Patent GB-1044231-A (GB)
Title: Curable mixtures suitable for the manufacture of shaped structures
IPC: C08G67/00
Filed: 1965-01-01
Abstract: Compounds containing at least two diketen groups <FORM:1044231/C2/1> may be prepared by heating a monocarboxylic acid halide R1-CH2-COX and a dicarboxylic acid halide XOC-CH2-R2-CH2-COX in the presence of a tertiary amine equivalent in amount to the acid halide groups in an inert solvent.  R1 and R2 are respectively monovalent and divalent aliphatic, aromatic, cycloaliphatic or arylaliphatic groups which may be interrupted in the carbon chain by O or S atoms, and may contain halogen atoms, and R1 may be H; X represents Cl, Br or I.  In examples such compounds are prepared in chlorobenzene by the action of triethylamine on the following acid chloride mixtures: (1) and (2) sebacic/propionic; (3) suberic/propionic; (4) sebacic/caproic; (5) pimelic/propionic; (6) pimelic/butyric; (7) azelaic/propionic; (8) sebacic/lauric; (9) sebacic/acetic.  The equivalents given for the products suggest that Examples (2), (4), (6) and (7) contain a little polymeric material, and Examples (1), (3), (5), (8) and (9) a substantial amount.ALSO:Curable compositions comprise (1) a compound containing at least two b -methylene-propiolactone (diketen) groups <FORM:1044231/C3/1> (2) a curing agent as defined below for cross-linking the polylactone (1), and (3), if desired, a basic curing accelerator. The polylactone (1) is prepared by reacting a monocarboxylic acid halide R1-CH2-COX and a dicarboxylic acid halide XOC-CH2-R2-CH2-COX in the presence of a tertiary amine in an amount equivalent to the acid halide groups, in an inert solvent.  R1 and R2 are respectively monovalent and divalent aliphatic, aromatic, cycloaliphatic or arylaliphatic groups which may be interrupted in the carbon chain by O or S atoms, and may contain halogen atoms, and R1 may be H; X represents Cl, Br or I.  The compounds (2) contain more than one hydroxyl, mercapto, carboxylic hydrazide and/or amide, and/or amino group, or are titanic acid esters, and include polyhydric alcohols and phenols, polymercaptans, polycarboxylic acid hydrazides, primary and secondary polyamines, including cyclic polyamines, and hydroxy-amines.  Other suitable curing agents (2) are tertiary amines, including cyclic amines.  Lists of acid halides suitable for preparing compounds (1), and long lists of suitable compounds (2) are provided In examples polylactones are prepared in chlorobenzene by the action of triethylamine or sebacic/propionic, suberic/propionic, sebacic/caproic, pimelic/propionic, pimelic/butyric, azelaic/propionic, sebacic/lauric and sebacic/acetic acid chloride mixtures, and are then crosslinked by reaction with glycerol, trimethylol propane, a hexanetriolstyrene oxide adduct, diaminodiphenylmethane, hexamethylene diamine, N,N1 - dicyclohexyl - ethylene diamine, ethylene dithiol, hydroquinone, bisphenol A, isophthalic acid dihydrazide, or diethanolamine in the presence of a tertiary amine, or by heating alone with c. 1% of a tertiary amine or tetrabutyl titanate.  The curable mixtures of the invention may be mixed with other resins, if compatible, e.g. aminoplasts, phenoplasts, polyacetals, or epoxy resins, or with fillers, plasticizers, pigments, dyestuffs, flame-inhibitors and/or mould lubricants, or with fibres of e.g. glass, polyester, polyacrylonitrile, silk or cotton, or with propellants for foaming. The equivalents given in the examples for the poly (diketen) compounds (1) prepared suggest that these may be partly polymerized during preparation, notably in Examples I, III, V, VIII and IX.