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A Detailed Investigation of the Free Radical Copolymerization Behavior of n-Butyl Acrylate Macromonomers

  • Anna-Marie Zorn
    Anna-Marie Zorn
    Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany
  • Tanja Junkers*
    Tanja Junkers
    Institute for Materials Research (IMO), Polymer Reaction Design Group, Universiteit Hasselt, Agoralaan, Gebouw D, BE-3590 Diepenbeek, Belgium
    *E-mail [email protected], Tel +49 721 608 45641 (C.B.-K.). E-mail [email protected], Tel +32 11 26 8318 (T.J.).
  • , and 
  • Christopher Barner-Kowollik*
    Christopher Barner-Kowollik
    Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany
    *E-mail [email protected], Tel +49 721 608 45641 (C.B.-K.). E-mail [email protected], Tel +32 11 26 8318 (T.J.).
Cite this: Macromolecules 2011, 44, 17, 6691–6700
Publication Date (Web):August 4, 2011
https://doi.org/10.1021/ma201345m
Copyright © 2011 American Chemical Society

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    Abstract

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    The free radical copolymerization of macromonomers with low molecular weight monomers represents a versatile tool for the formation of statistical copolymers featuring pendant side chains. In the current study n-butyl acrylate macromonomer (BAMM) has been synthesized via high temperature acrylate synthesis in a one-pot–one-step procedure and copolymerized with benzyl acrylate (BzA) as a comonomer up to 40% conversion in a free radical copolymerization with 1,1′-azobis(isobutyronitrile) (AIBN) as a source of radicals. The copolymers poly(BAMM)-co-poly(BzA) are fully characterized via size exclusion chromatography (SEC), nuclear magnetic resonance spectroscopy (NMR), and liquid adsorption chromatography at critical conditions (LACCC). The achievable molecular weight of the synthesized poly(BAMM)-co-poly(BzA) lies between 8000 and 77 000 g mol–1 with a polydispersity of 1.30–2.12. Calculated copolymer compositions from the integrals of the specific resonances Har and CH2 of the BzA compared to CH2 of the BAMM have been subjected to a (terminal model) Mayo–Lewis analysis, resulting in estimated reactivity ratios at ∼40% conversion of rBzA = 2.46 and rBAMM = 1.79, indicating a copolymer composition of FBA < 0.65 for the copolymers derived from fBzA > 0.9 up to a copolymer composition of FBA > 0.9 for copolymers with a comonomer feed of fBzA < 0.6. The poly(BAMM)-co-poly(BzA) have been analyzed under critical conditions of n-butyl acrylate (BA) on a normal phase column to obtain an image of the generated poly(BAMM)-co-poly(BzA).

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    Further analytical data of BAMM, the poly(BA) standards and copolymers, and LACCC measurements. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

    This article is cited by 14 publications.

    1. T. Pirman, M. Ocepek, B. Likozar. Radical Polymerization of Acrylates, Methacrylates, and Styrene: Biobased Approaches, Mechanism, Kinetics, Secondary Reactions, and Modeling. Industrial & Engineering Chemistry Research 2021, 60 (26) , 9347-9367. https://doi.org/10.1021/acs.iecr.1c01649
    2. Paul H. M. Van Steenberge, Joke Vandenbergh, Marie-Françoise Reyniers, Tanja Junkers, Dagmar R. D’hooge, Guy B. Marin. Kinetic Monte Carlo Generation of Complete Electron Spray Ionization Mass Spectra for Acrylate Macromonomer Synthesis. Macromolecules 2017, 50 (7) , 2625-2636. https://doi.org/10.1021/acs.macromol.7b00333
    3. Wenwen Wang, Weiyu Wang, Xinyi Lu, Sachin Bobade, Jihua Chen, Nam-Goo Kang, Qiuyu Zhang, and Jimmy Mays . Synthesis and Characterization of Comb and Centipede Multigraft Copolymers PnBA-g-PS with High Molecular Weight Using Miniemulsion Polymerization. Macromolecules 2014, 47 (21) , 7284-7295. https://doi.org/10.1021/ma501866t
    4. Joke Vandenbergh, Tanja Junkers. Synthesis of Macromonomers from High-Temperature Activation of Nitroxide Mediated Polymerization (NMP)-made Polyacrylates. Macromolecules 2013, 46 (9) , 3324-3331. https://doi.org/10.1021/ma400477t
    5. Joke Vandenbergh, Tanja Junkers. Macromonomers from AGET Activation of Poly(n-butyl acrylate) Precursors: Radical Transfer Pathways and Midchain Radical Migration. Macromolecules 2012, 45 (17) , 6850-6856. https://doi.org/10.1021/ma301233v
    6. Yohann Guillaneuf, Didier Gigmes, Tanja Junkers. Investigation of the End Group Fidelity at High Conversion during Nitroxide-Mediated Acrylate Polymerizations. Macromolecules 2012, 45 (13) , 5371-5378. https://doi.org/10.1021/ma300953b
    7. Boris Bizet, Etienne Grau, Henri Cramail, José M. Asua. Crosslinked isocyanate-free poly(hydroxy urethane)s – Poly(butyl methacrylate) hybrid latexes. European Polymer Journal 2021, 146 , 110254. https://doi.org/10.1016/j.eurpolymj.2020.110254
    8. Vishnu D. Deepak, Mario Gauthier. Synthesis of isoprenic polybutadiene macromonomers for the preparation of branched polybutadiene. European Polymer Journal 2019, 113 , 133-141. https://doi.org/10.1016/j.eurpolymj.2019.01.041
    9. Nicholas Ballard, Jose M. Asua. Radical polymerization of acrylic monomers: An overview. Progress in Polymer Science 2018, 79 , 40-60. https://doi.org/10.1016/j.progpolymsci.2017.11.002
    10. Joris J. Haven, Neomy Zaquen, Maarten Rubens, Tanja Junkers. The Kinetics of n ‐Butyl Acrylate Radical Polymerization Revealed in a Single Experiment by Real Time On‐line Mass Spectrometry Monitoring. Macromolecular Reaction Engineering 2017, 11 (4) https://doi.org/10.1002/mren.201700016
    11. Pieter Derboven, Paul H. M. Van Steenberge, Joke Vandenbergh, Marie‐Francoise Reyniers, Tanja Junkers, Dagmar R. D'hooge, Guy B. Marin. Improved Livingness and Control over Branching in RAFT Polymerization of Acrylates: Could Microflow Synthesis Make the Difference?. Macromolecular Rapid Communications 2015, 36 (24) , 2149-2155. https://doi.org/10.1002/marc.201500357
    12. Anthony Kermagoret, Benjamin Wenn, Antoine Debuigne, Christine Jérôme, Tanja Junkers, Christophe Detrembleur. Improved photo-induced cobalt-mediated radical polymerization in continuous flow photoreactors. Polymer Chemistry 2015, 6 (20) , 3847-3857. https://doi.org/10.1039/C5PY00299K
    13. Johannes Barth, Michael Buback, Christopher Barner‐Kowollik, Tanja Junkers, Gregory T. Russell. Single‐pulse pulsed laser polymerization–electron paramagnetic resonance investigations into the termination kinetics of n ‐butyl acrylate macromonomers. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50 (22) , 4740-4748. https://doi.org/10.1002/pola.26295
    14. Anna‐Marie Zorn, Christopher Barner‐Kowollik. Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50 (12) , 2366-2377. https://doi.org/10.1002/pola.26011

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