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Synthesis of block copolymer of vinyl acetate and methyl acrylate by cobalt-mediated radical polymerization in a packed column system: simultaneous control of molecular weight, separation, and purification

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Abstract

In this study, for the first time, we investigate cobalt-mediated radical block copolymerization of vinyl acetate (VAc) and methyl acrylate (MA) in a packed column system in the presence of cobalt(II) acetylacetonate (Co (acac)2) as a controlling agent. This copolymerization system has the capability to remove the residual catalyst and separate copolymers with different molecular weights, simultaneous to polymerization. Synthesis of high-purity poly (vinyl acetate)-b-poly(methyl acrylate-co-vinyl acctate) (PVAc-b-P(MA-co-VAc)) copolymers were successfully performed by initiating the radical copolymerization of MA and VAc from PVAc-Co (acac)2 macroinitiator in the packed column with silica gel particles. Copolymerization reaction proceeds via a controlled characteristic with first-order kinetics with respect to monomers, predetermined molecular weight, and relatively narrow molecular weight distribution. GPC, 1HNMR, and DSC analyses demonstrated that the PVAc-b-P(MA-co-VAc) was formed with a blocky structure. Based on the analyses, it was found that the VAc content in the block copolymer progressively increased with increasing conversion in the constant VAc initial ratio, indicating that the second block copolymer had a gradient sequence distribution. Moreover, the VAc and MA reactivity ratios in the packed column with silica gel particles were calculated using the extended Kelen–Tudos method to be rMA = 4.98 and rVAc = 0.62, respectively.

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References

  1. Summers GJ, Motsoeneng TS, Summers CA (2021) RAFT polymerization of styrene mediated by oxazolyl-functionalized trithiocarbonate RAFT agents. Polym Bull 78(4):2251–2285

    CAS  Google Scholar 

  2. Bignardi C, Oliveira LF, Pesqueira NM, Riga-Rocha BA, Machado AE, Carvalho-Jr VP, Goi BE (2022) Photoinduced organometallic mediating radical polymerization of acrylates mediated by CoII complexes of non-symmetrical tetradentate Schiff-base ligands. J Photochem Photobiol A 423:113595

    CAS  Google Scholar 

  3. Abedini H, Rostami MR, Shahsavar S (2022) Numerical simulation of atom transfer radical polymerization of styrene by moment and population balance models. Polym Bull 79(6):4303–4322

    CAS  Google Scholar 

  4. Kohestanian M, Pourjavadi A, Keshavarzi N (2022) Facile and tunable method for polymeric surface modification of magnetic nanoparticles via RAFT polymerization: preparation, characterization, and drug release properties. Eur Polymer J 167:111067–111080

    CAS  Google Scholar 

  5. Tilottama B, Manojkumar K, Haribabu P, Vijayakrishna K (2022) A short review on RAFT polymerization of less activated monomers. J Macromolecular Sci A 59(3):180–201

    CAS  Google Scholar 

  6. Uyar Z, Arslan U, Yuce Boyraz T, Degirmenci M (2022) A xanthate-type photofunctional chain transfer agent for the synthesis of macrophotoinitiators. ACS Appl Polymer Mater 4(10):7911–7922

    CAS  Google Scholar 

  7. Dau H, Jones GR, Tsogtgerel E, Nguyen D, Keyes A, Liu Y-S, Rauf H, Ordonez E, Puchelle V, Basbug Alhan H (2022) Linear block copolymer synthesis. Chem Rev 122(18):14471–14553

    CAS  PubMed  Google Scholar 

  8. Sabzevari A, Dadkhah AS, Kohestanian M, Mahdieh A, Semsarzadeh MA (2022) Cobalt -mediated radical polymerization of vinyl acetate in a packed column system: simultaneous effective control of molecular weight, separation, and purification. J Polymer Res 29(12). https://doi.org/10.1007/s10965-022-03365-z

  9. Semsarzadeh MA, Sabzevari A (2018) Highly effective organometallic-mediated radical polymerization of vinyl acetate using alumina-supported Co (acac) 2 catalyst: a case study of adsorption and polymerization. J Appl Polym Sci 135(13):46057–46060

    Google Scholar 

  10. Semsarzadeh MA, Sabzevari A (2020) Adsorption process of Co (acac) 2 catalyst on the surface of mesoporous silica gel particles: an effective method to make a new supported catalyst for the controlled radical polymerization of vinyl acetate. J Iran Chem Soc 17(9):2293–2305

    CAS  Google Scholar 

  11. Benchaphanthawee W, Peng CH (2021) Organo-cobalt complexes in reversible-deactivation radical polymerization. Chem Rec 21(12):3628–3647

