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Branched methyl methacrylate copolymer particles prepared by RAFT dispersion polymerization

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Reversible addition–fragmentation chain transfer (RAFT) dispersion copolymerization of methyl methacrylate (MMA) and tripropylene glycol diacrylate (TPGDA) was carried out in ethanol/water in the present work. S-1-Dodecyl-S′-(α,α-dimethyl-α″-aceticacid) trithiocarbonate (TTC) was used as a chain transfer agent to inhibit the occurrence of gelation. Branched poly(methyl methacrylate) (PMMA) particles with a very narrow size distribution was prepared by a two-stage method: the addition of a RAFT agent and a TPGDA agent to the system followed the nucleation stage. The particles had an average diameter within 1.9–2.7 μm and size distribution of 1.12–1.24. Molecular weight, molecular weight distribution, compositions and structure of copolymer were investigated by GPC and 1H NMR characterization. The GPC curves showed a bimodal distribution, indicating that MMA homopolymer was synthesised during the nucleation stage. In addition, 1H-NMR proved that MMA and TPGDA branched copolymer was synthesised after the nucleation stage. TPGDA fraction in the copolymer was lower than that in the initial monomer. It was determined that the intrinsic viscosity of the copolymer decreased with conversion and the Mark–Houwink exponent α of copolymer was reduced from 0.643 to 0.548, which further confirmed the branched structure of the copolymer.

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References

  1. Georges MK, Veregin RPN, Kazmaier PM, Hamer GK (1993) Narrow molecular weight resins by a free-radical polymerization process. Macromolecules 26:2987–2988

    Article  CAS  Google Scholar 

  2. Wang JS, Matyjaszewski K (1995) Controlled/“living” radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J Am Chem Soc 117:5614–5615

    Article  CAS  Google Scholar 

  3. Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition–fragmentation chain transfer: the RAFT process. Macromolecules 31:5559–5562

    Article  CAS  Google Scholar 

  4. Gabaston LI, Jackson RA, Armes SP (1998) Living free-radical dispersion polymerization of styrene. Macromolecules 31:2883–2888

    Article  CAS  Google Scholar 

  5. Hoelderle M, Baumert M, Muelhaupt R (1997) Comparison of controlled radical styrene polymerizations in bulk and nonaqueous dispersion. Macromolecules 30:3420–3422

    Article  CAS  Google Scholar 

  6. Shim SE, Jung H, Lee H, Biswas J, Choe S (2003) Living radical dispersion photopolymerization of styrene by a reversible addition–fragmentation chain transfer (RAFT) agent. Polymer 44:5563–5572

    Article  CAS  Google Scholar 

  7. Saikia PJ, Lee JM, Lee BH, Choe S (2007) Influence of a reversible addition–fragmentation chain transfer agent in the dispersion polymerization of styrene. J Polym Sci Polym Chem 45:348–360

    Article  CAS  Google Scholar 

  8. Lee JM, Lee BH, Choe S (2006) The effect of polystyrene-block-poly(4-vinylpyridine) prepared by a RAFT method in the dispersion polymerization of MMA. Polymer 47:3838–3844

    Article  CAS  Google Scholar 

  9. Song JS, Winnik MA (2006) Monodisperse, micron-sized reactive low molar mass polymer microspheres by two-stage living radical dispersion polymerization of styrene. Macromolecules 39:8318–8325

    Article  CAS  Google Scholar 

  10. Min K, Matyjaszewski K (2007) Atom transfer radical dispersion polymerization of styrene in ethanol. Macromolecules 40:7217–7222

    Article  CAS  Google Scholar 

  11. Wan WM, Pan CY (2007) Atom transfer radical dispersion polymerization in an ethanol/water Mixture. Macromolecules 40:8897–8905

    Article  CAS  Google Scholar 

  12. Fréchet JMJ, Henmi M, Gitsov I, Aoshima S, Leduc MR, Grubbs RB (1995) Self-condensing vinyl polymerization : an approach to dendritic materials. Science 269(5227):1080–1083

    Article  Google Scholar 

  13. Hawker CJ, Fréchet JMJ, Grubbs RB, Dao J (1995) Preparation of hyperbranched and star polymers by a “Living”, self-condensing free radical polymerization. J Am Chem Soc 117:10763–10764

    Article  CAS  Google Scholar 

  14. Weimer MW, Fréchet JMJ, Gitsov I (1998) Importance of active-site reactivity and reaction conditions in the preparation of hyperbranched polymers by self-condensing vinyl polymerization: highly branched vs. linear poly[4-(chloromethyl)styrene] by metal-catalyzed “living” radical polymerization. J Polym Sci Polym Chem 36:955–970

