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  • Unusual Mobility of Hypercrosslinked Polystyrene Networks: Swelling and Dilatometric Studies

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    Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene–divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briefly discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 °C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100–220 °C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid openwork structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility.

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    Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene–divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briefly discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 °C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100–220 °C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid openwork structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility.

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    Unusual Mobility of Hypercrosslinked Polystyrene Networks: Swelling and Dilatometric Studies

    Uploaded by

    Alexander
    Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene–divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briefly discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 °C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100–220 °C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid openwork structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility.

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    Unusual Mobility of Hypercrosslinked Polystyrene Networks: Swelling and Dilatometric Studies

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

    Received 17 May 1999; revised 8 March 2000; accepted 15 March 2000

    ABSTRACT: Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briey discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100 220 C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid openwork structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility. 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 15531563, 2000

    Keywords: hypercrosslinked polystyrene; network mobility; swelling; expansion; shrinking; thermodilatometric studies

    INTRODUCTION
    The mobility of polymer networks is well-known to be determined by the physical state of the polymer. When the material is in a glassy state, its mobility manifests itself in vibration movements of atomic groups only. Glassy polymers exhibit no unusual enlargement or shrinking with thermal treatment. When a slightly crosslinked polymer is in a rubberlike state, it can experience substantial deformations. For exam-

    Correspondence to: V. A. Davankov (E-mail: davank@ ineos.ac.ru)


    Journal of Polymer Science: Part B: Polymer Physics, Vol. 38, 15531563 (2000) 2000 John Wiley & Sons, Inc.

    ple, the rubbery network can be elongated along the axis of applied stress. However, the total volume of the polymer changes insignicantly with such mechanical or thermal treatment1 because in traditional networks, the polymeric chains are packed densely. A noticeable expansion of traditional networks takes place on treatment with solvents for which the energy of interaction with the polymer segments exceeds that of the polymerpolymer interactions. Nonsolvents for the corresponding linear polymer do not cause any swelling of the crosslinked polymer. Hypercrosslinked polystyrenes represent a fundamentally different type of network. These polymers strongly swell in any kind of liquid, independent of its thermodynamic afnity to
    1553

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