    CAS  PubMed  Google Scholar 

  12. Oliveira LF, Bignardi C, Pesqueira NM, Riga-Rocha BA, Machado AE, Carvalho Jr VP, Goi BE (2021) Photocontrolled reversible-deactivation radical polymerization of butyl acrylate mediated by Salen-type CoII complexes. Eur Polymer J 159:110757–110765

    CAS  Google Scholar 

  13. Wayland BB, Poszmik G, Mukerjee SL, Fryd M (1994) Living radical polymerization of acrylates by organocobalt porphyrin complexes. J Am Chem Soc 116(17):7943–7944

    CAS  Google Scholar 

  14. Arvanitopoulos L, Greuel M (1994) Harwood H Living free-radical polymerization using alkyl cobaloximes as photoinitiators. Abstracts of Papers of the American Chemical Society, 1994. American Chemical Society, Washington, DC, p 402

  15. Debuigne A, Caille JR, Jérôme R (2005) Highly efficient cobalt-mediated radical polymerization of vinyl acetate. Angew Chem 117(7):1125–1128

    Google Scholar 

  16. Kaneyoshi H, Matyjaszewski K (2005) Effect of ligand and n-butyl acrylate on cobalt-mediated radical polymerization of vinyl acetate. Macromolecules 38(20):8163–8169

    CAS  Google Scholar 

  17. Semsarzadeh MA, Sabzevari A (2017) Silica gel supported co (acac) 2 catalyst in the controlled radical polymerization of vinyl acetate: an easy and practical method to make crystallized poly (vinyl acetate) in a one step process. J Polym Res 24(11):177–186

    Google Scholar 

  18. Semsarzadeh MA, Alamdari P (2013) Cobalt-mediated radical polymerization of vinyl acetate in an alumina column using suspended polyvinyl acetate. J Polym Res 20(10):276–286

    Google Scholar 

  19. Debuigne A, Warnant J, Jérôme R, Voets I, de Keizer A, Cohen Stuart MA, Detrembleur C (2008) Synthesis of novel well-defined poly (vinyl acetate)-b-poly (acrylonitrile) and derivatized water-soluble poly (vinyl alcohol)-b-poly (acrylic acid) block copolymers by cobalt-mediated radical polymerization. Macromolecules 41(7):2353–2360

    CAS  Google Scholar 

  20. Debuigne A, Willet N, Jérôme R, Detrembleur C (2007) Amphiphilic poly (vinyl acetate)-b-poly (N-vinylpyrrolidone) and novel double hydrophilic poly (vinyl alcohol)-b-poly (N-vinylpyrrolidone) block copolymers prepared by cobalt-mediated radical polymerization. Macromolecules 40(20):7111–7118

    CAS  Google Scholar 

  21. Detrembleur C, Debuigne A, Hurtgen M, Jérôme C, Pinaud J, Fèvre M, Coupillaud P, Vignolle J, Taton D (2011) Synthesis of 1-vinyl-3-ethylimidazolium-based ionic liquid (co) polymers by cobalt-mediated radical polymerization. Macromolecules 44(16):6397–6404

    CAS  Google Scholar 

  22. Bryaskova R, Willet N, Debuigne A, Jérôme R, Detrembleur C (2007) Synthesis of poly (vinyl acetate)-b-polystyrene and poly (vinyl alcohol)-b-polystyrene copolymers by cobalt-mediated radical polymerization. J Polym Sci Part A Polym Chem 45(1):81–89

    CAS  Google Scholar 

  23. Bryaskova R, Willet N, Degée P, Dubois P, Jérôme R, Detrembleur C (2007) Copolymerization of vinyl acetate with 1-octene and ethylene by cobalt-mediated radical polymerization. J Polym Sci Part A Polym Chem 45(12):2532–2542

    CAS  Google Scholar 

  24. Piette Y, Debuigne A, Bodart V, Willet N, Duwez A-S, Jérôme C, Detrembleur C (2013) Synthesis of poly (vinyl acetate)-b-poly (vinyl chloride) block copolymers by Cobalt-Mediated Radical Polymerization (CMRP). Polym Chem 4(5):1685–1693

    CAS  Google Scholar 

  25. Falireas PG, Ladmiral V, Debuigne A, Detrembleur C, Poli R, Ameduri B (2019) Straightforward synthesis of well-defined Poly (vinylidene fluoride) and its block copolymers by cobalt-mediated radical polymerization. Macromolecules 52(3):1266–1276

    CAS  Google Scholar 

  26. Narayanan M, Choi KY (2021) High pressure semibatch emulsion and miniemulsion copolymerization of vinyl acetate and ethylene. J Appl Polym Sci 138(5):49784

    CAS  Google Scholar 

  27. Khalaf DM, Elkatlawy SM, Sakr AHA, Ebrahim SM (2020) Enhanced oil/water separation via electrospun poly (acrylonitrile-co-vinyl acetate)/single-wall carbon nanotubes fibrous nanocomposite membrane. J Appl Polym Sci 137(35):49033–49042