    Article  CAS  Google Scholar 

  15. Simon PFW, Radke W, Muller AHE (1997) Hyperbranched methacrylates by self-condensing group transfer polymerization. Macromol Rapid Chem 18:865–873

    Article  CAS  Google Scholar 

  16. Matyjasewski K, Gaynor SG, Muller AHE (1997) Preparation of hyperbranched polyacrylates by atom transfer radical polymerization. 2. Kinetics and mechanism of chain growth for the self-condensing vinyl polymerization of 2-((2-Bromopropionyl)oxy)ethyl acrylate. Macromolecules 30:7034–7041

    Article  Google Scholar 

  17. Matyjasewski K, Gaynor SG (1997) Preparation of hyperbranched polyacrylates by atom transfer radical polymerization. 3. Effect of reaction conditions on the self-condensing vinyl polymerization of 2-((2-Bromopropionyl)oxy)ethyl acrylate. Macromolecules 30:7042–7049

    Article  Google Scholar 

  18. O’Brien N, McKee A, Sherrington DC (2000) Facile, versatile and cost effective route to branched vinyl polymers. Polymer 41:6027–6031

    Article  Google Scholar 

  19. Slark AT, Sherrington DC, Titterton A, Martin IK (2003) Branched methacrylate copolymers from multifunctional comonomers: the effect of multifunctional monomer functionality on polymer architecture and properties. J Mater Chem 13:2711–2720

    Article  CAS  Google Scholar 

  20. Isaure F, Cormack PAG, Graham S, Sherrington DC, Armes SP, Bütün V (2004) Synthesis of branched poly(methyl methacrylate)s via controlled/living polymerisations exploiting ethylene glycol dimethacrylate as branching agent. Chem Commun (9):1138–1139

  21. Bannister I, Billingham NC, Armes SP, Rannard SP, Findlay P (2006) Development of branching in living radical copolymerization of vinyl and divinyl monomers. Macromolecules 39:7483–7492

    Article  CAS  Google Scholar 

  22. Liu BL, Kazlauciunas A, Guthrie JT, Perrier S (2005) One-pot hyperbranched polymer synthesis mediated by reversible addition fragmentation chain transfer (RAFT) polymerization. Macromolecules 38:2131–2136

    Article  CAS  Google Scholar 

  23. Vo CD, Rosselgong J, Armes SP, Billingham NC (2007) RAFT synthesis of branched acrylic copolymers. Macromolecules 40:7119–7125

    Article  CAS  Google Scholar 

  24. Rosselgong J, Armes SP, Barton W, Price D (2009) Observation of near-ideal behavior using raft polymerization. macromolecules, Articles ASAP (As Soon As Publishable), Publication Date (Web): June 25, 2009 (Article). doi:10.1021/ma900958a

  25. Rong R, You Y, Tao W (2007) Photoinitiated RAFT polymerization in the presence of trithiocarbonate. J Appl Polym Sci 105:398–404

    Article  Google Scholar 

  26. Lai TJ, Filla D, Shea R (2002) Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents. Macromolecules 35:6754–6756

    Article  CAS  Google Scholar 

  27. Kwak Y, Goto A, Fukuda T (2004) Rate retardation in reversible addition–fragmentation chain transfer (RAFT) polymerization: further evidence for cross-termination producing 3-arm star chain. Macromolecules 37:1219–1225

    Article  CAS  Google Scholar 

  28. Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW (1986) Uniform polymer particles by dispersion polymerization in alcohol. J Polym Sci Polym Chem 24:2995–3007

    Article  CAS  Google Scholar 

  29. Thomson B, Rudin A, Lajoie G (1996) Dispersion copolymerization of styrene and divinylbenzene. II. Effect of crosslinker on particle morphology. J Appl Polym Sci 59:2009–2028

    Article  CAS  Google Scholar 

  30. Song JS, Winnik MA (2005) Cross-linked, monodisperse, micron-sized polystyrene particles by two-stage dispersion polymerization. Macromolecules 38:8300–8307

    Article  CAS  Google Scholar 

  31. Costello PA, Martin IK, Slark AT, Sherrington DC, Titterton A (2002) Branched methacrylate copolymers from multifunctional monomers: chemical composition and physical architecture distributions. Polymer 43:245–254

    Article  CAS  Google Scholar 

  32. Brandrup J, Immergut EH (1975) Polymer handbook, 2nd edn. Wiley, New York

    Google Scholar 

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Correspondence to Rong Ran.

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Chen, Z., Wang, X., Su, J. et al. Branched methyl methacrylate copolymer particles prepared by RAFT dispersion polymerization. Polym. Bull. 64, 327–339 (2010). https://doi.org/10.1007/s00289-009-0143-y

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  • DOI: https://doi.org/10.1007/s00289-009-0143-y

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