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Synthesis of RAFT Block Copolymers in a Multi-Stage Continuous Flow Process Inside a Tubular Reactor

Christian H. Hornung A , Xuan Nguyen A , Stella Kyi A , John Chiefari A and Simon Saubern A B
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A CSIRO Materials Science & Engineering, Bag 10, Clayton South, Vic. 3169, Australia.

B Corresponding author. Email: simon.saubern@csiro.au

Australian Journal of Chemistry 66(2) 192-198 https://doi.org/10.1071/CH12479
Submitted: 19 October 2012  Accepted: 19 November 2012   Published: 11 December 2012

Abstract

This work describes a multi-stage continuous flow polymerisation process for the synthesis of block copolymers using the RAFT polymerization method. The process retains all the benefits and versatility of the RAFT method and has been adapted for a series of monomer combinations, including acrylates, acrylamides, and vinyl monomers. It resulted in polymers with molecular weights between 13500 and 34100 g mol–1, and dispersities typically between 1.21 and 1.58. Different architectures were prepared (including combinations of hydrophilic and hydrophobic blocks) which are soluble in a range of different solvents including aqueous and organic media.


References

[1]  J. Chiefari, Y. K. Chong, F. Ercole, J. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1998, 31, 5559.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXkvF2gs7k%3D&md5=7b317daf025894dcec376159155980ccCAS |

[2]  G. Moad, E. Rizzardo, S. H. Thang, Aust. J. Chem. 2005, 58, 379.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXltFymsL4%3D&md5=0464d702bb4d20d3f965209912e5cd9bCAS |

[3]  G. Moad, E. Rizzardo, S. H. Thang, Aust. J. Chem. 2006, 59, 669.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtFeqsr%2FM&md5=dbce39d0fb32872e6e9f9a55bde54681CAS |

[4]  G. Moad, E. Rizzardo, S. H. Thang, Aust. J. Chem. 2009, 62, 1402.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVers7bN&md5=fb2b73394696eb457b81af596f1722b8CAS |

[5]  G. Moad, E. Rizzardo, S. H. Thang, Aust. J. Chem. 2012, 65, 985.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtlWmu7%2FE&md5=395563a0a036624e8e9e399973caa44fCAS |

[6]  Y. K. Chong, T. P. T. Le, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1999, 32, 2071.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXht1art7k%3D&md5=572bd1689174c866b88fb2929cb7571dCAS |

[7]  J. F. Quinn, R. P. Chaplin, T. P. Davis, J. Polym. Sci. Pol. Chem. 2002, 40, 2956.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38Xmt12hu7k%3D&md5=d44f65f4d9e70edffc309b9be9d18175CAS |

[8]  A. W. York, S. E. Kirkland, C. L. McCormick, Adv. Drug Deliv. Rev. 2008, 60, 1018.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmtVWku7c%3D&md5=7ff9664561b46bc2011bc1899224b0b0CAS |

[9]  Y. Mitsukami, M. S. Donovan, A. B. Lowe, C. L. McCormick, Macromolecules 2001, 34, 2248.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXhtFymtLw%3D&md5=7644c7e7f71fc2d3a1dd0618eb5e4c8dCAS |

[10]  C. M. Schilli, M. Zhang, E. Rizzardo, S. H. Thang, Y. K. Chong, K. Edwards, G. Karlsson, A. H. E. Müller, Macromolecules 2004, 37, 7861.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXns12qs78%3D&md5=cf645d2e14bf2216852e324f58d3e21cCAS |

[11]  M. H. Stenzel, C. Barner-Kowollik, T. P. Davis, H. M. Dalton, Macromol. Biosci. 2004, 4, 445.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXjslWrsb0%3D&md5=4a7108e6442bb2aa3b89c668b5461476CAS |

[12]  D. Quémener, T. P. Davis, C. Barner-Kowollik, M. H. Stenzel, Chem. Commun. 2006, 5051.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  D. Roy, A. Ullah, B. S. Sumerlin, Macromolecules 2009, 42, 7701.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXht1SnsbvM&md5=31bddc083171b846c91b1295072e6c75CAS |

[14]  Micro Process Engineering: A Comprehensive Handbook (Eds V. Hessel, A. Renken, J. C. Schouten, J. Yoshida) 2009 (Wiley-VCH: Weinheim).

[15]  T. Wirth, Microreactors in Organic Synthesis and Catalysis 2008 (Wiley-VCH: Weinheim).

[16]  W. Ehrfeld, V. Hessel, H. Löwe, Microreactors: New Technology for Modern Chemistry 2000 (Wiley-VCH: Weinheim).

[17]  M. Baumann, I. R. Baxendale, S. V. Ley, Mol. Divers. 2011, 15, 613.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXpt1Cqtbo%3D&md5=00699e25c681cee3f6b9e4ac048903c0CAS |

[18]  R. L. Hartman, J. P. McMullen, K. F. Jensen, Angew. Chem. Int. Ed. 2011, 50, 7502.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXotVCns74%3D&md5=3b906f6c72f5fa042dfc75f84f4226b2CAS |

[19]  F. E. Valera, M. Quaranta, A. Moran, J. Blacker, A. Armstrong, J. T. Cabral, D. G. Blackmond, Angew. Chem. Int. Ed. 2010, 49, 2478.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXktVajsLk%3D&md5=1fcfd6beb62982b87b09953e68eaf40dCAS |

[20]  S. V. Ley, I. R. Baxendale, Chimia (Aarau) 2008, 62, 162.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXltFGiu7c%3D&md5=2b1fe75e6f0e274c9c45e4fe163ffb84CAS |

