Nitroxide-Mediated Polymerization of Styrene, Butyl Acrylate, or Methyl 
Methacrylate by Microflow Reactor Technology

Takahide Fukuyama; Yoshito Kajihara; Ilhyong Ryu; Armido Studer

doi:10.1055/s-0031-1290780

Synthesis, Table of Contents

Synthesis 2012; 44(16): 2555-2559
DOI: 10.1055/s-0031-1290780

special topic

Nitroxide-Mediated Polymerization of Styrene, Butyl Acrylate, or Methyl Methacrylate by Microflow Reactor Technology

Authors

Takahide Fukuyama

^aDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: +81(72)2549695 Email: ryu@c.s.osakafu-u.ac.jp
Yoshito Kajihara

^aDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: +81(72)2549695 Email: ryu@c.s.osakafu-u.ac.jp
Ilhyong Ryu*

^aDepartment of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Fax: +81(72)2549695 Email: ryu@c.s.osakafu-u.ac.jp
Armido Studer*

^bInstitute of Organic Chemistry and NRW Graduate School of Chemistry, University of Münster, Corrensstr. 40, 48149 Münster, Germany, Fax: +49(251)8336523 Email: studer@uni-muenster.de

Abstract

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Abstract

The nitroxide-mediated radical polymerization (NMP) of styrene and butyl acrylate in microflow tubular reactors was examined. In comparison with polymerizations conducted in a batch reactor under otherwise identical conditions, the microflow setup gave higher conversions and produced polymers with lower polydispersity indices. Block copolymers of the two monomers could be synthesized by connecting two microflow tubular reactors through a T-junction. The NMP of methyl methacrylate in a microflow tubular reactor was also investigated.

Key words

polymers - radical reactions - flow reactors - microfluidics

Full Text

References

References

1a Microreactors in Organic Synthesis and Catalysis. Wirth T. Wiley-VCH; Weinheim: 2008
1b Micro Process Engineering: A Comprehensive Handbook . Vols. 1–3. Hessel V, Renken A, Schouten JC, Yoshida J. Wiley-VCH; Weinheim: 2009
1c Ahmed-Omer B, Brandt JC, Wirth T. Org. Biomol. Chem. 2007; 5: 733
1d Watts P, Wiles C. Chem. Commun. (Cambridge) 2007; 443
1e Mason BP, Price KE, Steinbacher JL, Bogdan AR, McQuade DT. Chem. Rev. 2007; 107: 2300
1f McMullen JP, Jensen KF. Annu. Rev. Anal. Chem. 2010; 3: 19
1g Webb D, Jamison TF. Chem. Sci. 2010; 1: 675
1h Yoshida J.-i. Chem. Rec. 2010; 10: 332
1i Wegner J, Ceylan S, Kirschning A. Chem. Commun. (Cambridge) 2011; 47: 4583

2 For a review, see: Fukuyama T, Rahman MT, Sato M, Ryu I. Synlett 2008; 151

For our recent work using a microreactor, see:
3a Fukuyama T, Shinmen M, Nishitani S, Sato M, Ryu I. Org. Lett. 2002; 4: 1691
3b Liu S, Fukuyama T, Sato M, Ryu I. Org. Process Res. Dev. 2004; 8: 477
3c Rahman MT, Fukuyama T, Kamata N, Sato M, Ryu I. Chem. Commun. (Cambridge) 2006; 2236
3d Fukuyama T, Kippo T, Ryu I, Sagae T. Res. Chem. Intermed. 2009; 35: 1053
3e Min K.-I, Lee T.-H, Park CP, Wu Z.-Y, Girault HH, Ryu I, Fukuyama T, Mukai YD.-P. Kim. Angew. Chem. Int. Ed. 2010; 49: 7063
3f Tsutsumi K, Terao K, Yamaguchi H, Yoshimura S, Morimoto T, Kakiuchi K, Fukuyama T, Ryu I. Chem. Lett. 2010; 39: 828
3g Fukuyama T, Mukai Y, Ryu I. Beilstein J. Org. Chem. 2011; 7: 1288
3h Fukuyama T, Kajihara Y, Hino Y, Ryu I. J. Flow Chem. 2011; 1: 40

For radical reactions using a microreactor, see:
4a Sugimoto A, Sumino Y, Takagi M, Fukuyama T, Ryu I. Tetrahedron Lett. 2006; 47: 6197
4b Fukuyama T, Kobayashi M, Rahman MT, Kamata N, Ryu I. Org. Lett. 2008; 10: 533
4c Sugimoto A, Fukuyama T, Sumino Y, Takagi M, Ryu I. Tetrahedron 2009; 65: 1593
4d Wienhöfer IC, Studer A, Rahman MT, Fukuyama T, Ryu I. Org. Lett. 2009; 11: 2457
4e Fukuyama T, Rahman MT, Kamata N, Ryu I. Beilstein J. Org. Chem. 2009; 5: 34
4f Matsubara H, Hino Y, Tokizane M, Ryu I. Chem. Eng. J. (Amsterdam, Neth.) 2011; 167: 567
4g Odedra A, Geyer K, Gustafsson T, Gilmour R, Seeberger PH. Chem. Commun. (Cambridge) 2008; 3025

