Patent GB-576163-A (GB)
Title: Improvements in and relating to reaction products of aldehydes and bis-(diamino triazinyl) cyanoalkylene disulphides
IPC: C08G12/30
Filed: 1943-03-09
Abstract: Resinous condensation products are prepared by reacting togethe under alkaline conditions an aldehyde and a bis-(diamino triazinyl) cyanoalkylene disulphide, of the general formula <FORM:0576163/IV/1> in which n = 1 or 2 and R = hydrogen, methyl or ethyl.  Triazine derivatives mentioned are a b  - bis - (4.6.diamino - s - triazinyl) - 2 - cyanoethylene disulphide; Bis-(4.6.diamino-s-triazinyl)-2-cyanomethylene disulphide; a b -bis (4.6 - dimethylamino - s - triazinyl - 2) - cyanoethylene disulphide. If desired the reactants may be employed in the form of salts.  The term aldehyde includes polymeric aldehydes such as paraformaldehyde and aldehyde-addition products which yield aldehyde under the reaction conditions, e.g. dimethylol urea or trimethylol melamine.  A list of suitable aldehydes is given in the Specification.  The reaction may be performed at normal or elevated temperatures and at any pressure. Alkaline conditions may be obtained by addition of sodium, potassium or calcium hydroxide, sodium or potassium carbonate, or monodi- or tri-amines, or, as described in Specification 569,413 a primary (advantageously N- containing) condensation catalyst and a secondary condensation catalyst (usually a fixed alkali) may be present.  The reaction may take place in the presence of solvents, diluents, fillers, other natural or synthetic resinous bodies or, in the manner usual in the art, of other modifying bodies which may take part in the reaction.  A list of suitable modifying agents is given.  The method of incorporating them may be as described in Specification 542,973.  The products of the invention may be used as plasticizers for other synthetic resins or after incorporation with the usual adjuvants as moulding compositions.  Liquid intermediate condensation products may be concentrated or diluted to form coating compositions.  The products may also be used, for example, in the usual manner for such purposes as laminating, electrical insulation, or as bonding agents for abrasives.  All the examples use a b  - bis (diamino - s - triazinyl) - 2 - cyanoethylene disulphide.  In example 1 this compound is heated under reflux with alkaline formaldehyde, chloroacetamide is added as a curing catalyst and a moulding composition is prepared by addition of a -cellulose and zinc stearate, followed by drying and grinding. A list of other suitable curing catalysts is given and Specifications 9244/41 and 10917/41 (both open to inspection under Sect. 91) are referred to. In example 2, urea is added as a modifying reagent to the initial reaction mixture and in example 3 para-aminobenzene sulphonamide. Example 4 employs dimethylol urea in place of formaldehyde and example 5-acrolein.  Example 6 employs butyl alcohol as a modifying agent, and dehydrates the resinous syrup on a hot plate to yield a film-forming material soluble in ethyl alcohol, butyl alcohol or ethylene glycol, and suitable for spirit or baking varnishes or as a modifier of aminoplast or alkyd resin varnishes. Example 7 employs acetamide as a modifying agent to yield a resinous syrup which could be heat-cured with the acid of curing catalysts. Example 8 employs diethyl malonate as a modifying agent and Example 9 glycerine.  The products are similar to that of example 7.  Example 10 employs polyvinyl alcohol as a modifying agent and yields a resinous syrup which heat bodies to an elastic mass with good adhesive properties and which is heat curable with the aid of curing catalysts.  It is specially suitable as a baking varnish.  In example 11 the triazinyl compound is reacted with a syrupy condensation product prepared by condensing phenol and aqueous formaldehyde in presence of potassium carbonate.  The resulting resinous syrup was heat-curable with the aid of curing catalysts.  The starting materials of the invention may be prepared by heating together a diamino mercapto - s - triazine, a dihalogenated alkyl cyanide and a hydrohalide acceptor.  Thus a  - b  - bis - (4.6 - diamino - s - triazinyl) - 2 - cyanoethylene disulphide may be prepared by condensing thioammeline and a -b -dichlorpropionitrile together in alkaline, aqueous-alcoholic medium.  Bis - (diamino - s - triazinyl)-cyanomethylene disulphide may be produced in essentially the same way using an equivalent amount of dichloroacetonitrile.  For a  - b  - bis - (4 - 4 - di (methylamino) - s - triazinyl) - 2 - cyanoethylene disulphide, the thioammeline is replaced by 4.6-di(methylamino) - 2 - mercapto - s - triazine (obtainable by reacting 2-mercapto-4.6-dichloro-s-triazine with methyl amine. The ethyl analogue can be similarly prepared using ethyl amine.)