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Porous polymer monolith supported Suzuki-Miyaura catalysis in microreactors

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Deverell, JA (2011) Porous polymer monolith supported Suzuki-Miyaura catalysis in microreactors. PhD thesis, University of Tasmania.

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Abstract

Miniaturisation of reactions to the sub-millilitre scale, through the use of
microreactor technology, has the potential to reduce costs by drastically reducing
reaction times, improving yields and selectivities, as well as decreasing the
environmental impact by reducing reagent and solvent use. Further improvements
can be achieved by utilising heterogeneous and supported catalysts within
microreactors in order to increase reaction efficiency, reduce energy requirements,
and simplify product purification. This should also enable the integration of
microreactors with other existing microfluidic technologies allowing synthesis,
purification, analysis, and bio-testing to be performed on a single device in an
automated fashion.
In this work, novel microreactors were fabricated utilising porous polymer
monoliths (PPM's) prepared in situ within microfluidic devices as a support for the
immobilisation of palladium complexes. Poly(glycidyl methacrylate-co-ethylene
glycol dimethylacrylate) and poly(chloromethylstyrene-co-divinylbenzene)
monoliths were prepared by either thermal or UV initiated radical polymerisation in
several formats, including capillary, microchip, and column using both glass and
polymer substrates. This required the development of new methods for anchoring
PPM within polymer substrates with poor transmission in the deep UV region, which
is necessary for photografting, thus enabling the use of polymer substrates with
greater thermal resistance. The development of polymeric microreactors was pursued
as mass production of microfluidic devices with multiple components is considerably
easier and more economical compared to other substrates. Additionally, conditions
were developed to allow the formation of PPM in columns with an internal diameter
(ID) greater than 1 mm without the need for external compression to avoid
shrinkage. The preparation of PPM using light emitting diode light sources was investigated with the aim of reducing the cost associated with development of
photoinitiated PPM's, enabling greater access to this technique. The PPM's were
utilised to immobilise ligands that will bind palladium, 5-hydroxy-1,10-
phenanthroline, 5-amino-1,10-phenanthroline, and an N-methylimidazolium salt. In
order to demonstrate the feasibility of this technology, the Suzuki-Miyaura coupling
of iodobenzene and p-tolylboronic acid was performed under continuous flow in the
reactors, which produced quantitative yields with less than 0.01% of the immobilised
palladium leached over a 24 h reaction period. This is the first reported used on a
polymer microchip for supported Suzuki-Miyaura catalysis and also the first
demonstration of non-room temperature supported palladium catalysis within a
polymer microreactor. Novel technology was developed to allow easy interfacing
with a broad range of microchips and for producing PPM in batch via UV initiation
using low intensity light sources.

Item Type: Thesis (PhD)
Keywords: microreactor, microfluidics, catalysis, polymer monolith, synthesis, transitin metal
Copyright Holders: The Author
Copyright Information:

Copyright 2011 the Author

Date Deposited: 05 Dec 2011 23:19
Last Modified: 11 Mar 2016 05:53
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