. Synth Met 258:116188

    Article  Google Scholar 

  18. Göktaş M, Olgun B (2019) One-step synthesis and characterization of poly(ε-caprolactone)-b-poly(N-isopropylacrylamide) thermo-responsive block copolymers via RAFT and ROP techniques. Polym Sci Ser B 61:421–429

    Article  Google Scholar 

  19. Sütekin SD, Güven O (2018) Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents. Radiat Phys Chem 142:82–87

    Article  Google Scholar 

  20. Beija M, Marty JD, Destarac M (2011) RAFT/MADIX polymers for the preparation of polymer/inorganic nanohybrids. Prog Polym Sci 36:845–886

    Article  CAS  Google Scholar 

  21. Roy D, Sumerlin BS (2011) Block copolymerization of vinyl ester monomers via RAFT/MADIX under microwave irradiation. Polymer 52:3038–3045

    Article  CAS  Google Scholar 

  22. Uchiyama M, Satoh K, Kamigaito M (2021) Stereospecific cationic RAFT polymerization of bulky vinyl ethers and stereoblock poly(vinyl alcohol) via mechanistic transformation to radical RAFT polymerization of vinyl acetate. Giant 5:100047

    Article  CAS  Google Scholar 

  23. Zhou J, Lin Y, Wang L, Zhou L, Yu B, Zou X, Luo Z, Hu H (2021) Poly(carboxybetaine methacrylate) grafted on PVA hydrogel via a novel surface modification method under near-infrared light for enhancement of antifouling properties. Colloids Surf APhysicochem Eng Asp 617:126369

    Article  CAS  Google Scholar 

  24. Kartal B, Yildiko U, Ozturk S, Ata AC, Cakmak I (2014) Study of solution polymerization of styrene in the presence of poly(ethylene glycol)-RAFT agents possessing benzoyl xanthate derivatives. J Macromol Sci A 51:990–998

    Article  CAS  Google Scholar 

  25. Goel V, Pietrasik J, Poling-Skutvik R, Jackson A, Matyjaszewski K, Krishnamoorti R (2018) Structure of block copolymer grafted silica nanoparticles. Polymer 159:138–145

    Article  CAS  Google Scholar 

  26. Wang Y, Ren R, Ling J, Sun W, Shen Z (2018) One-pot “grafting-from” synthesis of amphiphilic bottlebrush block copolymers containing PLA and PVP side chains via tandem ROP and RAFT polymerization. Polymer 138:378–386

    Article  CAS  Google Scholar 

  27. Mishra AK, Choi C, Maiti S, Seo Y, Lee KS, Kim E, Kim JK (2018) Sequential synthesis of well-defined poly(vinyl acetate)-block-polystyrene and poly(vinyl alcohol)-block-polystyrene copolymers using difunctional chloroamide-xanthate iniferter. Polymer 139:68–75

    Article  CAS  Google Scholar 

  28. Bernard J, Favier A, Davis TP, Barner-Kowollik C, Stenzel MH (2006) Synthesis of poly(vinyl alcohol) combs via MADIX/RAFT polymerization. Polymer 47:1073–1080

    Article  CAS  Google Scholar 

  29. Perrier S, Takolpuckdee P (2005) Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization. J Polym Sci A Polym Chem 43:5347–5393

    Article  CAS  Google Scholar 

  30. Barthet C, Wilson J, Cadix A, Destarac M, Chassenieux C, Harrisson S (2018) Influence of sodium dodecyl sulfate on the kinetics and control of RAFT/MADIX polymerization of acrylamide. J Polym Sci A Polym Chem 56:760–765

    Article  CAS  Google Scholar 

  31. Smith AE, Xu X, McCormick CL (2010) Stimuli-responsive amphiphilic (co)polymers via RAFT polymerization. Prog Polym Sci 35:45–93

    Article  CAS  Google Scholar 

  32. Conzatti G, Cavalie S, Combes C, Torrisani J, Carrere N, Tourrette A (2017) PNIPAM grafted surfaces through ATRP and RAFT polymerization: chemistry and bioadhesion. Colloid Surf B 151:143–155

    Article  CAS  Google Scholar 

  33. Moad G, Rizzardo E, Thang SH (2009) Living radical polymerization by the RAFT process asecond update. Aust J Chem 62:1402–1472

    Article  CAS  Google Scholar 

  34. Gregory A, Stenzel MH (2012) Complex polymer architectures via RAFT polymerization: From fundamental process to extending the scope using click chemistry and nature’s building blocks. Prog Polym Sci 37:38–105

    Article  CAS  Google Scholar 

  35. Barsbay M, Güven O (2020) Nanostructuring of polymers by controlling of ionizing radiation-induced free radical polymerization, copolymerization, grafting and crosslinking by RAFT mechanism. Radiat Phys Chem 169:107816

    Article  CAS  Google Scholar 

  36. Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: features, developments, and perspectives. Prog Polym Sci 32:93–146

    Article  CAS  Google Scholar 

  37. Tian J, Zhang W (2019) Synthesis, self-assembly and applications of functional polymers based on porphyrins. Prog Polym Sci 95:65–117

    Article  CAS  Google Scholar 

Download references

Funding

The authors gratefully acknowledge the support for this work from the Scientific and Technological Research Council of Turkey (TUBITAK) (Project No: 112T716).

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Correspondence to Ümit Yildiko.

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CagriAta, A., Yildiko, Ü., Cakmak, İ. et al. Synthesis and characterization of polyvinyl alcohol-g-polystyrene copolymers via MADIX polymerization technique. Iran Polym J 30, 885–895 (2021). https://doi.org/10.1007/s13726-021-00940-x

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  • DOI: https://doi.org/10.1007/s13726-021-00940-x

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