Photonic crystals in biology

Poster Session, Tuesday, June 15
Theme A1 - B702
Interlamellar Controlled/Living Radical Copolymerization of
Maleic Anhydride and Itaconic Acid with Butylmethactylate
Via Preintercalated RAFT-Agent/Organoclays Complexes
Zakir M. O. Rzayev, Ernur A. Söylemez,
Department of Chemical Engineering, Faculty of Engineering, Hacettepe University, Beytepe, 06800 Ankara, Turkey
Abstract– We have developed a new approach for the synthesis of polymer nanocomposites using a bifunctional reversible addition-fragmentation chain transfer
(RAFT) agent, two types of organo-montmorillonites, such as a non-reactive dimethyldodecyl ammonium (DMDA)-MMT and a reactive octadecyl amine (ODA)-
MMT organo-clays), and a radical initiator. This simple and versatile method can be applied to a wide range of monomers and donor-acceptor type
monomer/comonomer systems for the preparation of completely exfoliated nanoarchitectures for high performance engineering nanomaterial applications.
In the last years, many researchers attempt to utilize the
controlled/living polymerization methods [1-6] for the preparation of
the polymer/silicate nanocomposites. Of the methods used in the
preparation of polymer-silicate nanocomposites, in situ polymerization
offers the ability to impart significant control over both the polymer
architecture and the final structure of the composite. The
polymer/silicate nanocomposites, with well-dispersed (exfoliated)
silicate layers, can be produced using atom transfer radical
polymerization (ATRP) and nitroxide-mediated polymerization (NMP)
methods. The interlamellar controlled/living radical (co)polymerization
of monomers using reversible addition-fragmentation chain transfer
(RAFT) technique in the presence of mineral clay has been scarcely
investigated. It is known that RAFT polymerization method does not
rely on a metal catalyst and can polymerize a wide range of monomers,
theoretically all those monomers that can polymerize via a radical
intermediate.
In this work, we have been described our preliminary results on
synthesis and characterization of new RAFT...O-MMT complexes as
the reactive RAFT-nanofillers and their utilization in the interlamellar
controlled/living complex-radical copolymerization of MA and IA with
BMA as a internal plastisization agent in-situ processing to prepare
new generation of polymer nanocomposites with complete exfoliated
nanoarchitectures, lower (2.5 wt. %) and controlled content of organo-
MMT, molecular weight, and polydispersity of matrix-polymer chains.
Synthetic partways of these pre-intercalated complexes and functional
copolymer/organo-clay nanosystems can be represented as follows:
Figure 1. SEM images (scale: 1 m at x1000 magnification) of (a) MA and
(b) IA containing nanosystems prepared by controlled/living radical RAFT
copolymerization in the presence of RAFT...O-MMT complexes.
Figure 2. TEM images of (a) MA and (b) IA-containing nanocomposites.
SEM and TEM images of synthesized nanocomposites were illustrated in
Figures 1 and 2. In the case of reactive organoclay (ODA-MMT), relative fine
distributed morphology was observed. As seen from these images, the dispersed
phase significantly reduced in the IA containing nanosystem and in the nanocomposites
prepared with RAFT…ODA-MMT complex. This observed fact can
be explained by chemical in situ processing through amine/anhydride (or acid)
reactions which are carried out in nano scale between silicate galleries.
We have developed a facile and effective strategy for the design and synthesis
of polymer/organo-silicate nanoarchitectures by an interlamellar complexradical
RAFT copolymerization method. Unlike the known methods , the novel
approach involves the use of physically and chemically modified and intercalated
RAFT/organo-MMT nanofillers in interlamellar complex-radical copolymerizations
of functional monomer systems and synthesis of well exfoliated
polymer/silicate layered nanocomposites with a relatively low concentration of
organo-MMT (2.5-5.0 wt. %) and high performance thermal and mechanical
properties. This strategy can also be broadly utilized to other hydrophilic/
hydrophobic polymer/silicate hybrid nanomaterials.
Scheme: Complex-radical interlamellar controlled/living RAFT
copolymerization.
*Corresponding author: zmo@hacettepe.edu.tr
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2. Hawker,C. J. Acc. Chem. Res. 1997, 30, 373.
3. Puts R. D., Sogah, D.Y. Macromolecules 1996, 29, 3323. .
4. Kato M., Usuki, A. In Polymer-Clay Nanocomposites; Pinnavaia, T. J., Beall,
G. W., Eds.: John Wiley & Sons: New York, 2000, p 97.
5. Zeng C. H., J. Macromol. Sci. Part C: Polym. Rev. 2005, 45, 171.
6. Di J., Sogah, D. Y. Macromolecules 2006, 39, 1020.
6th Nanoscience and Nanotechnology Conference, zmir, 2010 290