Patent GB-1088727-A (GB)
Title: Polyiminolactones and their preparation and conversion to polyamide-esters and polyimides
IPC: C08F2/48
Filed: 1964-11-20
Abstract: The invention comprises polyiminolactams having recurring units of formula <FORM:1088727/C3/1> where R and R1 are aromatic and the carbonyl group and imido group in each ring are bonded to mutually ortho or peri carbon atoms in R. The polymer may be prepared by reacting the corresponding polyamide-acid with a fatty acid halide, a halogenated fatty acid halide, a halogenated fatty acid anhydride, an aryl phosphinic dihalide, a thionyl halide or an N,N1-disubstituted carbodimide.  This reaction may be at room temp. in a solvent. Solvents specified include benzenes, dimethylacetamide, tetrahydrofuran and cyclohexane.  Cyclizing agents specified include: di-n-butylcarbodiimide, diphenyl carbodiimide, di-m- or p-tolyl carbodiimide, di - m- or p - chlorophenyl-carbodiimide, di - m - nitrophenyl carbodiimide, dicyclohexycarbodiimide, di - p - methoxyphenyl carbodiimide, di - a  - naphthylcarbodiimide, trifluoroacetic anhydride, acetyl chloride, valeryl chloride, thionyl chloride, propionyl fluoride, bromoacetyl bromide, phenyl phosphonic dichloride, and mixtures of chloroacetic anhydride with 2-methyl pyrazine and phenyl phosphonic dichloride with pyridine. Shaped polyiminolactone articles may be formed by treating a shaped polyamide-acid article with a cyclizing agent.  The polyamide-acid may have an inherent viscosity of at least 0.05 and may be produced from the corresponding tetracarboxylic acid anhydride and diamine in an organic solvent.  A 0.05-40% solution may be used and the reaction may take place at up to 175 DEG  C.  Chain terminators and aliphatic diamines and tetracarboxylic acid dianhydrides may be present. Reactants specified include the dianhydrides of: pyromellitic acid, naphthalene - 2,3,6,7 - tetracarboxylic acid, naphthalene - 1,2,5,6 - tetracarboxylic acid, diphenyl - 3,31,4,41 - tetracarboxylic acid, diphenyl - 2,21,3,31 - tetracarboxylic acid, 2,2-diphenyl propane - 31,311,41,411 - tetracarboxylic acid, diphenyl sulphone-3,31,4,41-tetracarboxylic acid, diphenyl ether - 3,31,4,41 - tetracarboxylic acid, perylene - 3,4,9,10 - tetracarboxylic acid, and benzophenone - 3,4,31,41 - tetracarboxylic acid, m- and p-phenylene diamines, naphthylene diamines, diphenylene diamines, anthrylene diamines, furylene diamines, benzfurylene diamines, 2,2 - bis - (4 - aminophenyl) propane, bis - (4 - aminophenyl) methane, bis - (4-aminophenyl) ether, bis - (4 - aminophenyl) sulphone, bis - (4 - aminophenyl) sulphide, 2,4 - diamino cumene and diamines where R1 is of formula <FORM:1088727/C3/2> and R3 is -CO-NR4-, -COO-, -NR4-, -SiR4R5-, -O-SiR4R5-O-, -P(O)R4- or -O-P(O)R4-O-, where R4 and R5 are alkyl, aryl, substituted alkyl or substituted aryl. Solvents specified for the polyamide-acid formation include dimethyl acetamide.  A polyamide-ester having recurring units of formula <FORM:1088727/C3/3> where R2 is alkyl or aryl and X is O or S may be prepared by reacting the corresponding polyiminolactone or an article made therefrom with an alcohol, phenol or thiol.  The reaction may be in solution.  The polyiminolactone and polyamide-ester may both have inherent viscosities of at least 0.1.  Alcohols, phenols and thiols specified include C1- 12 aliphatic alcohols, e.g. methanol, ethanol, n- or isopropanol, butanol, hexanol, 2-ethyl-hexanol, isooctanol and lauryl alcohol, aromatic alcohols, phenols, e.g. phenol, and C1- 12 aliphatic thiols, e.g. ethane thiol. Solvents specified include benzene and triethylamine is specified as a catalyst.  The polyiminolactone and polyamide-ester may be converted to polyimide by heating it above 150 DEG  C. In addition the polyiminolactone may be treated with triethyl ammonium acetate. Fillers may be added to the polyiminolactones, polyamide-ester or polyimide.  The products may be made into laminates and self-supporting films.  A cellular polymer may be produced by adding a blowing agent and optionally a filler to one of the intermediate polymers and heating the mix to decompose it. Alternatively, bubbles of air, CO2, or N2 may be dispersed in a melt or solution of the intermediate polymer.ALSO:Polyiminolactones having recurring units of formula:  <FORM:1088727/B1-B2/1> where R and R1 are aromatic and the carbonyl and imido groups of each ring are on mutually ortho or peri carbon atoms in R, and polyamide-esters having recurring units of formula:  <FORM:1088727/B1-B2/2> where R2 is aliphatic or aromatic and X is O or S may be applied to a substrate and heated form a coating of polyimide. The coating may be applied by doctoring, rolling, dipping, brushing or spraying.  Substrates specified, are copper, brass, aluminium, steel, asbestos, glass, regenerated cellulose wood and paper, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyimides, polyamides, polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, and polyurethanes.  The substrate can be metallized before coating.