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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

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Abstract

Cobalt-mediated radical polymerization (CMRP) of vinyl acetate (VAc) has been suggested as one of the major methods to reduced some of the problems in the synthesis of Poly(vinyl acetate) (PVAc), but the color impurities have been the major disadvantage of this method. An easy and practical method to make a crystallized PVAc in a one step process is to use silica gel particles. The particles have been used as a catalyst support of cobalt(II) acetylacetonate (Co(acac)2). It was found that using silica gel supported-Co(acac)2 in VAc polymerization yields polymers with controlled molecular weight, narrow molecular weight distribution, and high purity. For the silica gel supported CMRP (SS-CMRP) changing the polymerization mechanism resulted in a 2.5 times increase in polymerization rate (kapp) and a drop in the induction time while maintaining the control of the VAc polymerization. In addition PVAc synthesized through SS-CMRP method compared to the one synthesized using unsupported-CMRP has a higher crystallinity.

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References

  1. Morin AN, Detrembleur C, Jérôme C, De Tullio P, Poli R, Debuigne A (2013) Effect of head-to-head addition in vinyl acetate controlled radical polymerization: why is co (acac) 2-mediated polymerization so much better? Macromolecules 46(11):4303–4312

    Article  CAS  Google Scholar 

  2. Kermagoret A, Jérôme C, Detrembleur C, Debuigne A (2015) In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization. Eur Polym J 62:312–321

    Article  CAS  Google Scholar 

  3. Chauvin F, Alb AM, Bertin D, Tordo P, Reed WF (2002) Kinetics and molecular weight evolution during controlled radical polymerization. Macromol Chem Phys 203(14):2029–2041

    Article  CAS  Google Scholar 

  4. Smith KM, McNeil WS, Abd-El-Aziz AS (2010) Organometallic-mediated radical polymerization: developing well-defined complexes for reversible transition metal-alkyl bond homolysis. Macromol Chem Phys 211(1):10–16

    Article  CAS  Google Scholar 

  5. Proietti Silvestri I, Cellesi F (2015) AGET ATRP of poly [poly (ethylene glycol) methyl ether methacrylate] catalyzed by hydrophobic iron (III)–porphyrins. Macromol Chem Phys 216(20):2032–2039

    Article  CAS  Google Scholar 

  6. Poli R, Allan LE, Shaver MP (2014) Iron-mediated reversible deactivation controlled radical polymerization. Prog Polym Sci 39(10):1827–1845

    Article  CAS  Google Scholar 

  7. Matyjaszewski K, Tsarevsky NV (2014) Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc 136(18):6513–6533

    Article  CAS  Google Scholar 

  8. Konkolewicz D, Wang Y, Zhong M, Krys P, Isse AA, Gennaro A, Matyjaszewski K (2013) Reversible-deactivation radical polymerization in the presence of metallic copper. A critical assessment of the SARA ATRP and SET-LRP mechanisms. Macromolecules 46(22):8749–8772

    Article  CAS  Google Scholar 

  9. Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45(10):4015–4039

    Article  CAS  Google Scholar 

  10. Tsarevsky NV, Matyjaszewski K (2007) “Green” atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials. Chem Rev 107(6):2270–2299

    Article  CAS  Google Scholar 

  11. Farrokhi M, Abdollahi M, Rekabdar F, Hemmati M (2015) Reverse iodine transfer radical copolymerization of vinyl acetate and dibutyl maleate: synthesis and characterization of alternating and block copolymers. J Polym Res 22(4):43

    Article  Google Scholar 

  12. Wang FS, Yang TY, Hsu CC, Chen YJ, Li MH, Hsu YJ, Chuang MC, Peng CH (2016) The mechanism and thermodynamic studies of CMRP: different control mechanisms demonstrated by CoII (TMP), CoII (salen*), and CoII (acac) 2 mediated polymerization, and the correlation of reduction potential, equilibrium constant, and control mechanism. Macromol Chem Phys 217(3):422–432

    Article  CAS  Google Scholar 

  13. Debuigne A, Poli R, Jérôme R, Jérôme C, Detrembleur C (2009) Key role of metal-coordination in cobalt-mediated radical polymerization of vinyl acetate. ACS Symp Ser 1014:131–148

  14. Debuigne A, Poli R, Jérôme C, Jérôme R, Detrembleur C (2009) Overview of cobalt-mediated radical polymerization: roots, state of the art and future prospects. Prog Polym Sci 34(3):211–239

