Highly unsaturated polymers of polyethynylpolyarene and polyazopolyarene series

Abstract

Two new classes of highly unsaturated polymers—polyethynylpolyarenes and polyazopolyarenes are synthesized by oxidative polycondensation of polyethynylarenes in the first case and of aromatic diamines in the second one and investigated. The polymers have common formulas H[(CC)kAr(CC)k]nH and H2NArN(NArN)NArNH2 respectively. The polymers either keep the conjugation along the main chain or the conjugation is intentionally broken. This is attained by changing the structure of the arylenic part of the monomers. Depending on the structure, electrical properties of the polymers vary in a wide range. For example the conductivity at 20°C. varies from 10−2 to 10−20 ω−1 cm.−1. The temperature dependence of conductivity is σ = σ0 exp {−E/kT}. The activation energy is specially predetermined by the structure and can vary in the range of 0.1 to 4.7 e.v. Similarly magnetic, dielectric, catalytic and other properties and solubility can be changed by varying the structure.

Azo Polymers

“…The catalyzed oxidative coupling of aromatic diamines has been intensively studied for the synthesis of polymers containing stable azo groups (69)(70)(71)(72)(73)(74)(75)(76)(77)(78)(79)(80)(81)(82)(83)(84)(85)(86). For example, aromatic amines have been studied with molecular oxygen in the presence of a Cu + /pyridine catalyst (87).…”

“…For example, aromatic amines have been studied with molecular oxygen in the presence of a Cu + /pyridine catalyst (87). This reaction has been used with a variety of primary aromatic diamines (69)(70)(71)(72)(73)(74)(75)(76)(77)(78)(79)(80)(81)(82)(83)(84)(85)(86).…”

“…Thermal stability is the most frequently studied property of azo polymers (69)(70)(71)(72)(73)(74)(75)(76)(77)(78)(79), and decomposition occurs above 350 • C. It has been suggested that a high degree of conjugation might lead to organic conductors or semiconductors. Electrical conductivity has been determined (53,54,73), and x-ray measurements made on cylindrical films (Debye-Scherrer measurements) of (49) and (47) have shown a high degree of crystallinity (77).…”