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Received February 2, 2014
Accepted April 29, 2014
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This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits
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Reversible addition-fragmentation chain transfer polymerization of vinyl acetate and vinyl pivalate in supercritical carbon dioxide
1School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749, Korea 2Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang, Vietnam 3Daegu Regional Environmental Office, Ministry of Environment, Government Complex, Hwaam-ro, Dalseo-gu, Daegu 704-841, Korea
Korean Journal of Chemical Engineering, November 2014, 31(11),
10.1007/s11814-014-0129-9
10.1007/s11814-014-0129-9
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Abstract
Two highly supercritical CO2-soluble, poly(vinyl acetate) (PVAc)-based macro-reversible addition-fragmentation chain transfer (RAFT) agents were synthesized. The RAFT agents were used for the first time in RAFT/macromolecular design via the interchange of xanthates (MADIX) and polymerization of vinyl acetate (VAc) and vinyl pivalate (VPi) in supercritical carbon dioxide (scCO2). A homopolymer PVAc and a block copolymer PVAc-b-PVPi made by RAFT/MADIX polymerization were characterized, and the effects of time and RAFT agents on polymerization_x000D_
were examined. For the 8.4 wt% RAFT agent in VAc, the molecular mass (Mn) of homopolymer PVAc was 26,000 g mol^(-1) and PDI was 1.35. For the copolymerization of VPi using 9.8 wt% PVAc-RAFT agent in VPi for 24 h, the Mn and PDI of PVAc-b-PVPi reached 32,400 g mol^(-1) and 1.42, respectively. These results suggest that the polydispersity can be controlled during the clean production of PVAc and PVPi by RAFT/MADIX polymerization in scCO2.
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References
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Cooper AI, J. Mater. Chem., 10, 207 (2000)
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McHale R, Aldabbagh F, Zetterlund PB, Minami H, Okubo M, Macromolecules, 39(20), 6853 (2006)
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Minami H, Kagawa Y, Kuwahara S, Shigematsu J, Fujii S, Okubo M, Des. Monomers Polym., 7, 553 (2004)
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Benaglia M, Chen M, Chong YK, Moad G, Rizzardo E, Thang SH, Macromolecules, 42(24), 9384 (2009)
Gody G, Maschmeyer T, Zetterlund PB, Perrier S, Nat. Commun., DOI:10.1038/ncomms3505. (2013)
Wong KH, Davis TP, Bamer-Kowollik C, Stenzel MH, Polymer, 48(17), 4950 (2007)
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Repollet-Pedrosa MH, Weber RL, Schmitt AL, Mahanthappa MK, Macromolecules, 43(19), 7900 (2010)
Lipscomb CE, Mahanthappa MK, Macromolecules, 42(13), 4571 (2009)
Stenzel MH, Cummins L, Roberts GE, Thomas PD, Vana P, Barner-Kowollik C, Macromol. Chem. Phys., 204, 1160 (2003)
Barner-Kowollik C, Handbook of RAFT polymerization, Wiley-VCH, Weinheim (2008)
Destarac M, Charmot D, Franck X, Zard SZ, Macromol. Rapid Commun., 21(15), 1035 (2000)
Lee H, Pack JW, Wang WX, Thurecht KJ, Howdle SM, Macromolecules, 43(5), 2276 (2010)
Girard E, Tassaing T, Marty JD, Destarac M, Polym. Chem., 2, 2222 (2011)
Girard E, Tassaing T, Camy S, Condoret JS, Marty JD, Destarac M, J. Am. Chem. Soc., 134(29), 11920 (2012)
Girard E, Tassaing T, Ladaviere C, Marty JD, Destarac M, Macromolecules, 45(24), 9674 (2012)
Moad G, Rizzardo E, Thang SH, Aust. J. Chem., 58, 379 (2005)
Canelas DA, Betts DE, DeSimone JM, Yates MZ, Johnston KP, Macromolecules, 31(20), 6794 (1998)
Shen Z, McHugh MA, Xu J, Belardi J, Kilic S, Mesiano A, Bane S, Karnikas C, Beckman E, Enick R, Polymer, 44(5), 1491 (2003)
Raveendran P, Wallen SL, J. Am. Chem. Soc., 124(25), 7274 (2002)
Lee H, Terry E, Zong M, Arrowsmith N, Perrier S, Thurecht KJ, Howdle SM, J. Am. Chem. Soc., 130(37), 12242 (2008)
Bamford CH, Dyson RW, Eastmond GC, Polymer, 10, 885 (1969)
Guan Z, Combes JR, Menceloglu YZ, Desimone JM, Macromolecules, 26, 2663 (1993)
Simms RW, Davis TP, Cunningham MF, Macromol. Rapid Commun., 26(8), 592 (2005)
Russum JP, Barbre ND, Jones CW, Schork FJ, J. Polym. Sci. A: Polym. Chem., 43(10), 2188 (2005)
Pham QL, Nguyen VH, Haldorai Y, Shim JJ, Korean J. Chem. Eng., 30(5), 1153 (2013)
