1. Synthesis Of Macrocyclic Monoaza Crown Ethers And Its Cross-Linked Polyrotaxane 2. Free Radical Copolymerization Of Vinyl Macrocyclic Monoaza Crown Ether With Styrene

Polyrotaxanes, as functional polymer materials, in which rotaxane structure units are incorporated into macromolecules, have basic properties of rotaxanes and polymers, thus polyrotaxanes are perfect materials for producing molecular sensor devices such as molecular switch and molecular wire and so forth.In this thesis, the first part depicted syntheses of monoaza-m-phenylene-34-crown-11 and monoaza-m-phenylene-34-crown-11 alcohol derivatives, which compounds were prepared by using resorcinol, tetraethylene glycol, p-tolenesulfonyl chloride and 2-bromoethanol as starting materials under high dilution condition. The latter compound reacted with poly(methacyloyl chloride) to give novel polyrotaxane macromolecule, where the macrocyclic azacrown ethers are threaded by linear segments with no covalent bonds between the two species. Their structures were characterized by ~1H-NMR, DSC, MS and IR.In the second part, described synthesis of N-(4-vinylhenzyl)-l-aza-m-phenylene-34-crown-11 (VCE) monomer and its homo- and copolymerization behavior. The monomer was obtained by using resorcinol, tetraethylene glycol, p-tolenesulfonyl chloride and 4-vinylbenzyl chloride, adopting above method. Free radical polymerize VCE monomer or copolymerize VCE with styrene, by the conventional initiator 2,2'-azobisisobutyronitrile(AIBN) to afford the polymers, containing macrocyclic aza crown ether unit, their number average molecular weight and molecular weight distribution were determined by GPC. The reactivity ratio of styrene and VCE, determined by the Fineman -Ross method, gave values 1.4 for styrene and 0.6 for VCE respectively. Thermal properties of the homopolymers and copolymers were investigated by using DSC and TGA.