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Original Articles

A Mechanistic Perspective on Solvent Effects in Free-Radical Copolymerization

Pages 567-593 | Published online: 10 Mar 2008

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Jian Hao, Feng An, Chunxiang Lu & Yaodong Liu. (2019) Solvent effects on radical copolymerization of acrylonitrile and methyl acrylate: solvent polarity and solvent-monomer interaction. Journal of Macromolecular Science, Part A 56:11, pages 1012-1021.
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Benjamin B. Noble & Michelle L. Coote. (2013) First principles modelling of free-radical polymerisation kinetics. International Reviews in Physical Chemistry 32:3, pages 467-513.
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RamanaG. V. Reddy, Juby Thomas & P. K. Radhakrishnan. (2008) Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate. Designed Monomers and Polymers 11:2, pages 159-171.
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Cornel Hagiopol. (2006) Solvent Effect in Binary Copolymerization. Journal of Macromolecular Science, Part A 43:3, pages 487-495.
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Pengyu Chen, Zheyuan Zhang, Zach Rouse, Shefford P. Baker, Jingjie Yeo & Rong Yang. (2023) Engineering solvation in initiated chemical vapour deposition for control over polymerization kinetics and material properties. Nature Synthesis 2:4, pages 373-383.
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Shanglin Li, Bingqian Han, Donggen Zhou, Yin Gu, Bao Li, Jianxin Ma, Rongxin Fu, Xiao Qi & Peng Liu. (2023) One-Stop Extraction and In Situ RT-qPCR for Ultrasensitive Detection of Highly Diluted SARS-CoV-2 in Large-Volume Samples from Aquatic Environments . Analytical Chemistry 95:4, pages 2339-2347.
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Nhu Q. Nguyen, Ryan L. Hamblin & Kateri H. DuBay. (2022) Emergent Sequence Biasing in Step-Growth Copolymerization: Influence of Non-Bonded Interactions and Comonomer Reactivities. The Journal of Physical Chemistry B 126:34, pages 6585-6597.
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Hitoshi Tanaka, Misato Kii, Yusuke Yamamoto & Hiroyuki Tsuiki. (2021) Dependence of polymer tacticity and polymerization rate on conversion, solvent, chain length in radical polymerization of captodative-substituted ethyl acetoxyacrylate. Polymer Bulletin 79:8, pages 6547-6564.
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Tomohiro Hirano, Ryota Kamiike, Takumi Yuki, Daishi Matsumoto & Koichi Ute. (2022) Determination of monomer reactivity ratios from a single sample using multivariate analysis of the 1H NMR spectra of poly[(methyl methacrylate)-co-(benzyl methacrylate)]. Polymer Journal 54:5, pages 623-631.
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Bert Klumperman, Rueben Pfukwa & Albena Lederer. 2022. Macromolecular Engineering. Macromolecular Engineering 1 51 .
Ryan L. Hamblin, Nhu Q. Nguyen & Kateri H. DuBay. (2022) Selective solvent conditions influence sequence development and supramolecular assembly in step-growth copolymerization. Soft Matter 18:5, pages 943-955.
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Lara Riemann, Sarah Brandt & Philipp Vana. (2021) Refining Reactivity Ratios in the Copolymerization of Styrene and Methyl Methacrylate by EasySpin/MATLAB Simulations and Electron Paramagnetic Resonance Spectroscopy. Macromolecular Theory and Simulations 30:6, pages 2100048.
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Peter Deglmann, Klaus-Dieter Hungenberg & Hugo M. Vale. (2021) Dependence of Copolymer Composition in Radical Polymerization on Solution Properties: a Quantitative Thermodynamic Interpretation. Industrial & Engineering Chemistry Research 60:29, pages 10566-10583.
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Michael A. Tallon & Osama M. Musa. 2021. Handbook of Pyrrolidone and Caprolactam Based Materials. Handbook of Pyrrolidone and Caprolactam Based Materials 645 755 .
Yeasmin Nahar, James Horne, Vinh Truong, Alex C. Bissember & Stuart C. Thickett. (2021) Preparation of thermoresponsive hydrogels via polymerizable deep eutectic monomer solvents . Polymer Chemistry 12:2, pages 254-264.
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Cengiz Soykan & Hilal Obuz. (2019) Spectroscopic characterization of glycidyl methacrylate with acrylonitrile copolymers and monomer reactivity ratios. Microscopy Research and Technique 83:1, pages 22-34.
