Pastukhov A.V., Tsyurupa M.P., Davankov V.A. Hypercrosslinked polystyrene: a polymer in a non-classical physical state J. Polymer. Sci.

, Part B: Polym. Phys. 1999. V.37. P.2324-2333.

Hypercrosslinked Polystyrene: A Polymer in a Non-Classical Physical State

ALEXANDER V. PASTUKHOV, MARIA P. TSYURUPA, VADIM A. DAVANKOV Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences, 117813 Moscow, Russian Federation

Received 15 June 1998; revised 23 February 1999; accepted 15 April 1999

ABSTRACT: Deformation and relaxation properties of hypercrosslinked polystyrene networks have been studied by thermomechanical method at a uniaxial compression using individual spherical beads of the polymer. The networks examined were prepared by postcrosslinking of highly swollen beads of a styrene-0.3% DVB copolymer with 0.3 0.75 mole of monochlorodimethyl ether, which results in the introduction of 0.6 1.5 methylene bridges between each two polystyrene phenyl rings. The polymers obtained are shown to belong neither to typical glassy materials, nor to typical elastomers. Though no characteristic plateau of rubberlike elasticity was observed on the deformation curves of the beads, the polymers exhibit two fundamentally important features of the rubberlike state: The deformations are large (up to 30 40% of the initial diameter) and reversible. Relaxation of residual deformations, however, requires prolonged heating of the sample, or a cycle of swelling and drying. The deformation can start in the temperature range from 70 to 150C depending on pressure applied. The crosslinking degree in the range from 40 100% and higher does not affect noticeably the behavior of the hypercrosslinked polystyrene. Nature of the high mobility of the hypercrosslinked network is discussed. 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2324 2333, 1999

Keywords: hypercrosslinked polystyrene; thermomechanical curves; deformation; relaxation; physical state of polymers

INTRODUCTION
Three physical states, glassy, rubberlike (or rubbery) and viscous-ow states, are well known to be characteristic of amorphous linear high molecular weight polymers.1,2 The transition of polymers from one state to another proceeds in response to changing temperature which affects the accumulated heat energy of macromolecules and, therefore, their mobility. Introduction of crosslinks between linear chains of the polymer restricts the chain mobility, which manifests itself in the elimination of the viscous-ow state and the shift of the glass transition
Correspondence to: A. V. Pastukhov (E-mail: davank @ineos.ac.ru)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 37, 2324 2333 (1999) 1999 John Wiley & Sons, Inc. CCC 0887-6266/99/172324-10

temperature, Tg, towards higher values. If the network was prepared in the absence of any solvent, the entrapped entanglements or, which is the same, interpenetration of network meshes are so signicant that even a moderate amount of chemical crosslinks can fully deprive the network of becoming elastic up to the temperature of chemical degradation. In styrene-DVB copolymers, such an elimination of the rubberlike state takes place at the DVB content of above 25%. Concomitantly, such a polymer does not swell with solvents, at all. However, a network does not necessarily need to lose its mobility with increasing crosslinking degree, if the conditions for the preparation of the network are selected in such a manner as to substantially reduce the interpenetration of the network meshes formed in the process of crosslinking.

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