| Budget Amount *help |
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1999: ¥2,600,000 (Direct Cost: ¥2,600,000)
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| Research Abstract |
We investigated the photoreaction of alkyl muconate derivatives in the solid state and the relationship between the topochemical polymerization reactivity and crystal structure. The halogen-substituted dibenzyl muconate derivatives also topochemically polymerized, similarly to the ethyl ester. Furthermore, we have successfully determined single crystal structures of a series of the benzyl esters of (Z, Z)- and (E, E)-muconic acid. X-ray structure analysis has revealed that the stacking of the diene plane of the monomer influences the reactivity of the photopolymerization in crystalline state.
Topochemical polymerization was efficiently induced by the introduction of 1-naphthyl-methylammonium moiety as the countercation into 1, 3-diene mono- and dicarboxylate derivatives. The polymerization proceeded for not only the (Z, Z)-muconic acid derivatives, but also the (E, E)- muconic and sorbic acid derivatives. The naphthylmethylammonium group is suitable for the formation of the columnar str
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ucture, which is advantageous for topochemical polymerization. It was also revealed from the analysis of the polymer chain structure that the meso-diisotactic polymers were produced, irrespective of the configuration of monomers. The stereoregularity of the resulting polymers during topochemical polymerization is closely related to the molecular packing in the monomer crystals.
Some alkylammonium sorbate derivatives were also polymerized via a topochemical mechanism. The polymer was confirmed to be of a stereoregular and high molecular weight polymer. The main chain structure of the polymer was erythro-disotactic-trans-2, 5-structure. Based on the crystal structure determined by single crystal structure analysis, we discussed the molecular packing of the monomers appropriate for topochemical polymerization. We also succeeded in a ladder polymer synthesis using radical polymerization in the crystalline state. p-xylylenediammonium disorbate as the bifunctional monomer was efficiently polymerized by topochemical polymerization. The polymerization mechanism has also been revealed based on the results of the single crystal structure analysis and ESR spectroscopy. Less
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