Neue Polyoxazinonamide sowie Verfahren zu deren Herstellung

摘要

1,230,952. Polyamide - acids; polybenzoxazinone-amides. INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LUBRIFIANTS. 28 Feb., 1969 [28 Feb., 1968], No. 10961/69. Headings C3C and C3R. Polyamide-acids comprise a chain of recurring units (I) in which Ar is a trivalent radical comprising # 1 aromatic ring; R is a divalent radical comprising # aromatic or heterocyclic ring which may be substituted with alkoxy, alkyl, or halogen; if Ar or R contain >1 ring, these are condensed or linked by a direct bond or by -O-, -S-, -SO-, -SO 2 -, -CO-, CH 2 -, CMe 2 -, -SiMe 2 - or CONH-; R1 is H or monovalent hydrocarbon radical; the polyamide-acids have inherent viscosity #0À1 dl/g. (30‹ C.) for 0.5% solution in N-dimethylacetamide. The polyamide-acids may be formed by reacting at least one compound (III) with one or more compounds (IV) where Y reacts with the amino groups of (III) to form a carbonamide group, Ymay be -OR11, where R11 = H- or monovalent aliphatic or aromatic hydrocarbon radical preferably containing 1-20 C atoms; or Y may be -NH 2 or halogen. The reaction temperature may be -30‹ to 220‹ C. The reactions are preferably performed with equimolar proportions of (III) and (IV), though up to 50% excess of either may be used. Reaction media are preferably polar solvents e.g. N,N - dialkyl - carbonoxamides, dimethyl sulphoxide, dimethyl sulphone, or N - methylpyrrolidone, or mixtures thereof with each other or with C 6 H 6 or C 6 H 5 CH 3 . Alkali or alkaline-earth metal salts e.g. halides, may be added to increase the solubility of the polymer. Polyphosphoric acid may be used as reaction medium. If Y in (IV) is a halogen, tertiary amines may be added to act as acid acceptor. Interfacial polycondensation may also be used to form the polyamide-acids from a waterimmiscible solution of (IV) and aqueous (III). The polyamide-acids may be isolated by precipitation in a large excess of salts; the polymers are then crushed, washed, and dried to white powders soluble in polar solvents. Uses: Solutions of polyamide-acids may be used to form films or fibres; or they may be used to form expanded polybenzoxazinone-amides e.g. by gas-release during cyclization, e.g. using formic acid. Polybenzoxazinone - amides having recurring units (II) may be obtained by reacting (II) and (IV) at -30‹ to 400‹ C.; a polymer having solubility lower than 0.5 wt. per cent in dimethylacetamide at 30‹ C. may be obtained thus. Alternatively, the polyamide-acid may first be formed as above and then converted to polybenzoxazinoneamide by heating at 200-400‹ C. or by reacting the polyamide-acid at -30‹ to 100‹ C. with an aliphatic or aromatic acid anhydride, in the presence of a tertiary amine under reduced pressure.