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Synthesis and properties of the addition polymer of benzenedithiol with divinylbenzene
Author(s) -
Kobayashi Eiichi,
Kuribayashi Ryotaro,
Aoshima Sadahito
Publication year - 1995
Publication title -
polymers for advanced technologies
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.61
H-Index - 90
eISSN - 1099-1581
pISSN - 1042-7147
DOI - 10.1002/pat.1995.220060603
Subject(s) - divinylbenzene , materials science , polymer , polymer science , polymer chemistry , chemical engineering , copolymer , composite material , styrene , engineering
Polyaddition of 1,4‐benzenedithiol (BDT) to 1,4‐divinylbenzene (DVB) was carried out with 2,2′‐azobisisobutyronitrile initiator in toluene at 75°C under a nitrogen atmosphere. The polymerization proceeded without an induction period, to give a white polymer with a high molecular weight (M̄ w = 110,000) in ca. 90% yield for 2 hr. It was confirmed by 1 H‐NMR (nuclear magnetic resonance), IR (infrared) and sulfur contents that the polymer had an alternating structure of DVB and BDT units. The end‐capping reaction of the polymer was also achieved by addition of thiophenol and/or styrene to the polymerization solution at a final stage of the polymerization. The polymer film exhibited a reversible phase transition between a transparent state and an opaque one by thermal mode. The thermal property of the polymer was studied by differential scanning calorimetry (DSC) analysis and polarized optical microscope observation with the polymer film. The detailed DSC analysis showed that the end‐capped polymer with a relatively low molecular weight (M̄ W = 4400–9600) exhibited similar to liquid crystalline behavior. A diffuse reflectance spectrum of the polymer coated on an aluminum plate showed a marked difference in reflective light intensity in the ultraviolet and visible regions: the reversible phase transition between an opaque and a transparent polymer layers was induced by thermal mode. The light transmittance of the polymer film, which was measured by depolarized light intensity method, was very sensitive toward the temperature variation.