GB1226711A - - Google Patents

Abstract

1,226,711. Oxazole, thiazole, and imidazole polymers. TORAY INDUSTRIES Inc. 4 July, 1969 [5 July, 1968], No. 33897/69. Heading C3R. Heat-resisting mouldings are formed by pressmoulding at from the secondary transition pt. or up to 300‹ C. higher and at 50-3000 kg.cm.<SP>-2</SP>, a powdered polymer (P) having oxazole, thiazole or imidazole repeating unit where A = O, S or NR; R = H or a hydrocarbon group; R 1 is atomatic; R 2 is a group having # 3 C atoms; R 3 is a group having # 2 C atoms. R 1 may be R 2 may be and R 3 may be where Z is a C-C bond, or -O-CO-O-, -O-CO-, -OC-O-CO-, -O-, -CH 2 -, -C(CH) 3 -, -NH-, -CONH-, or -SO 2 -. The powder may have average grain size 0À01- 300 Ám., or up to 50 mesh Japanese Industrial Standard. Also included may be 0-30% wt., based on (P), of a fluorinated polymer, metal powders, MoS 2 , a polyamide, e.g. poly-(N- methyl - p - phenyleneterephthalamide) or poly- (N-methyl-p-phenyleneisophthalamide), graphite, quartz powder, glass powder, glass fibres, or mica powder. These additives may be mixed with (P) powder or added to (P) solution and precipitated together with (P). (P) may be formed by reaction of tetracarboxylic anhydride and diamine (III) H 2 N-R 3 -NH 2 . Also present may be a tetracarboxylic anhydride where R 4 contains # 4 C atoms and may be aliphatic, cycloaliphatic, or aromatic; or a triamine or tetramine. A poly(ortho-substituted amide acid) is formed, and on heating this to > 100‹ C., e.g. 250‹ C. in air or 350‹ C. in vacuo, ring closure occurs and (P) is formed. (II) is obtained by condensing where Y is halogen, e.g. by contacting in an organic solvent at - 50‹ to 0‹ C. The polymerization may be performed by solution polymerization, using as solvent, e.g. dimethylformamide, dimethylacetamide, dimethylformamide, acetamide, diethyl acetamide, N - methyl - 2 - pyrrolidone, N - methylcaprolactam, tetramethylurea, pyridine, dimethyl sulphone, butyrolactone, and/or N- acetyl-2-pyrrolidone, with or without benzene, toluene, nitrobenzene, chlorobenzene, dioxane, or cyclohexane. The solvent should preferably be H 2 O-free but may contain a small quantity of H 2 O. The solvent usually dissolves 0À05- 50% solid components. The reaction temperature is preferably - 60‹ to 130‹ C. (P) may be obtained as a powder by dissolving it in a polar organic solvent and adding a non-solvent, e.g. a liquid hydrocarbon, ether, halogenated hydrocarbon, benzonitrile, or a mixture of an alcohol or ketone with water; or a catalyst, e.g. a tertiary amine, may be added to the solution; or a film of (P) may be east from the solution and pulverized. (P) can be formed into bearings, packings, gears, bushings, cams, piston-rings, flanges, heat-resisting materials and electricalinsulating materials.