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Neomy Zaquen, Wan A. A. W. Azizi, Jonathan Yeow, Rhiannon P. Kuchel, Tanja Junkers, Per B. Zetterlund & Cyrille Boyer. (2019) Alcohol-based PISA in batch and flow: exploring the role of photoinitiators. Polymer Chemistry 10:19, pages 2406-2414.
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Loretta Idowu & Robin Hutchinson. (2019) Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate. Polymers 11:3, pages 487.
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Thomas R. Rooney & Robin A. Hutchinson. (2018) Monomer Structure and Solvent Effects on Copolymer Composition in (Meth)acrylate Radical Copolymerization. Industrial & Engineering Chemistry Research 57:15, pages 5215-5227.
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Elena Yu. Kozhunova, Alexey A. Gavrilov, Mikhail Yu. Zaremski & Alexander V. Chertovich. (2017) Copolymerization on Selective Substrates: Experimental Test and Computer Simulations. Langmuir 33:14, pages 3548-3555.
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Denis M. Kamorin, Misha Rumyantsev, Oleg A. Kazantsev, Alexey P. Sivokhin & Sofia I. Kamorina. (2017) Influences of monomer self-association on the radical solution homopolymerization of N-[3-(dimethylamino)propyl](meth)acrylamide. Journal of Applied Polymer Science 134:4.
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Michael Buback, Hendrik Schroeder & Hendrik Kattner. (2016) Detailed Kinetic and Mechanistic Insight into Radical Polymerization by Spectroscopic Techniques. Macromolecules 49:9, pages 3193-3213.
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Oleg A. Kazantsev, Sofia I. Kamorina, Misha Rumyantsev, Denis M. Kamorin & Alexey P. Sivokhin. (2016) Radical copolymerization of higher alkyl methacrylates with acrylic esters and amides in toluene: influence of monomer association on copolymer composition. Journal of Polymer Research 23:5.
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Jan E. S. Schier & Robin A. Hutchinson. (2016) The influence of hydrogen bonding on radical chain-growth parameters for butyl methacrylate/2-hydroxyethyl acrylate solution copolymerization. Polymer Chemistry 7:27, pages 4567-4574.
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Krystyna Plochocka, Xuejun Liu, Michael A. Tallon & Osama M. Musa. 2016. Handbook of Maleic Anhydride Based Materials. Handbook of Maleic Anhydride Based Materials 211 250 .
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Hendrik Kattner & Michael Buback. (2014) Chain-Length-Dependent Termination of Vinyl Acetate and Vinyl Pivalate Bulk Homopolymerizations Studied by SP-PLP-EPR. Macromolecular Chemistry and Physics 215:12, pages 1180-1191.
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Yi Chen, Hui Zhang & Qing Liu. (2014) FT-IR spectroscopy combined with DFT calculation to explore solvent effects of vinyl acetate. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 126, pages 122-128.
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A.P. Sivokhin, S.I. Samodurova, O.A. Kazantsev, K.V. Shirshin, D.M. Kamorin & D.V. Orekhov. (2018) The Influence of the Synthesis Conditions on the Compositional Inhomogeneity of Copolymers of Higher N -alkyl Acrylamides and n -docecyl (meth)Acrylate . International Polymer Science and Technology 41:1, pages 43-50.
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Christopher Magee, Yusuke Sugihara, Per B. Zetterlund & Fawaz Aldabbagh. (2014) Chain transfer to solvent in the radical polymerization of structurally diverse acrylamide monomers using straight-chain and branched alcohols as solvents. Polymer Chemistry 5:7, pages 2259.
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MICHELLE L. COOTE & THOMAS P. DAVIS. 2014. Handbook of Solvents. Handbook of Solvents 811 833 .
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O. A. Kazantsev, A. P. Sivokhin, S. I. Samodurova, D. M. Kamorin & D. V. Orekhov. (2012) Effect of the synthesis conditions on the compositional heterogeneity of copolymers of higher N-alkylacrylamides and butyl (meth)acrylate. Russian Journal of Applied Chemistry 85:5, pages 804-811.
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Sema Sevimli, Sharon Sagnella, Maria Kavallaris, Volga Bulmus & Thomas P. Davis. (2012) Synthesis, self-assembly and stimuli responsive properties of cholesterol conjugated polymers. Polymer Chemistry 3:8, pages 2057.
