Abstract
Rigid methacrylate-based and acrylamide-based polymer monoliths with well-defined macropores have been synthesized from different monomers by organotellurium-mediated living radical polymerization (TERP) accompanied by phase separation. Glycerol 1,3-dimethacrylate (GDMA), trimethylolpropane trimethacrylate (Trim), and N,N-methylenebis(acrylamide) (BIS) were used as monomers. In each system, poly(ethylene oxide) (PEO) effectively induced spinodal decomposition with the progress of polymerization. The resultant polymer monoliths possessed macropores with narrow size distributions and the macropore size can be controlled simply by varying the amount of PEO. Starting from GDMA and BIS, polymer monoliths with unimodal macropores can be obtained due to the collapse of micro- and mesopores, which were originally embedded in macropore skeletons, by large shrinkage during drying. In contrast, starting from Trim, the obtained polymer monoliths included not only macropores but also micro- and mesopores, which led to high specific surface area (470 m2 g−1), owing to the higher crosslinking density.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Peters EC, Svec F, Fréchet JMJ (1999) Rigid macroporous polymer monoliths. Adv Mater 11:1169–1181. doi:10.1002/(SICI)1521-4095(199910)11:14<1169:AID-ADMA1169>3.0.CO;2-6
Svec F, Fréchet JMJ (1996) Science 273:205–211. doi:10.1126/science.273.5272.205
Courtois J, Fischer G, Sellergren B, Irgum K (2006) Molecularly imprinted polymers grafted to flow through poly(trimethylolpropane trimethacrylate) monoliths for capillary-based solid phase extraction. J Chromatogr A 1109:92–99. doi:10.1016/j.chroma.2005.12.014
Zou H, Huang X, Ye M, Luo Q (2002) Monolithic stationary phases for liquid chromatography and capillary electrochromatography. J Chromatogr A 954:5–32. doi:10.1016/S0021-9673(02)00072-9
Aoki H, Tanaka N, Kubo T, Hosoya K (2008) Poly(glycerin 1,3-dimethacrylate)-based monolith with a bicontinuous structure tailored as HPLC column by photoinitiated in situ radical polymerization via viscoelastic phase separation. J Polym Sci A Polym Chem 46:4651–4673. doi:10.1002/pola.22786
Xie S, Svec F, Fréchet JMJ (1997) Rigid porous polyacrylamide-based monolithic columns containing butyl methacrylate as a separation medium for the rapid hydrophobic interaction chromatography of proteins. J Chromatogr A 775:65–72. doi:10.1016/S0021-9673(97)00254-9
Zeng CM, Liao JL, Nakazato K, Hjertén S (1996) Hydrophobic-interaction chromatography of proteins on continuous beds derivatized with isopropyl groups. J Chromatogr A 753:227–234. doi:10.1016/S0021-9673(96)00550-X
Hogger D, Freitag R (2001) Acrylamide-based monoliths as robust stationary phases for capillary electrochromatography. J Chromatogr A 914:211–222. doi:10.1016/S0021-9673(00)01119-5
Pliva FM, Andersson J, Galaev IY, Mattiasson B (2004) Characterization of polyacrylamide based monolithic columns. J Sep Sci 27:828–836. doi:10.1002/jssc.200401836
Zhu G, Yuan H, Zhao P, Zhang L, Liang Z, Zhang W, Zhang Y (2006) Macroporous polyacrylamide-based monolithic columns with immobilized pH gradient for protein analysis. Electrophoresis 27:3578–3583. doi:10.1002/elps.200600189
Tokudome Y, Fujita K, Nakanishi K, Miura K, Hirao K (2007) Synthesis of monolithic Al2O3 with well-defined macropores and mesostructured skeletons via the sol-gel process accompanied by phase separation. Chem Mater 19:3393–3398. doi:10.1021/cm063051p
Goto A, Kwak Y, Fukuda T, Yamago S, Iida K, Nakajima M, Yoshida J (2003) Mechanism-based invention of high-speed living radical polymerization using organotellurium compounds and azo-initiators. J Am Chem Soc 125:8720–8721. doi:10.1021/ja035464m
Kanamori K, Hasegawa J, Nakanishi K, Hanada T (2008) Facile synthesis of macroporous cross-linked methacrylate gels by atom transfer radical polymerization. Macromolecules 41:7186–7193. doi:10.1021/ma800563p
Kanamori K, Nakanishi K, Hanada T (2006) Rigid macroporous poly(divinylbenzene) monoliths with a well-defined bicontinuous morphology prepared by living radical polymerization. Adv Mater 18:2407–2411. doi:10.1002/adma.200601026
Hasegawa J, Kanamori K, Nakanishi K, Hanada T, Yamago S (2009) Pore formation in poly(divinylbenzene) networks derived from organotellurium-mediated living radical polymerization. Macromolecules 42:1270–1277. doi:10.1021/ma802343a
Rezwan K, Chen QZ, Blaker JJ, Boccaccini AR (2006) Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering. Biomaterials 27:3413–3431. doi:10.1016/j.biomaterials.2006.01.039
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2013 Springer Japan
About this chapter
Cite this chapter
Hasegawa, G. (2013). Extension of Living Radical Polymerization Accompanied by Phase Separation to Methacrylate- and Acrylamide-based Polymer Monoliths. In: Studies on Porous Monolithic Materials Prepared via Sol–Gel Processes. Springer Theses. Springer, Tokyo. https://doi.org/10.1007/978-4-431-54198-1_3
Download citation
DOI: https://doi.org/10.1007/978-4-431-54198-1_3
Published:
Publisher Name: Springer, Tokyo
Print ISBN: 978-4-431-54197-4
Online ISBN: 978-4-431-54198-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)