Skip to main content
Disciplines
Automotive Business IT + Informatics Construction + Real Estate Electrical Engineering + Electronics Energy + Sustainability Insurance + Risk Finance + Banking Management + Leadership Marketing + Sales Mechanical Engineering + Materials
Events
DE
EN
Books
Journals
Topic Page
Marketing
Start single access now
Access for companies
EXTENDED SEARCH
Log in
Top
Polymer Bulletin
Published in: Polymer Bulletin 11/2023

21-12-2022 | ORIGINAL PAPER

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

Authors: Alireza Sabzevari, Arezoo Sh Dadkhah, Mohammad Kohestanian, Athar Mahdieh, Mohammad Ali Semsarzadeh

Published in: Polymer Bulletin | Issue 11/2023

Log in

Activate our intelligent search to find suitable subject content or patents.

search-config
loading …

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.

Graphical abstract

previous article Utilization of electron beam irradiation vulcanization to reuse devulcanized rubber in polypropylene-montmorillonite nanocomposites
next article Separation of copper and nickel from synthetic wastewater by polymer inclusion membrane containing di(2-ethylhexyl)phosphoric acid

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

  • über 102.000 Bücher
  • über 537 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Finance + Banking
  • Management + Führung
  • Marketing + Vertrieb
  • Maschinenbau + Werkstoffe
  • Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

  • über 67.000 Bücher
  • über 390 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Maschinenbau + Werkstoffe




 

Jetzt Wissensvorsprung sichern!

inform now
Literature
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
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
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
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
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
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
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):14471–14553PubMed
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
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
11.
Benchaphanthawee W, Peng CH (2021) Organo-cobalt complexes in reversible-deactivation radical polymerization. Chem Rec 21(12):3628–3647PubMed
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
29.
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
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
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
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
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
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
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
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
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
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
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
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
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
44.
Nguyen JV, Jones CW (2004) Design, behavior, and recycling of silica-supported CuBr−bipyridine ATRP catalysts. Macromolecules 37(4):1190–1203
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
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
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
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
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
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
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
53.
Mori S, Barth HG (2013) Size exclusion chromatography. Springer Science & Business Media, New York
54.
Wu C-S (2003) Handbook of size exclusion chromatography and related techniques: revised and expanded, vol 91. CRC Press, Boca Raton
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
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
58.
Zhao H, Simon SL (2011) Methyl methacrylate polymerization in nanoporous confinement. Polymer 52(18):4093–4098
Metadata
Title
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
Authors
Alireza Sabzevari
Arezoo Sh Dadkhah
Mohammad Kohestanian
Athar Mahdieh
Mohammad Ali Semsarzadeh
Publication date
21-12-2022
Publisher
Springer Berlin Heidelberg
Published in
Polymer Bulletin / Issue 11/2023
Print ISSN: 0170-0839
Electronic ISSN: 1436-2449
DOI
https://doi.org/10.1007/s00289-022-04652-x

Other articles of this Issue 11/2023

Polymer Bulletin 11/2023 Go to the issue

ORIGINAL PAPER

Phthalic acid-derived diluents as an effective alternative to styrene in optimization of vinyl ester resins properties

ORIGINAL PAPER

Enhancing the mechanical properties and foaming performance of polypropylene through melt grafting reaction by using trimethylolpropane triacrylate

REVIEW PAPER

Exploring the advancement of polymer-based nano-formulations for ocular drug delivery systems: an explicative review

ORIGINAL PAPER

Separation of copper and nickel from synthetic wastewater by polymer inclusion membrane containing di(2-ethylhexyl)phosphoric acid

REVIEW PAPER

Effects of carbon nanotubes on structure, performance and properties of polymer nanocomposite membranes for water/wastewater treatment applications: a comprehensive review

ORIGINAL PAPER

Urethane- and urea-modified polymeric sorbents enable efficient and selective removal of mercury(II) from water

Premium Partners

    Image Credits