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  16. Semsarzadeh MA, Amiri S (2013) Synthesis and characterization of PSt-b-PVAc diblock copolymers via combination of atom transfer radical polymerization and cobalt-mediated radical polymerization. J Polym Res 20(5):139

    Article  Google Scholar 

  17. 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

    Article  CAS  Google Scholar 

  18. 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

    Article  CAS  Google Scholar 

  19. 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

    Article  CAS  Google Scholar 

  20. 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

    Article  CAS  Google Scholar 

  21. Cordella D, Kermagoret A, Debuigne A, Rl R, German I, Isik M, Jérôme C, Mecerreyes D, Taton D, Detrembleur C (2014) Direct route to well-defined poly (ionic liquid) s by controlled radical polymerization in water. ACS Macro Lett 3(12):1276–1280

    Article  CAS  Google Scholar 

  22. Dréan M, Guégan P, Detrembleur C, Jérôme C, Rieger J, Debuigne A (2016) Controlled synthesis of poly (vinylamine)-based copolymers by organometallic-mediated radical polymerization. Macromolecules 49(13):4817–4827

    Article  Google Scholar 

  23. 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

    Article  Google Scholar 

  24. Debuigne A, Michaux C, Jérôme C, Jérôme R, Poli R, Detrembleur C (2008) Cobalt-mediated radical polymerization of acrylonitrile: kinetics investigations and DFT calculations. Chem Eur J 14(25):7623–7637

    Article  CAS  Google Scholar 

  25. Kermagoret A, Debuigne A, Jérôme C, Detrembleur C (2014) Precision design of ethylene-and polar-monomer-based copolymers by organometallic-mediated radical polymerization. Nat Chem 6(3):179–187

    Article  CAS  Google Scholar 

  26. Weiss-Maurin M, Cordella D, Jérôme C, Taton D, Detrembleur C (2016) Direct one-pot synthesis of poly (ionic liquid) nanogels by cobalt-mediated radical cross-linking copolymerization in organic or aqueous media. Polym Chem 7(14):2521–2530

    Article  CAS  Google Scholar 

  27. Cordella D, Debuigne A, Jérôme C, Kochovski Z, Taton D, Detrembleur C (2016) One-pot synthesis of double poly (ionic liquid) block copolymers by cobalt-mediated radical polymerization-induced self-assembly (CMR-PISA) in water. Macromol Rapid Commun 37(14):1181–1187

    Article  CAS  Google Scholar 

  28. Shen Y, Zhu S, Zeng F, Pelton R (2000) Synthesis of methacrylate macromonomers using silica gel supported atom transfer radical polymerization. Macromol Chem Phys 201(13):1387–1394

    Article  CAS  Google Scholar 

  29. Shen Y, Tang H, Ding S (2004) Catalyst separation in atom transfer radical polymerization. Prog Polym Sci 29(10):1053–1078

    Article  CAS  Google Scholar 

  30. 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

    Article  CAS  Google Scholar 

  31. Ding M, Jiang X, Zhang L, Cheng Z, Zhu X (2015) Recent progress on transition metal catalyst separation and recycling in ATRP. Macromol Rapid Commun 36(19):1702–1721

    Article  CAS  Google Scholar 

  32. Sciannamea V, Debuigne A, Piette Y, Jerome R, Detrembleur C (2006) Supported cobalt mediated radical polymerization (SCMRP) of vinyl acetate and recycling of the cobalt complex. Chem Commun 40:4180–4182

    Article  Google Scholar 

  33. 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

    Article  CAS  Google Scholar 

  34. Ding D, Pan X, Zhang Z, Li N, Zhu J, Zhu X (2016) A degradable copolymer of 2-methylene-1, 3-dioxepane and vinyl acetate by photo-induced cobalt-mediated radical polymerization. Polym Chem 7(33):5258–5264

    Article  CAS  Google Scholar 

  35. Liao C-M, Hsu C-C, Wang F-S, Wayland BB, Peng C-H (2013) Living radical polymerization of vinyl acetate and methyl acrylate mediated by co (Salen*) complexes. Polym Chem 4(10):3098–3104

    Article  CAS  Google Scholar 

  36. Maria S, Kaneyoshi H, Matyjaszewski K, Poli R (2007) Effect of electron donors on the radical polymerization of vinyl acetate mediated by [co (acac) 2]: degenerative transfer versus reversible homolytic cleavage of an organocobalt (III) complex. Chem Eur J 13(9):2480–2492

