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Russian Chemical Bulletin, International Edition, Vol. 56, No. 3, pp. 484493, March, 2007

Deformation of styrenedivinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption
A. V. Pastukhov,a V. A. Davankov,a E. V. Sidorova,b E. I. Shkolnikov,b and V. V. Volkovc
aA.

N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation. Fax: +7 (495) 135 6471. E mail: avpastukhov@mail.ru bScience and Engineering Center for Energy Efficient Processes and Equipment, Joint Institute for High Temperatures, Russian Academy of Sciences, 28/19 ul. Izhorskaya, 125412 Moscow, Russian Federation cA. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prosp., 119991 Moscow, Russian Federation

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk defor mation in these processes was studied for a series of cross linked polymers, viz., gel type and porous styrenedivinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differ ences in their physical structures. An unusual effect of a sharp decrease followed by a tempo rary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Key words: polymer swelling, bulk deformation, desorption, styrene copolymers, poly(di vinylbenzene), hypercrosslinked polystyrene, porous polymers.

Swelling of cross linked polymers in solvents can be studied by different experimental methods, which detect changes in either the weight16 or the size of samples.79 Methods of NMR,10 ESR, UV, and IR spectroscopy6 are more rarely used to study changes in other properties of systems caused by polymer swelling. A special dilatomet ric technique based on the monitoring of the volume of the sorbent layer in a solvent washed cylindrical cell was described.11 The swelling pressure and the kinetics of bulk swelling of vulcanized rubbers in different aliphatic and cyclic hydrocarbons were investigated.6,12 Most of known methods cannot be used for studying fast changes in the geometric sizes of liquid contacting materials. However, these data are necessary for optimization of various tech nological processes, particularly, of sorption processes. In this connection, the aim of the present study was to investigate fast deformations of individual granules of cross linked polystyrene type polymers during solvent absorption and desorption. We studied samples of three main types of polystyrene networks, viz., nonporous gel type styrenedivinylbenzene copolymers, macroporous styrenedivinylbenzene copolymers, and macroporous

poly(divinylbenzenes), and hypercrosslinked styrene co polymers,13,14 which predominantly have a microporous structure. Experimental
Known cross linked polystyrene type polymers are similar in the chemical composition and properties but differ in the structure of the polymer matrix and the pore structure. Due to this, cross linked polystyrenes, such as nonporous copolymers, macroporous copolymers, macroporous poly(divinylbenzenes), and hypercrosslinked copolymers, differ in the main physical properties (Table 1). Gel type nonporous copolymers were prepared by sus pension free radical polymerization of styrene with divinyl benzene in an aqueous medium.14 Nonporous copolymers are denoted SD1.4, SD2.7, etc., where S is styrene, D is divinylbenzene, and the numbers correspond to the percent age (wt.%) of divinylbenzene in the copolymer. These polymers have a density of amorphous polystyrene and are nonporous (see Table 1). Macroporous styrenedivinylbenzene copolymers and macroporous poly(divinylbenzenes) were synthesized analo gously with the use of pore forming solvents (toluene or hep

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467476, March, 2007. 1066 5285/07/5603 0484 2007 Springer Science+Business Media, Inc.