Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States

Design and Preparation of Porous Polymers

Owing to their immense potential in energy conversion and storage, catalysis, photocatalysis, adsorption, separation and life science applications, significant interest has been devoted to the design and synthesis of hierarchically porous materials. The hierarchy of materials on porosity, structural, morphological, and component levels is key for high performance in all kinds of applications. Synthesis and applications of hierarchically structured porous materials have become a rapidly evolving field of current interest. A large series of synthesis methods have been developed. This review addresses recent advances made in studies of this topic. After identifying the advantages and problems of natural hierarchically porous materials, synthetic hierarchically porous materials are presented. The synthesis strategies used to prepare hierarchically porous materials are first introduced and the features of synthesis and the resulting structures are presented using a series of examples. These involve templating methods (surfactant templating, nanocasting, macroporous polymer templating, colloidal crystal templating and bioinspired process, i.e. biotemplating), conventional techniques (supercritical fluids, emulsion, freeze-drying, breath figures, selective leaching, phase separation, zeolitization process, and replication) and basic methods (sol–gel controlling and post-treatment), as well as self-formation phenomenon of porous hierarchy. A series of detailed examples are given to show methods for the synthesis of hierarchically porous structures with various chemical compositions (dual porosities: micro–micropores, micro–mesopores, micro–macropores, meso–mesopores, meso–macropores, multiple porosities: micro–meso–macropores and meso–meso–macropores). We hope that this review will be helpful for those entering the field and also for those in the field who want quick access to helpful reference information about the synthesis of new hierarchically porous materials and methods to control their structure and morphology.

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Hierarchically porous materials: synthesis strategies and structure design

High internal phase emulsion templating as a route to well-defined porous polymers

PolyHIPEs: Recent advances in emulsion-templated porous polymers

Porous polymer monoliths: amazingly wide variety of techniques enabling their preparation.

Preparation and characterisation of poly(high internal phase emulsion) methacrylate monoliths and their application as separation media

An oil-in-water high internal phase emulsion I consisting of acrylic acid, water, and a crosslinker (N,N'-methylene bisacrylamide) as the water phase, and toluene as the oil phase was successfully stabilised to sustain thermal initiation of radical polymerisation resulting in porous open-cellular monolithic material. The type of initiator used influenced the average pore size ranging from approx. 708 nm to approx. 1 087 nm, as determined by mercury porosimetry.

Acrylic Acid “Reversed” PolyHIPEs

Preparation of highly porous (up to 80% pore volume) open-cellular monolithic cross-linked polymers from 2-hydroxyethyl methacrylate is reported. Oil-in-water and water-in-oil high internal phase emulsions are applied as porosity templates, resulting in an interconnected porous structure with void diameters between 550 nm and 18 μm. Significantly larger voids were obtained in the case of oil-in-water emulsions (between 5 and 18 μm) as opposed to water in oil emulsions (approx 600 nm). Controlled coarsening exploiting limited kinetical stability of emulsions was used to obtain monoliths with larger voids, diameters being enlarged 3-fold.

Highly Porous Open-Cellular Monoliths from 2-Hydroxyethyl Methacrylate Based High Internal Phase Emulsions (HIPEs): Preparation and Void Size Tuning

4-Vinylbenzyl chloride (VBC) based water-in-oil-in-water emulsions with 85% pore volume and 70% VBC in organic phase were prepared and polymerised by free radical polymerisation. Porous spherical particles of diameters between 50 and 150 μm were obtained and their morphological structure and reactivity studied by FTIR spectroscopy, elemental analysis, optical microscopy, scanning electron microscopy and mercury intrusion porosimetry. Strong influence of the suspension stabiliser, namely poly(N-vinylpyrrolidone) (PVP), on the particle form was found. Diameters of spherical polymers particles depend on the PVP concentration, being larger with the lower concentration of PVP. Reactivity of novel supports was demonstrated by the reactions with piperidine, piperazine, tris(hydroxymethyl)methylamine and tris(2-aminoethyl)amine, all yielding corresponding amine derivatives.

4-Vinylbenzyl chloride based porous spherical polymer supports derived from water-in-oil-in-water emulsions

Water-in-oil high-internal-phase emulsions (HIPEs), containing 4-nitrophenyl acrylate and 2,4,6-trichlorophenyl acrylate as reactive monomers, were prepared and polymerized, and highly porous monolithic materials resulted. The novel materials were studied by combustion analysis, Fourier transform infrared spectroscopy scanning electron microscopy, mercury porosimetry, and N2 adsorption/desorption analysis. With both esters, cellular macroporous monolithic polymers were obtained; the use of 4-nitrophenyl acrylate resulted in a cellular material with void diameters between 3 and 7 μm and approximately 3-μm interconnects, whereas the use of 2,4,6-trichlorophenyl acrylate yielded a foam with void diameters between 2 and 5 μm, most interconnects being around 1 μm. The resulting monoliths proved to be very reactive toward nucleophiles, and possibilities of functionalizing the novel polymer supports were demonstrated via reactions with amines bearing additional functional groups and via the synthesis of an acid chloride derivative. Tris(hydroxymethyl)aminomethane and tris(2-aminoethyl)amine derivatives were obtained. The hydrolysis of 4-nitrophenylacrylate removed the nitrophenyl group, yielding a monolithic acrylic acid polymer. Furthermore, functionalization to immobilized acid chloride was performed very efficiently, with more than 95% of the acid groups reacting. The measurement of the nitrogen content in 4-nitrophenyl acrylate poly(HIPE)s after various times of hydrolysis showed the influence of the total pore volume of the monolithic polymers on the velocity of the reaction, which was faster with the more porous polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 296–303, 2005

Dejan Štefanec

Papers

Preparation and characterisation of poly(high internal phase emulsion) methacrylate monoliths and their application as separation media

Acrylic Acid “Reversed” PolyHIPEs

Highly Porous Open-Cellular Monoliths from 2-Hydroxyethyl Methacrylate Based High Internal Phase Emulsions (HIPEs): Preparation and Void Size Tuning

4-Vinylbenzyl chloride based porous spherical polymer supports derived from water-in-oil-in-water emulsions

Aryl acrylate based high‐internal‐phase emulsions as precursors for reactive monolithic polymer supports