[21]  B. P. Mason, K. E. Price, J. L. Steinbacher, A. R. Bogdan, D. T. McQuade, Chem. Rev. 2007, 107, 2300.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXjtF2msr0%3D&md5=61920aa9737ff27dfaee69fe54945546CAS |

[22]  T. Iwasaki, N. Kawano, J. Yoshida, Org. Process Res. Dev. 2006, 10, 1126.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XpsF2hs7c%3D&md5=dd37d5551b5a8485f534af2f7ce9de58CAS |

[23]  C. Rosenfeld, C. Serra, C. Brochon, G. Hadziioannou, Chem. Eng. Sci. 2007, 62, 5245.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXpsFOltLg%3D&md5=a24b693c719ba523166098cafcec9444CAS |

[24]  N. Chan, S. Boutti, M. F. Cunningham, R. Hutchinson, Macromol. React. Eng. 2009, 3, 222.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXpt1emu78%3D&md5=a79c10914799fd6515ceee7b88dacff0CAS |

[25]  N. Chan, M. F. Cunningham, R. Hutchinson, Polym. Chem. 2012, 3, 1322.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XkvV2nsbo%3D&md5=a0f6a0606a1a429048c09d0a46651c75CAS |

[26]  T. Fukuyama, Y. Kajihara, I. Ryu, A. Studer, Synthesis 2012, 44, 2555.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhsFaksLvL&md5=61052f787594af9752f242813dd306aeCAS |

[27]  W. W. Smulders, C. W. Jones, F. J. Schork, Macromolecules 2004, 37, 9345.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXpvVGgtL8%3D&md5=180abb9b257cc026b060d1040a822f87CAS |

[28]  R. M. Paulus, T. Erdmenger, C. R. Becer, R. Hoogenboom, U. S. Schubert, Macromol. Rapid Commun. 2007, 28, 484.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXjsFCmtbg%3D&md5=5207391468c181c841d81e4b39ff3583CAS |

[29]  J. Vandenbergh, T. Junkers, Polym. Chem. 2012, 3, 2739.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xht1yksrvL&md5=05c71391ca1534e05b8e13b0d549b933CAS |

[30]  J. Chiefari, C. H. Hornung, S. Saubern, Continuous Flow Polymerisation Process, 2010, WO2012037596, 2010–09–22.

[31]  C. H. Hornung, C. Guerrero-Sanchez, M. Brasholz, S. Saubern, J. Chiefari, G. Moad, E. Rizzardo, S. H. Thang, Org. Process Res. Dev. 2011, 15, 593.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXivFygs7w%3D&md5=15ca10d5c3401d3e38eac3e61c9cc890CAS |

[32]  C. H. Hornung, A. Postma, S. Saubern, J. Chiefari, Macromol. React. Eng. 2012, 6, 246.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XovFWluro%3D&md5=f0d5b50d1c9c6bc6d98b01c67f243450CAS |

[33]  C. H. Hornung, X. Nguyen, G. Dumsday, S. Saubern, Macromol. React. Eng. 2012, 6, 458.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xhtlahsr%2FN&md5=9df96524f253a159f4644606009d5cb2CAS |

[34]  C. H. Hornung, M. R. Mackley, Chem. Eng. Sci. 2009, 64, 3889.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXptVGhs7w%3D&md5=f2b81aeebea7dc4516d18c0db24332c8CAS |

[35]  S. H. Thang, Y. K. Chong, R. Mayadunne, G. Moad, E. Rizzardo, Tetrahedron Lett. 1999, 40, 2435.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXhvVeksL0%3D&md5=d6ba9c2ba52321df7b4d1a14103f5ac9CAS |

[36]  Vapourtec Ltd2012 , http://www.vapourtec.co.uk/home

[37]  J. Chiefari, J. Jeffery, R. T. A. Mayadunne, G. Moad, E. Rizzardo, S. H. Thang, Macromolecules 1999, 32, 7700.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXmtlClurk%3D&md5=f526439839ebc12895f1ec063680897dCAS |

[38]  Y. K. Chong, J. Krstina, T. P. T. Le, G. Moad, A. Postma, E. Rizzardo, S. H. Thang, Macromolecules 2003, 36, 2256.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXitVemuro%3D&md5=be1b7c9c3c7f9a31c2251b589d41e6e5CAS |

[39]  G. Moad, R. T. A. Mayadunne, E. Rizzardo, M. Skidmore, S. H. Thang, ACS Symp. Ser. 2003, 854, 520.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXlslWmsrk%3D&md5=c89ab899be5e8f9a65e1251b6adb3f6dCAS |

[40]  A. Postma, T. P. Davis, G. Li, G. Moad, M. S. O’Shea, Macromolecules 2006, 39, 5307.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xms1Kntbw%3D&md5=0f8b8d319007360f4688c28a49bf2450CAS |

[41]  C. H. Hornung, K. von Känel, S. Kyi, X. Nguyen, A. Postma, S. Saubern, J. Chiefari, RAFT Polymerization and Post-Processing Using a Multi-Stage Continuous Flow Approach, in Proceedings of the 33rd Australasian Polymer Symposium 2012, Hobart, Australia.

[42]  C. H. Hornung, K. von Känel, S. Kyi, X. Nguyen, A. Postma, S. Saubern, J. Chiefari, Sequential Continuous Flow Polymerization for the Synthesis of RAFT Block Copolymers, in Proceedings of Polymer Reaction Engineering VIII 2012, Cancun, Mexico.