Pastukhov A.V., Davankov V.A. Anomalous deswelling of porous network polymers Doklady Chemistry. 2006. V.410. Part 2. P.

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ISSN 0012-5008, Doklady Chemistry, 2006, Vol. 410, Part 2, pp. 182184. Pleiades Publishing, Inc., 2006. Original Russian Text A.V. Pastukhov, V.A. Davankov, 2006, published in Doklady Akademii Nauk, 2006, Vol. 410, No. 6, pp. 767770.

CHEMISTRY

Anomalous Deswelling of Porous Network Polymers

A. V. Pastukhov and V. A. Davankov
Presented by Academician A. R. Khokhlov May 11, 2006 Received May 15, 2006

DOI: 10.1134/S0012500806100053

The phenomenon of deswelling (or volume shrinking) of various organic and inorganic materials during removal of water or other solvents is well known. Indeed, since manufacturing of many commercial products includes processes of removal of water or other liquids, all the characteristics of drying have been studied in detail. It is known that, in making many polymer articles, it is necessary to take into account the decrease in their volume during removal of residual solvents and washing liquids. Therefore, it was quite unexpected when we detected a noticeable (sometimes temporary) increase in the volume (which generally decreases in a regular manner) of polymers of various classes with porous structure during removal of water or other solvents. Such an anomalous deswelling is characteristic not only of hydrophobic hypercrosslinked polystyrenes, porous copolymers of styrene with divinylbenzene, and porous polydivinylbenzenes (including the well-known commercial sorbent XAD-4 (Rohm and Haas Co.)), but also of hydrophilic commercial ionexchange materials based on macroporous copolymers of styrene with divinylbenzene: Amberlyst-15, CT-151, and CT-175 (sulfonic cation-exchange resins) (Purolite Int.) and the polyacrylate-type anion-exchange resin A830 (Purolite Int.) [1]. In studying swelling and subsequent drying of polymer sorbents, we rst applied a method for automatically recording the sizes of individual granules. Note that, previously, it was universally accepted to observe the behavior of a large sample of a granular material, where increases and decreases in the volumes of individual granules combined, thus completely masking the true behavior of the material. The sample size in swelling and deswelling was determined with a UIP-70 standard instrument for thermomechanical testing of polymers (Central Design Bureau, USSR Academy of Sciences). The sample was a single granule of regular spherical shape. Its diameter (0.60.8 mm) was accu-

rately (0.001 mm) measured under a microscope. The sample was placed in a specially drilled polished spherical cavity (1.2 mm in diameter, 1.0 mm in radius, and 0.2 mm in depth) in a quartz plate. Changes in the granule diameter were detected with a mobile quartz rod connected to a capacitive transducer of the instrument. The rod with a polished at end (2.7 mm in diameter) touched the sample with a minimal load of 0.5 g without distorting the regular spherical shape of the sample in swelling or deswelling. Swelling and deswelling were also studied using hypercrosslinked polystyrenes obtained as a block. Test samples (~2 2 2 mm) were cut from a small block of synthesized hypercrosslinked product after its crushing and washing; in measurements, a test sample was placed on a at quartz plate. The volumetric strain esw in solvent absorption or desorption was calculated by the equation D sw 3 ( v sw v ) e sw = ---------------------- = -------- 1 100 , D v where D and v are the diameter (or height) and volume of the dry sample, respectively, and Dsw and vsw are the diameter (or height) and volume of the sample in its swelling or drying, respectively. Porous copolymers of styrene with divinylbenzene (15 wt % in terms of pure divinylbenzene) (SD15H60) and polydivinylbenzene (DH60) were obtained by suspension free-radical polymerization in an aqueous medium in the presence of the initiator 2,2'-azobis(isobutyronitrile) and heptane as a porogenic agent (60 weight parts per 100 weight parts of monomers). Commercial styrene was puried by distillation. Divinylbenzene (Merck) was used without additional purication; it contained 65 wt % of the main substance (a mixture of m and p isomers) and 33 wt % of a mixture of m- and p-ethylvinylbenzenes. Hypercrosslinked polystyrene samples were obtained by a known procedure [2]: granular samples were produced by the reaction in which granules of geltype copolymers of styrene with divinylbenzene (0.2 2.7% divinylbenzene) that are swollen to the limit in dichloroethane are crosslinked with monochlorodimethyl ether, and block samples were obtained by the

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia

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