Fast RAFT aqueous polymerization in a continuous tubular reactor: consecutive synthesis of a double hydrophilic block copolymer

作者: Zhen Li , Weijie Chen , Lifen Zhang , Zhenping Cheng , Xiulin Zhu

DOI: 10.1039/C5PY00847F

关键词: Polymer chemistryLiving polymerizationEnd-groupPolymerizationChain transferChain-growth polymerizationPrecipitation polymerizationChemistryReversible addition−fragmentation chain-transfer polymerizationCopolymer

摘要: In this work, double hydrophilic diblock copolymer poly(3-sulfopropyl methacrylate potassium salt)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (PSPMA-b-PPEGMA) was successfully synthesized via a fast reversible addition–fragmentation chain transfer (RAFT) polymerization at 70 °C in continuous tubular reactor water without handling the intermediate macro-RAFT agent. An extremely high conversion reached relatively short time (less than 2 h). 4-Cyano-4-(thiobenzoylthio)pentanoic acid (CTBCOOH) used as agent and 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIBI) initiator. Typical “living”/controlled characteristics of system were demonstrated: first-order kinetics, linear increase molecular weight with monomer conversion, narrow distribution for resultant polymer. 1H NMR spectroscopy chain-extension experiments confirmed attachment “livingness” RAFT terminal group obtained polymer ends.

参考文章(32)
Andreas Kirschning, Wladimir Solodenko, Klaas Mennecke, Combining enabling techniques in organic synthesis: continuous flow processes with heterogenized catalysts. Chemistry: A European Journal. ,vol. 12, pp. 5972- 5990 ,(2006) , 10.1002/CHEM.200600236
Christian H. Hornung, Xuan Nguyen, Stella Kyi, John Chiefari, Simon Saubern, Synthesis of RAFT Block Copolymers in a Multi-Stage Continuous Flow Process Inside a Tubular Reactor Australian Journal of Chemistry. ,vol. 66, pp. 192- 198 ,(2013) , 10.1071/CH12479
Nicky Chan, Michael F. Cunningham, Robin A. Hutchinson, Continuous controlled radical polymerization of methyl acrylate with copper wire in a CSTR Polymer Chemistry. ,vol. 3, pp. 486- 497 ,(2012) , 10.1039/C2PY00509C
Peter J. Dowding, James W. Goodwin, Brian Vincent, Production of porous suspension polymer beads with a narrow size distribution using a cross-flow membrane and a continuous tubular reactor Colloids and Surfaces A: Physicochemical and Engineering Aspects. ,vol. 180, pp. 301- 309 ,(2001) , 10.1016/S0927-7757(00)00777-9
James P. Russum, Christopher W. Jones, F. Joseph Schork, Continuous Reversible Addition-Fragmentation Chain Transfer Polymerization in Miniemulsion Utilizing a Multi-Tube Reaction System Macromolecular Rapid Communications. ,vol. 25, pp. 1064- 1068 ,(2004) , 10.1002/MARC.200400086
Youqing Shen, Shiping Zhu, Faquan Zeng, Robert H. Pelton, Atom Transfer Radical Polymerization of Methyl Methacrylate by Silica Gel Supported Copper Bromide/Multidentate Amine Macromolecules. ,vol. 33, pp. 5427- 5431 ,(2000) , 10.1021/MA000277J
F. Joseph Schork, Juchen Guo, Continuous Miniemulsion Polymerization Macromolecular Reaction Engineering. ,vol. 2, pp. 287- 303 ,(2008) , 10.1002/MREN.200800003
Joke Vandenbergh, Thales de Moraes Ogawa, Thomas Junkers, Precision synthesis of acrylate multiblock copolymers from consecutive microreactor RAFT polymerizations Journal of Polymer Science Part A. ,vol. 51, pp. 2366- 2374 ,(2013) , 10.1002/POLA.26593
Yosiharu Simamura, Masayoshi Okubo, Kunio Kataoka, Naoto Ohmura, Masato Kouzu, Emulsion polymerization of styrene in a continuous Taylor vortex flow reactor Chemical Engineering Science. ,vol. 50, pp. 1409- 1416 ,(1995) , 10.1016/0009-2509(94)00515-S