The thesis is devoted to the design and synthesis of the ether-containing monomers with perfluoroaromatic mono- and biphenylene fragments, different types of reaction groups (both nucleophilic and electrophilic nature) and functional substituents, as well as the fluorinated poly(arylene ether)s (FPAEs) synthesis of various chemical composition, molecular architecture and structure, functionalization of FPAEs using their main and side chains.
As a result of the work, two types of the ether-containing monomers have been synthesized. The first type is monomers with tetrafluoro(diphenoxy)benzene or octafluoro(diphenoxy)biphenylene fragments. The non-fluorinated aromatic fragments were used for the introduction different types of terminal reactive groups (OH, -N3, -Br, epoxy, allyl, etc.) as well as various functional substituents into the monomers’ structures. Additionally, in the framework of the monomers of the first type, the monomers with a variable length of the conjugation chain (by means of azobenzene or azomethine groups variation introduction of azobenzene, azomethine groups) and a given configuration (by means of isomeric component variation) were synthesized. The second type of monomers are compounds with two perfluoroaromatic units separated (or connected) by ether-containing aromatic fragments of variable chemical structure. In this case, monomers with terminal perfluorinated either mono- or biphenylene moieties were obtained.
The synthesis methods of polyfunctional FPAEs with different electro-conformational structures and molecular architectures were developed. These polyethers were mainly synthesized from the monomers obtained in this work. Hence, simple strategy to prepare meta-linked perfluorophenyl or hydroxyl-terminated fluorinated aromatic oligoethers and FPAEs as well as the statistical and alternating FPAE copolymers with the same composition was proposed. Next, several FPAEs were synthesized using tetrafluorobenzene-containing monomers with isomeric fragments, allyl or acetyl groups along backbone. The cross-linked materials were prepared from the obtained allyl-containing FPAEs. Moreover, the design and synthesis of FPAE/silica cross-linked materials through a sol-gel process by using the triethoxysilyl-containing FPAEs as precursors for both organic and inorganic networks formation were described. Finally, FPAEs with perfluorinated aromatic units as well as rigid dibenzodioxin and spirobisindane fragments simultaneously were successfully obtained by interaction of the synthesized core-fluorinated monomers with 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane. The structures and properties of the synthesized polymers, such as solubility, molecular-weight characteristics, tensile strength, thermal stability as well as dielectric, gas transport, sorption, and liquid crystal were thoroughly investigated.