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B. Klumperman. 2012. Polymer Science: A Comprehensive Reference. Polymer Science: A Comprehensive Reference 433 453 .
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Christoph J. Dürr, Sebastian G. J. Emmerling, Andreas Kaiser, Sven Brandau, Axel K. T. Habicht, Michael Klimpel & Christopher Barner‐Kowollik. (2011) A Detailed investigation of the experimental conditions for the reversible addition fragmentation chain transfer‐mediated copolymerization of acrylonitrile and butadiene. Journal of Polymer Science Part A: Polymer Chemistry 50:1, pages 174-180.
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Michelle L. Coote & Ching Y. Lin. 2011. Computational Methods for Large Systems. Computational Methods for Large Systems 435 474 .
Margarita Droulia, Athina Anastasaki, Alexandros Rokotas, Marinos Pitsikalis & Patrina Paraskevopoulou. (2011) Statistical copolymers of methyl methacrylate and 2‐methacryloyloxyethyl ferrocenecarboxylate: Monomer reactivity ratios, thermal and electrochemical properties. Journal of Polymer Science Part A: Polymer Chemistry 49:14, pages 3080-3089.
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Robert A. Cockburn, Rebekka Siegmann, Kevin A. Payne, Sabine Beuermann, Timothy F. L. McKenna & Robin A. Hutchinson. (2011) Free Radical Copolymerization Kinetics of γ-Methyl-α-methylene-γ-butyrolactone (MeMBL). Biomacromolecules 12:6, pages 2319-2326.
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Marc A. Dubé & Somaieh Salehpour. 2011. Green Polymerization Methods. Green Polymerization Methods 143 161 .
Kun Liang & Robin A. Hutchinson. (2010) Solvent Effects on Free-Radical Copolymerization Propagation Kinetics of Styrene and Methacrylates. Macromolecules 43:15, pages 6311-6320.
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Xuewei Zhang, Olivia Giani, Sophie Monge & Jean-Jacques Robin. (2010) RAFT polymerization of N,N-diethylacrylamide: Influence of chain transfer agent and solvent on kinetics and induction period. Polymer 51:14, pages 2947-2953.
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Yuya Maki, Hideharu Mori & Takeshi Endo. (2010) Controlled Synthesis of Alternating Copolymers by RAFT Copolymerization of N -Vinylphthalimide with N -Isopropylacrylamide . Macromolecular Chemistry and Physics 211:10, pages 1137-1147.
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Veronika Strehmel, Hans Rexhausen & Peter Strauch. (2010) Influence of imidazolium bis(trifluoromethylsulfonylimide)s on the rotation of spin probes comprising ionic and hydrogen bonding groups. Physical Chemistry Chemical Physics 12:8, pages 1933.
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Michelle L. Coote. (2009) Quantum-Chemical Modeling of Free-Radical Polymerization. Macromolecular Theory and Simulations 18:7-8, pages 388-400.
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Somaieh Salehpour, Marc A. Dubé & Maya Murphy. (2009) Solution polymerization of styrene using biodiesel as a solvent: Effect of biodiesel feedstock. The Canadian Journal of Chemical Engineering 87:1, pages 129-135.
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Veronika Strehmel, Hendrik Wetzel, André Laschewsky, Evelin Moldenhauer & Thorsten Klein. (2008) Influence of imidazolium-based ionic liquids on the synthesis of amphiphilic copolymers based on n -butylmethacrylate and a zwitterionic methacrylate . Polymers for Advanced Technologies 19:10, pages 1383-1390.
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Hideharu Mori, Ikumi Kato, Motonobu Matsuyama & Takeshi Endo. (2008) RAFT Polymerization of Acrylamides Containing Proline and Hydroxyproline Moiety: Controlled Synthesis of Water-Soluble and Thermoresponsive Polymers. Macromolecules 41:15, pages 5604-5615.
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Somaieh Salehpour & Marc A Dubé. (2008) The use of biodiesel as a green polymerization solvent at elevated temperatures. Polymer International 57:6, pages 854-862.
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S. Kuchanov, S. Pogodin, G. ten Brinke & A. Khokhlov. (2008) Polymer Globule as a Nanoreactor. Macromolecules 41:7, pages 2689-2693.
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G. V. Ramana Reddy, N. Gayathri Devi & Jayakishore Panda. (2007) Microemulsion and conventional emulsion copolymerizations of styrene with methyl methacrylate. Journal of Applied Polymer Science 105:6, pages 3391-3401.
