Abstract
Synthesis and anionic polymerization of the fluorine-substituted phenyl methacrylates are herein reported. A series of mono-, di-, and multi-substituted fluorophenyl methacrylates H2C=C(CH3)C(O)OC6H4F-4 (M 1a), H2C=C(CH3)C(O)OC6H4F-3 (M 1b), H2C=C(CH3)C(O)OC6H3F2-2,4 (M 2), H2C=C(CH3)C(O)OC6H2F3-2,3,4 (M 3), H2C=C(CH3)C(O)OC6HF4-2,3,5,6 (M 4), and H2C=C(CH3)C(O)OC6F5 (M 5) were synthesized and characterized. Initially, the polymerization was carried out on the monomer M 1a by using nBuLi, tBuLi, and KH as the respective catalysts; this approach produced the polymers in yields of 12%–50%, but with lower molecular weights. Similar results were obtained by using tBuLi for catalytically polymerizing the other five monomers. By introducing a co-catalyst MeAl(BHT)2, the catalysts NaH, LiH, and tBuOLi each were tested to polymerize M1a, which gave the polymers in very low yields (3%–7%). Polymer yields of 13%–27% were obtained by each of the catalysts LiAlH4, nBuLi, PhLi, and tBuLi in connection with MeAl(BHT)2, but a better yield (61%) was achieved with KH/MeAl(BHT)2. The KH/MeAl(BHT)2 catalyst system was further employed to polymerize M 1b and M 2, which afforded respective polymer yields of 12%–63% and 10%–53%, depending on the molar ratios of KH:MeAl(BHT)2 as well as on the monomer concentrations. All of the polymers produced were syndiotactically rich in structure, as indicated by either 1H or 19F NMR data. The polymerization mechanism by the combined catalyst system is proposed.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Ameduri B. From vinylidene fluoride (VDF) to the applications of VDF-containing polymers and copolymers: recent developments and future trends. Chem Rev, 2009, 109: 6632–6686
Dumas L, Fleury E, Portinha D. Wettability adjustment of PVDF surfaces by combining radiation-induced grafting of (2,3,4,5,6)-pentafluorostyrene and subsequent chemoselective “click-type” reaction. Polymer, 2014, 55: 2628–2634
Ren Y, Lodge TP, Hillmyer MA. A simple and mild route to highly fluorinated model polymers. Macromolecules, 2001, 34: 4780–4787
Ameduri B, Boutevin B, Nouiri M. Synthesis and properties of fluorinated telechelic macromolecular diols prepared by radical grafting of fluorinated thiols onto hydroxyl-terminated polybutadienes. J Polym Sci, Part A: Polym Chem, 1993, 31: 2069–2080
Chuvatkin NN, Panteleeva IY. Polyfluoroacrylates. New York: Wiley, 1997: 191–206
Boutevin B, Rousseau A, Bosc D. Accessible new acrylic-monomers and polymers as highly transparent organic materials. J Polym Sci, Part A: Polym Chem, 1992, 30: 1279–1286
Blazejewski JC, Hofstraat JW, Lequesne C, Wakselman C, Wiersum UE. Halogenoaryl acrylates: preparation, polymerization and optical properties. J Fluorine Chem, 1999, 97: 191–199
Chua GBH, Roth PJ, Duong HTT, Davis TP, Lowe AB. Synthesis and thermoresponsive solution properties of poly oligo(ethylene glycol) (meth)acrylamides: biocompatible PEG analogues. Macromolecules, 2012, 45: 1362–1374
Barz M, Tarantola M, Fischer K, Schmidt M, Luxenhofer R, Janshoff A, Théato P, Zentel R. From defined reactive diblock copolymers to functional HPMA-based self-assembled nanoaggregates. Biomacromolecules, 2008, 9: 3114–3118
Roth PJ, Davis TP, Lowe AB. Novel α,α-bischolesteryl functional (co)polymers: RAFT radical polymerization synthesis and preliminary solution characterization. Macromol Rapid Commun, 2014, 35: 813–820
Günay KA, Schüwer N, Klok HA. Synthesis and postpolymerization modification of poly(pentafluorophenyl methacrylate) brushes. Polym Chem, 2012, 3: 2186–2192
Zhang QL, Schattling P, Théfato P, Hoogenboom R. Tuning the upper critical solution temperature behavior of poly(methyl methacrylate) in aqueous ethanol by modification of an activated ester comonomer. Polym Chem, 2012, 3: 1418–1426