    CAS  Google Scholar 

  28. Azevedo GD, Pinto JC (2020) Alkaline hydrolysis of P (VAc-co-MMA) particles for vascular embolization procedures. J Appl Polym Sci 137(42):49298–49309

    CAS  Google Scholar 

  29. Gadhave RV, Vineeth S (2022) Synthesis and characterization of starch stabilized polyvinyl acetate-acrylic acid copolymer-based wood adhesive. Polym Bull. https://doi.org/10.1007/s00289-022-04558-8

    Article  Google Scholar 

  30. Zhang N, Wang S, Gibril ME, Kong F (2020) The copolymer of polyvinyl acetate containing lignin-vinyl acetate monomer: Synthesis and characterization. Eur Polymer J 123:109411

    CAS  Google Scholar 

  31. Semsarzadeh MA, Alamdari P (2015) Co (acac)2 mediated controlled radical copolymerization of vinyl acetate and methyl acrylate initiated by benzoyl peroxide. Macromol Res 23(2):139–144

    CAS  Google Scholar 

  32. Hurtgen M, Debuigne A, Jérôme C, Detrembleur C (2009) Solving the problem of bis (acetylacetonato) cobalt (II)-mediated radical polymerization (CMRP) of acrylic esters. Macromolecules 43(2):886–894

    Google Scholar 

  33. Allaoua I, Goi BE, Obadia MM, Debuigne A, Detrembleur C, Drockenmuller E (2014) (Co) Polymerization of vinyl levulinate by cobalt-mediated radical polymerization and functionalization by ketoxime click chemistry. Polym Chem 5(8):2973–2979

    CAS  Google Scholar 

  34. Koumura K, Satoh K, Kamigaito M (2009) Mn2 (CO) 10-induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments. J Polym Sci A Polym Chem 47(5):1343–1353

    CAS  Google Scholar 

  35. Kulkarni N, Krishnamurti N, Chatterjee P, Sivasamban M (1970) Determination of reactivity ratios for the copolymerisation of vinyl acetate with methyl acrylate by proton magnetic resonance spectroscopy. Die Makromolekulare Chemie: Macromolecular Chem Phys 139(1):165–170

    CAS  Google Scholar 

  36. Abdollahi M, Mahdavian AR, Nouri A (2007) Kinetic study of radical polymerization VIII. A comprehensive study of solution copolymerization of vinyl acetate and methyl acrylate by 1H‐NMR spectroscopy. J Macromolecular Sci Part A Pure Appl Chem 44 (8):839–848

  37. Semsarzadeh MA, Abdollahi M (2009) Atom transfer radical homo-and copolymerization of styrene and methyl acrylate initiated with trichloromethyl-terminated poly (vinyl acetate) macroinitiator: a kinetic study. J Appl Polym Sci 114(4):2509–2521

    CAS  Google Scholar 

  38. Semsarzadeh MA, Rostami Daronkola MR, Abdollahi M (2007) Kinetic study of atom transfer radical copolymerization of methyl acrylate and methyl methacrylate initiated with poly (vinyl acetate) macroinitiator. J Macromol Sci Part A Pure Appl Chem 44(9):953–961

    CAS  Google Scholar 

  39. Wu W, Chiu W, Liau W (1997) Casting solvent effect on crystallization behavior of poly (vinyl acetate)/poly (ethylene oxide) blends: DSC study. J Appl Polym Sci 64(3):411–421

    CAS  Google Scholar 

  40. Zhang Y-F, Tang J, Li T, Liu Y, Li Y (2022) UV-mediated atom transfer radical polymerization of acrolein. Polym Bull 79(2):1057–1068

    CAS  Google Scholar 

  41. Andriotis EG, Koumbis AE, Achilias DS (2021) Nitroxide-mediated polymerization of styrene and limonene in the framework of synthesis of potentially functional polymers using naturally occurring terpenes. Polym Bull 78(8):4609–4628

    CAS  Google Scholar 

  42. Sun Y, Zhai G (2022) Conventional and controlled radical polymerization redox-initiated by Cerium (IV) and Acrylamide as an intrinsically reducing inimer: a facile strategy to branched polyacrylamide. Polym Bull 79(3):1751–1765

    CAS  Google Scholar 

  43. Shen Y, Zhu S, Zeng F, Pelton RH (2000) Atom transfer radical polymerization of methyl methacrylate by silica gel supported copper bromide/multidentate amine. Macromolecules 33(15):5427–5431

    CAS  Google Scholar 

  44. Nguyen JV, Jones CW (2004) Design, behavior, and recycling of silica-supported CuBr−bipyridine ATRP catalysts. Macromolecules 37(4):1190–1203

