Patent GB-704299-A (GB)
Title: A process and compositions for preparing hard resinous products and the resulting hard resinous products
IPC: C08G59/40
Filed: 1952-02-22
Abstract: Glycidyl ethers of dihydric phenols are hardened by means of 0.1-5 per cent. of a mono-, di- or tri-sulphonic acid or of a corresponding sulphonyl halide.  If desired the glycidyl ether may be mixed with a urea-formaldehyde condensate or a urea-formaldehyde condensate, which has been etherified preferably with a saturated monohydric alcohol of 2-8 carbon atoms, e.g. butyl alcohol.  Hardening will take place at ordinary temperature but is preferably effected between 100 DEG C. and 250 DEG C. Lists of suitable sulphonic acids are given.  Some examples are methanesulphonic, ethanesulphonic, propane sulphonic, butanesulphonic, hexanesulphonic, decanesulphonic, hexadecanesulphonic, ethenesulphonic, diisobutylenesulphonic, cyclohexane sulphonic, methane disulphonic, ethane disulphonic, ethanetrisulphonic, benzenesulphonic, toluene sulphonic, di- or tri-methylbenzene sulphonic, naphthalenesulphonic, benzylsulphonic, phenylethane sulphonic, benzene di- or tri-sulphonic, and toluenedisulphonic acid.  Halides of the acids are also listed. Solvents, pigments, e.g. titanium dioxide, antimony oxide, lead oxide, carbon blacks, chrome yellow, zinc oxide or para red, plasticizers or other resins or fillers, e.g. wood flour, talc, and cellulose or zinc sulphide may be included in the compositions.  A variety of solvents is mentioned including ketones, esters, ether alcohols and chlorinated solvents. Diluents, e.g. benzene, toluene, xylene, or ethyl, iso-propyl, or butyl alcohol may also be included. When the glycidyl ether is the sole resin-forming compenent of the composition, a polysulphonic acid or halide is preferably used as hardener.  The hardening agent may be added as a solution.  The products are suitable for laminating or as varnishes or enamels.  If desired the varnish and the hardening agent may be sprayed, the solutions entering a two-nozzle gun as described in Specification 566,543, [Group XXIX], separately and mixing in the zone of atomization. In the examples, glycidyl ethers from epichlorhydrin and 2, 2-bis(4-hydroxyphenyl)propane were employed.  In example 1 the glycidyl ether was dissolved in ethylene glycol monoethyl ether acetate, methyl isobutyl ketone, and toluene and the solution sprayed together with a butyl acetate solution of m-benzenedisulphonic acid. In a modification the ether was mixed with chlorinated diphenyl. Alkali-resistant coatings were produced.  In examples 2 and 3 films were formed from similar compositions by dipping steel panels into them and backing.  The films were tested for resistance to water and solvents, and for flexibility.  In example 4 a heat-convertible phenolic resin sold under the RTM "Resimene" was incorporated into the composition. The curing agent was p-toluene-sulphonic acid. Other examples exemplify the following features-(1) addition of a butylated urea-formaldehyde resin to the composition with any of the following catalysts, viz., mixed C1-C4 alkanesulphonic acids; m-benzenedisulphonic acid; p-toluenesulphonic acid; methanedisulphonyl chloride; methanedisulphonic acid; (2) the addition of titanium dioxide as pigment to yield an enamel and the use of naphthalene sulphonic acid as the curing agent.