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Daria E. Lonsdale, Geoffrey Johnston-Hall, Amanda Fawcett, Craig A. Bell, Carl N. Urbani, Michael R. Whittaker & Michael J. Monteiro. (2007) Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent. Journal of Polymer Science Part A: Polymer Chemistry 45:16, pages 3620-3625.
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Bert Klumperman. 2007. Macromolecular Engineering. Macromolecular Engineering 813 838 .
R. Vijayaraghavan & D.R. MacFarlane. (2006) Synthesis, reactivity ratios and characterization of hydroquinone promoted CT co-polymerization of styrene and methyl methacrylate in a room temperature ionic liquid. European Polymer Journal 42:10, pages 2736-2742.
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Michelle L. Coote. 2002. Encyclopedia of Polymer Science and Technology. Encyclopedia of Polymer Science and Technology.
R. Cuervo‐Rodríguez, R. París‐Escribano, M. C. Fernández‐Monreal, E. L. Madruga & M. Fernández‐García. (2005) Influence of aggregate formation in the copolymerization of ethyl α‐hydroxymethylacrylate with methyl methacrylate. Journal of Polymer Science Part A: Polymer Chemistry 43:18, pages 4187-4195.
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Per B. Zetterlund, Masami Takenaka & Anthony F. Johnson. (2005) Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ 13 C NMR Measurements of Individual Monomer Reaction Rates . Macromolecules 38:6, pages 2173-2179.
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Graeme Moad & David H. Solomon. 2005. The Chemistry of Radical Polymerization. The Chemistry of Radical Polymerization 413 449 .
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Sang-Do Yeo & Erdogan Kiran. (2004) Copolymerization of Acrylonitrile with Methyl Methacrylate and 2-Chlorostyrene in Supercritical CO 2 . Macromolecules 37:22, pages 8239-8248.
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Francisco López-Serrano, Jorge E. Puig & Jesús Álvarez. (2004) Integrodifferential Approach to the Estimation of Copolymerization Reactivity Ratios. Industrial & Engineering Chemistry Research 43:23, pages 7361-7372.
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Per B. Zetterlund, Shinji Tagashira, Kyoko Izumi, Yutaka Nagano, Makoto Azukizawa, Hirotomo Yamazoe, Masatsugu Kumagai & Bunichiro Yamada. (2002) Penultimate Unit Effects in Free Radical Copolymerization Studied Using the Individual Propagating Radical Concentrations from Electron Spin Resonance Spectroscopy. Macromolecules 35:21, pages 8209-8215.
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Carmen Fernández-Monreal, Gerardo Martínez, Manuel Sánchez-Chaves & Enrique López Madruga. (2001) Solvent effect on the free-radical copolymerization of 2-hydroxyethyl methacrylate with t -butyl acrylate . Journal of Polymer Science Part A: Polymer Chemistry 39:12, pages 2043-2048.
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Hong Hua & Marc A. Dubé. (2001) Off-line monitoring of butyl acrylate, methyl methacrylate and vinyl acetate homo- and copolymerizations in toluene using ATR-FTIR spectroscopy. Polymer 42:14, pages 6009-6018.
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Hong Hua & Marc A. Dubé. (2001) Terpolymerization monitoring with ATR‐FTIR spectroscopy. Journal of Polymer Science Part A: Polymer Chemistry 39:11, pages 1860-1876.
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Michelle L Coote & Thomas P Davis. (2000) Propagation rate coefficients for styrene solution polymerization in dimethyl formamide and acetonitrile. European Polymer Journal 36:11, pages 2423-2427.
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Kazunobu Yamada, Tamaki Nakano & Yoshio Okamoto. (2000) Free-radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio. Journal of Polymer Science Part A: Polymer Chemistry 38:1, pages 220-228.
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M.L. Coote & T.P. Davis. (1999) The mechanism of the propagation step in free-radical copolymerisation. Progress in Polymer Science 24:9, pages 1217-1251.
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Manuel S�nchez-Chaves, Gerardo Mart�nez & Enrique L�pez Madruga. (1999) Low- and high-conversion studies of the free radical copolymerization of 2-hydroxyethyl methacrylate with styrene inN,N?-dimethylformamide solution. Journal of Polymer Science Part A: Polymer Chemistry 37:15, pages 2941-2948.
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