    Article  CAS  Google Scholar 

  37. 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

    Article  CAS  Google Scholar 

  38. Debuigne A, Detrembleur C, Bryaskova R, Caille J-R, Jérôme R (2006) Cobalt-mediated radical polymerization of vinyl acetate: a new tool for macromolecular engineering. ACS Symp Ser 944:372–386

  39. 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

    Article  Google Scholar 

  40. Kolyakina EV, Grishin ID, Poddel’sky AI, Grishin DF (2016) Mechanistic studies of methyl methacrylate polymerization in the presence of cobalt complex with sterically-hindered redox-active ligand. J Polym Res 23(11):222–234

    Article  Google Scholar 

  41. Kermagoret A, Chau NDQ, Grignard B, Cordella D, Debuigne A, Jérôme C, Detrembleur C (2016) Cobalt-mediated radical polymerization of vinyl acetate and acrylonitrile in supercritical carbon dioxide. Macromol Rapid Commun 37(6):539–544

    Article  CAS  Google Scholar 

  42. Bryaskova R, Detrembleur C, Debuigne A, Jérôme R (2006) Cobalt-mediated radical polymerization (cmrp) of vinyl acetate initiated by redox systems: toward the scale-up of CMRP. Macromolecules 39(24):8263–8268

    Article  CAS  Google Scholar 

  43. Boor J (1979) Ziegler-Natta catalysts and polymerizations. Academic Press, New York,

    Google Scholar 

  44. Panchenko V, Zakharov V, Paukshtis E (2006) DRIFTS and DRS studies of Phillips ethylene polymerization catalysts. Appl Catal A Gen 313(2):130–136

    Article  CAS  Google Scholar 

  45. Peng C-H, Yang T-Y, Zhao Y, Fu X (2014) Reversible deactivation radical polymerization mediated by cobalt complexes: recent progress and perspectives. Org Biomol Chem 12(43):8580–8587

    Article  CAS  Google Scholar 

  46. Monoi T, Ikeda H, Ohira H, Sasaki Y (2002) Ethylene polymerization with silica-supported Cr [N (SiMe3) 2] 3/Alumoxane catalyst. Polym J 34(6):461–465

    Article  CAS  Google Scholar 

  47. Gaspar A, Dieguez L (2002) The influence of Cr precursors in the ethylene polymerization on Cr/SiO 2 catalysts. Appl Catal A Gen 227(1):241–254

    Article  CAS  Google Scholar 

  48. Semsarzadeh MA, Abdollahi M (2008) Kinetic study of atom transfer radical homo-and copolymerization of styrene and methyl methacrylate initiated with trichloromethyl-terminated poly (vinyl acetate) macroinitiator. Polymer 49(13):3060–3069

    Article  CAS  Google Scholar 

  49. Semsarzadeh MA, Amiri S (2012) Controlled free radical polymerization of vinyl acetate with cobalt acetoacetonate. J Chem Sci 124(2):521–527

    Article  CAS  Google Scholar 

  50. Semsarzadeh M, Amiri S, Azadeh M (2012) Controlled radical polymerization of vinyl acetate in presence of mesoporous silica supported TiCl4 heterogeneous catalyst. Bull Mater Sci 35(5):867–874

    Article  CAS  Google Scholar 

  51. 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

    Article  CAS  Google Scholar 

  52. Ye Z, Zhu S, Wang WJ, Alsyouri H, Lin Y (2003) Morphological and mechanical properties of nascent polyethylene fibers produced via ethylene extrusion polymerization with a metallocene catalyst supported on MCM-41 particles. J Polym Sci B Polym Phys 41(20):2433–2443

    Article  CAS  Google Scholar 

  53. Dong X, Wang L, Wang W, Jiang G, Chen Y, Zhao Z, Wang J (2005) Preparation of Nano-polyethylene fibers and floccules by extrusion polymerization under atmospheric pressure using the SBA-15-supported Cp2ZrCl2 catalytic system. Macromol Mater Eng 290(1):31–37

    Article  CAS  Google Scholar 

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  1. Polymer Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box: 14155/143, Tehran, Iran

    Mohammad Ali Semsarzadeh & Alireza Sabzevari

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  1. Mohammad Ali Semsarzadeh
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  2. Alireza Sabzevari
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Correspondence to Mohammad Ali Semsarzadeh.

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Semsarzadeh, M.A., Sabzevari, A. 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, 177 (2017). https://doi.org/10.1007/s10965-017-1328-y

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