Odian G. Principles of Polymerization. 4th Ed. New York: Wiley, 2004: 372–374
Baskaran D. Strategic developments in living anionic polymerization of alkyl (meth)acrylates. Prog Polym Sci, 2003, 28: 521–581
Chen EYX. Coordination polymerization of polar vinyl monomers by single-site metal catalysts. Chem Rev, 2009, 109: 5157–5214
Flory PJ. Tensile strength in relation to molecular weight of high polymers. J Am Chem Soc, 1945, 67: 2048–2050
Fox TG, Flory PJ. Viscosity-molecular weight and viscositytemperature relationships for polystyrene and polyisobutylene1,2. J Am Chem Soc, 1948, 70: 2384–2395
Duque L, Menges B, Borros S, Förch R. Immobilization of biomolecules to plasma polymerized pentafluorophenyl methacrylate. Biomacromolecules, 2010, 11: 2818–2823
Blazejewski JC, Hofstraat JW, Lequesne C, Wakselman C, Wiersum UE. Formation of monomeric halogenoaryl acrylates in the presence of hindered pyridine bases. J Fluorine Chem, 1998, 91: 175–177
Eberhardt M, Mruk R, Zentel R, Théato P. Synthesis of pentafluorophenyl(meth)acrylate polymers: new precursor polymers for the synthesis of multifunctional materials. Eur Polym J, 2005, 41: 1569–1575
Teng HX, Yang L, Mikes F, Koike Y, Okamoto Y. Property modification of poly(methyl methacrylate) through copolymerization with fluorinated aryl methacrylate monomers. Polym Adv Technol, 2007, 18: 453–457
Shreve AP, Mulhaupt R, Fultz W, Calabrese J, Robbins W, Ittel SD. Sterically hindered aryloxide-substituted alkylaluminum compounds. Organometallics, 1988, 7: 409–416
Oh SG, Lee JU, Kim JS, Lee JY, Kim JH. Production of photosensitive acrylic polymer allowing penetration of extreme UV for photoresist composition, and method for forming resist pattern. KR2012065745A
Minagawa Y. Surface modification method, surface-modified elastomer, syringe gasket and tire thereof. PRC Patents: CN103570965A
Minagawa Y. Surface-modification of vulcanized rubbers or thermoplastic elastomers. PRC Patents: CN103224643A
Bovey FA, Mirau PA. NMR of Polymers. San Diego, CA: Academic Press, 1996
Bulai A, Jimeno ML, Alencar de Queiroz AA, Gallardo A, San Román J. 1H and 13C nuclear magnetic resonance studies on the stereochemical configuration of bis(N,N-dimethyl-2,4-dimethylglutarylamide) and poly(N,N-dimethylacrylamide). Macromolecules, 1996, 29: 3240–3246
Ferguson RC, Ovenall DW. High resolution nmr analysis of the stereochemistry of poly(methyl methacrylate). Macromolecules, 1987, 20: 1245–1248
Subramanian R, Allen RD, McGrath JE, Ward TC. Tacticity and thermal-analysis of some novel poly methyl-methacrylate (PMMA) homopolymers. Polym Prepr, 1985, 26: 238–240
Due to low molecular weight, the precipitation of the polymer is only realized in the n-hexane rather than the methanl solvent.
Jiang B. Synthesis and characterization of fluorine-containing functionalized olefin polymer. Undergraduate Thesis. Xiamen: Xiamen University, 2008
Rodriguez-Delgado A, Chen EYX. Single-site anionic polymerization. Monomeric ester enolaluminate propagator synthesis, molecular structure, and polymerization mechanism. J Am Chem Soc, 2005, 127: 961–974
Miyake GM, Mariott WR, Chen EYX. Asymmetric coordination polymerization of acrylamides by enantiomeric metallocenium ester enolate catalysts. J Am Chem Soc, 2007, 129: 6724–6725
Hu YJ, Gustafson LO, Zhu HP, Chen EYX. Anionic polymerization of mma and renewable methylene butyrolactones by resorbable potassium salts. J Polym Sci, Part A: Polym Chem, 2011, 49: 2008–2017
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, B., Zhou, P., Chen, Y. et al. Anionic polymerization of fluorine-substituted phenyl methacrylates. Sci. China Chem. 58, 107–113 (2015). https://doi.org/10.1007/s11426-014-5247-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-014-5247-z