    CAS  Google Scholar 

  45. Abdollahi M, Semsarzadeh MA (2009) Effect of nanoclay and macroinitiator on the kinetics of atom transfer radical homo-and copolymerization of styrene and methyl methacrylate initiated with CCl3-terminated poly (vinyl acetate) macroinitiator. Eur Polymer J 45(4):985–995

    CAS  Google Scholar 

  46. Lewis FM, Walling C, Cummings W, Briggs ER, Mayo FR (1948) Copolymerization. IV. Effects of temperature and solvents on monomer reactivity ratios. J Am Chem Society 70 (4):1519–1523

  47. Greenley RZ (1980) Recalculation of some reactivity ratios. J Macromolec Sci A-Chem 14(4):445–515

    Google Scholar 

  48. Casinos I (1991) Reactivity ratios for grafting of vinyl acetate and methyl acrylate mixtures onto cellulose at high conversions. Die Makromolekulare Chemie: Macromolec Chem Phys 192(5):1091–1097

    CAS  Google Scholar 

  49. Koumura K, Satoh K, Kamigaito M, Okamoto Y (2006) Iodine transfer radical polymerization of vinyl acetate in fluoroalcohols for simultaneous control of molecular weight, stereospecificity, and regiospecificity. Macromolecules 39(12):4054–4061

    CAS  Google Scholar 

  50. Shibata T, Satoh K, Kamigaito M, Okamoto Y (2006) Simultaneous control of the stereospecificity and molecular weight in the ruthenium-catalyzed living radical polymerization of methyl and 2-hydroxyethyl methacrylates and sequential synthesis of stereoblock polymers. J Polym Sci Part A Polym Chem 44(11):3609–3615

    CAS  Google Scholar 

  51. Kamigaito M, Satoh K (2006) Stereospecific living radical polymerization for simultaneous control of molecular weight and tacticity. J Polym Sci Part A Polym Chem 44(21):6147–6158

    CAS  Google Scholar 

  52. Yamada K, Nakano T, Okamoto Y (2000) Free-radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio. J Polym Sci Part A Polym Chem 38(1):220–228

    CAS  Google Scholar 

  53. Mori S, Barth HG (2013) Size exclusion chromatography. Springer Science & Business Media, New York

    Google Scholar 

  54. Wu C-S (2003) Handbook of size exclusion chromatography and related techniques: revised and expanded, vol 91. CRC Press, Boca Raton

    Google Scholar 

  55. Ng SM, Si O, Aida T, Koyano KA, Tatsumi T (1997) Free radical polymerization within mesoporous zeolite channels. Macromol Rapid Commun 18(12):991–996

    CAS  Google Scholar 

  56. Kageyama K, Ng SM, Ichikawa H, Aida T (2000) Macromolecular synthesis using mesoporous zeolites. macromolecular Symposia 157 (1): 137–142

  57. Ikeda K, Kida M, Endo K (2009) Polymerization of Methyl Methacrylate with Radical Initiator Immobilized on the Inside Wall of Mesoporous Silica. Polym J 41(8):672–678

    CAS  Google Scholar 

  58. Zhao H, Simon SL (2011) Methyl methacrylate polymerization in nanoporous confinement. Polymer 52(18):4093–4098

    CAS  Google Scholar 

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Authors and Affiliations

  1. Polymer Faculty, Biomedical Engineering Department, Meybod University, Meybod, Yazd, Iran

    Alireza Sabzevari

  2. Polymer Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran

    Arezoo Sh Dadkhah & Mohammad Ali Semsarzadeh

  3. Department of Chemistry, Technical University, Copenhagen, Denmark

    Mohammad Kohestanian

  4. Department of Chemistry, University of Oslo, 0315, Oslo, Norway

    Athar Mahdieh

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  1. Alireza Sabzevari
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  2. Arezoo Sh Dadkhah
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  3. Mohammad Kohestanian
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  4. Athar Mahdieh
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  5. Mohammad Ali Semsarzadeh
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Contributions

AS contributed to experimental and data analysis & interpretation, methodology, data collection, and original draft preparation. ASD contributed to systems design, methodology, and material preparation. MK contributed to experimental data analysis & interpretation, writing, reviewing, and editing. AM contributed to experimental data analysis & interpretation, writing, reviewing, and editing. MAS contributed to investigation & supervision. All authors read and approved the final manuscript.

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Correspondence to Alireza Sabzevari.

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Sabzevari, A., Dadkhah, A.S., Kohestanian, M. et al. Synthesis of block copolymer of vinyl acetate and methyl acrylate by cobalt-mediated radical polymerization in a packed column system: simultaneous control of molecular weight, separation, and purification. Polym. Bull. 80, 12157–12176 (2023). https://doi.org/10.1007/s00289-022-04652-x

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