For reviews, see:
5a Steinbacher JL, McQuade DT. J. Polym. Sci., Part A: Polym. Chem. 2006; 44: 6505
5b Wilms D, Klos J, Frey H. Macromol. Chem. Phys. 2008; 209: 343
5c Bally F, Serra CA, Hessel V, Hadziioannou G. Macromol. React. Eng. 2010; 4: 543

6a Matyjaszewski K, Xia J. Chem. Rev. 2001; 101: 2921
6b Kamigaito M, Ando T, Sawamoto M. Chem. Rev. 2001; 101: 3689
6c Tsarevsky NV, Matyjaszewski K. Chem. Rev. 2007; 107: 2270
6d Ouchi M, Terashima T, Sawamoto M. Acc. Chem. Res. 2008; 41: 1120

7a Barner-Kowollik C, Davis TP, Heuts JP. A, Stenzel MH, Vana P, Whittaker M. J. Polym. Sci., Part A: Polym. Chem. 2003; 41: 365
7b Favier A, Charreyre M.-T. Macromol. Rapid Commun. 2006; 27: 653
7c Barner-Kowollik C, Perrier S. J. Polym. Sci., Part A: Polym. Chem. 2008; 46: 5715
7d Moad G, Rizzardo E, Thang SH. Acc. Chem. Res. 2008; 41: 1133

8 David G, Boyer C, Tonnar J, Ameduri B, Lacroix-Desmazes P, Boutevin B. Chem. Rev. 2006; 106: 3936
9 Yamago S. Chem. Rev. 2009; 109: 5051
10 Poli R. Angew. Chem. Int. Ed. 2006; 45: 5058

11a Hawker CJ, Bosman AW, Harth E. Chem. Rev. 2001; 101: 3661
11b Studer A. Chem. Soc. Rev. 2004; 33: 267
11c Studer A, Schulte T. Chem. Rec. 2005; 5: 27
11d Sciannamea V, Jérôme R, Detrembleur C. Chem. Rev. 2008; 108: 1104
11e Grubbs RB. Polym. Rev. 2011; 51: 104
11f Tebben L, Studer A. Angew. Chem. Int. Ed. 2011; 50: 5034

12a Iwasaki T, Yoshida J.-i. Macromolecules 2005; 38: 1159
12b Iwasaki T, Kawano N, Yoshida J.-i. Org. Process Res. Dev. 2006; 10: 1126

13a Wu T, Mei Y, Cabral JT, Xu C, Beers KL. J. Am. Chem. Soc. 2004; 126: 9880
13b Xu C, Wu T, Drain CM, Batteas JD, Beers KL. Macromolecules 2005; 38: 6

14a Russum JP, Jones CW, Schork FJ. Macromol. Rapid Commun. 2004; 25: 1064
14b Diehl C, Laurino P, Azzouz N, Seeberger PH. Macromolecules 2010; 43: 10311
14c Hornung CH, Guerrero-Sanchez C, Brasholz M, Saubern S, Chiefari J, Moad G, Rizzardo E, Thang SH. Org. Process Res. Dev. 2011; 15: 593

15a Enright TE, Cunningham MF, Keoshkerian B. Macromol. Rapid Commun. 2005; 26: 221
15b Rosenfeld C, Serra C, Brochon C, Hessel V, Hadziioannou G. Chem. Eng. Sci. 2007; 62: 5245
15c Rosenfeld C, Serra C, Brochon C, Hadziioannou G. Chem. Eng. J. (Amsterdam, Neth.) 2008; 135: S242
15d Enright TE, Cunningham MF, Keoshkerian B. Macromol. React. Eng. 2010; 4: 186
15e Zitlalpopoca-Soriano AG, Vivaldo-Lima E, Flores-Tlacuahuac A. Macromol. React. Eng. 2010; 4: 516
15f Zitlalpopoca-Soriano AG, Vivaldo-Lima E, Flores-Tlacuahuac A. Macromol. React. Eng. 2010; 4: 599

16a Charleux B, Nicolas J, Guerret O. Macromolecules 2005; 38: 5485
16b Nicolas J, Dire C, Mueller L, Belleney J, Charleux B, Marque SR. A, Bertin D, Magnet S, Couvreur L. Macromolecules 2006; 39: 8274
16c Dire C, Charleux B, Magnet S, Couvreur L. Macromolecules 2007; 40: 1897

17 Miele S, Nesvadba P, Studer A. Macromolecules 2009; 42: 2419

For other highly sterically hindered 2,2,6,6-tetraethyl-piperidine-N-oxyl regulators, see:
18a Knoop CA, Studer A. J. Am. Chem. Soc. 2003; 125: 16327
18b Wetter C, Gierlich J, Knoop CA, Müller C, Schulte T, Studer A. Chem. Eur. J. 2004; 10: 1156
18c Siegenthaler KO, Studer A. Macromolecules 2006; 39: 1347
18d Chang C.-C, Studer A. Macromolecules 2006; 39: 4062