The effect of molecular imprinting on the pore size distribution of polymers
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		    The effect of molecular imprinting on the pore size distribution of polymers Mohammad Al Kobaisi · Margaret Tate · Colin Rix · Timur S. Jakubov · David E. Mainwaring
 
 Received: 16 April 2007 / Revised: 7 August 2007 / Accepted: 24 September 2007 / Published online: 18 October 2007 © Springer Science+Business Media, LLC 2007
 
 Abstract Molecular imprinting techniques are becoming an increasingly important domain of porous polymers generally, to achieve molecule specific recognition through morphology or stereochemistry of cavities. Imprinting is sought to increase both selectivity and sensitivity where the polymer may be present as particulate, membrane or thin film forms. Here, we detail mechanisms involved in the formation, stability and adsorption of binding sites, through the influence of polymerisation conditions and templates on the porosity of highly crosslinked molecularly imprinted polymers (MIPs). Environmental control represents an important area for porous polymers, here we focus on two template fungicides, iprodione and pyrimethanil, for ethylene glycol dimethacrylate (EGDMA) based polymers. In general, control of the pre-polymerisation interactions were able to vary the surface areas of polymers from 40–60 m2 g−1 to 300– 436 m2 g−1 while pore sizes fell into distributions (a) close to the micropore region at ∼3.8 nm, (b) in the 10 to 20 nm mesopore region and (c) in the 20 to 50 nm mesopore region. The importance of intermolecular interactions and aggregation in the pre-polymerisation solution to the Brunauer, Emmett, Teller (BET) surface areas and pore size distribution of final polymers has been demonstrated by systematic variation of chemical functionality. These effects confirm recent molecular dynamic simulation studies of MIP formation and cavity stability.
 
 M. Al Kobaisi · M. Tate · C. Rix · T.S. Jakubov () · D.E. Mainwaring School of Applied Sciences, Royal Melbourne Institute of Technology, Melbourne 3001, Australia e-mail: [email protected]
 
 Keywords Biochemical, energy and environmental applications · Fundamentals of adsorption · Liquid phase adsorption Abbreviations ACM
 
 acrylamide
 
 AIBN
 
 α,α  -azoisobutyronitrile
 
 D
 
 pore diameter
 
 DVB
 
 divinylbenzene
 
 GCMC
 
 Grand Canonical Monte Carlo
 
 Iprodione
 
 EGDMA
 
 ethylene glycol dimethacrylate
 
 MAA
 
 methacrylic acid
 
 NIP P P0 P/P0
 
 non-imprinted polymer pressure (Pa) saturated pressure (101325 Pa) relative pressure
 
 316
 
 Adsorption (2007) 13: 315–321
 
 Pyrimethanil
 
 4-VP
 
 4-vinyl pyridine
 
 VC
 
 1-vinyl carbazole
 
 VI
 
 vinyl imidazole
 
 TAC
 
 2,4,6-tris(2-propenyloxy)-1,3,5-triazine
 
 TAIC
 
 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione
 
 molecule. Assembly of a supramolecular complex prior to polymerisation and the subsequent removal of the template has formed the basis of MIPs showing molecular recognition characteristics attributed to the presence of these imprinted binding sites. Ulbricht and Malaisamy (2005) have related the final interstitial porosity to both the polymer phase inversion and particle morphology during MIP membrane format		
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