Patent GB-580405-A (GB)
Title: Improvements in and relating to synthetic resinous condensation products
IPC: C08G14/06
Filed: 1943-03-19
Abstract: Synthetic resinous condensation products are prepared by reacting together under alkaline conditions an aldehyde and a compound corresponding to the formula <FORM:0580405/IV/1> in which n=1 or 2. The term aldehyde includes polymeric aldehydes and aldehyde addition products which yield aldehyde under the conditions of the reaction. The reaction may be performed at atmospheric, sub-atmospheric or super-atmospheric pressures.  The alkaline reaction medium may be produced by sodium, potassium or calcium hydroxide, sodium or potassium carbonates or amines.  If desired, a primary condensation catalyst which is a nitrogen-containing basic compound may be employed together with a secondary condensation catalyst which is a fixed alkali.  The reaction may be performed in presence of solvents or diluents, fillers, other natural or synthetic resinous bodies or of other conventional modifiers, e.g. urea, thiourea, their derivatives, acid amides, other aminodiazines, e.g. 2.4.6-triaminopyrimidine, aminotriazines, e.g. melamine, ammeline, phenols, alcohols, amines, hydrolysed wood products, formalised cellulose derivatives, lignin, protein-aldehyde condensation products, aminotriazine-aldehyde condensation products, aminotriazole-aldehyde condensation products, urea-aldehyde condenation products, phenol-aldehyde condensation products, polyhydrin alcohol-polycarboxylic acid condensation products, water-soluble cellulose derivatives, natural gums and resins, or polyvinyl compounds.  The modifying reactants may be incorporated as described in Specification 542,973.  Thermoplastic condensation products according to the invention are of value as plasticisers for other synthetic resins.  The thermosetting products alone or mixed with fillers, dyes, pigments, lubricants, plasticisers or curing agents may be used for moulding compositions.  Liquid intermediate condensation products may be concentrated or diluted with volatile solvents to form paints, varnishes, lacquers, enamels, adhesives, or may be used for laminating or as coating resins.  They may also be used for bonding mica flake or abrasive grains, or for electrical insulation purposes.  Curing catalysts which may be employed with the resins are, for example, mono-, di- or tri-chloracetamide, citric, phthalic, malonic or oxalic acid, sodium chloroacetate, N-diethyl chloroacetamide, glycine ethyl ester hydrochloride, p chloroacetonitriles, a b -dibromopropionitrile, aminoacetamide hydrochloride, aminoacetonitrile hydrochloride, ethylene diamine monohydrochloride, diethanolamine hydrochloride, nitrourea, chloroacetyl urea, chloroacetone, glycine, sulphamic acid, citric diamide or phenacyl chloride.  In example 1, a b -bis-(4,6-diamino pyrimidyl-2) cyanoethylene disulphide and aqueous formaldehyde are refluxed in alkaline medium, chloracetamide is added, the syrup mixed with a -cellulose flock and zinc stearate and dried and ground to form a moulding powder.  Examples 2, 3 and 4 are similar, but have urea, paratoluene sulphonamide and dimethylol urea respectively present during the initial condensation. Example 5 describes the heating of a syrupy phenolic resin from phenol and alkaline formaldehyde, with a b -bis-(4,6-diamino pyrimidyl-2) cyanoethylene disulphide followed by addition of oxalic acid, a -cellulose and zinc stearate to form a moulding powder.  Example 6 describes the preparation of a resin from a b -bis-(4,6-diamino pyrimidyl-2) cyanoethylene disulphide and acroline, while example 7 employs furfural as the aldehyde. Example 8 describes a butyl-alcohol modified resin which is soluble in ethylene glycol or "Carbitol" (Registered Trade Mark) and useful for varnishes.  Example 9 employs acetamide in the reaction mixture with the diazine and formaldehyde. A slow-curing resin is useful as a modifier for rapidly curing aminoplasts. Example 10 is similar to example 9, but employs diethyl malonate in place of the acetamide and example 11 employs polyvinyl alcohol as the additional modifying ingredient.  A list of suitable aldehydes or aldehyde addition products which may be used according to the mixture is given in the Specification.  a b -Bis-(4,6-diaminopyrimidyl-2) cyanoethylene disulphide is prepared by heating together 4,6-diamino, 2-mercapto pyrimidine, caustic soda and a b -dichloropropionitrile in aqueous alcoholic medium.  a b -Bis-(2,6-diaminopyrimidyl-4) cyanoethylene disulphide is similarly prepared using 2,6-diamino, 4-mercapto pyrimidine as a starting material.  Bis-(4,6-diaminopyrimidyl-2) cyanomethylene disulphide is similarly prepared using dichloroacetonitrile as starting material. As open to inspection under Sect. 91, the Specification includes the use of diazine derivatives of the general formula <FORM:0580405/IV/2> where n = 1 or 2, R = H, or a monovalent hydrocarbon or substituted hydrocarbon radical, of which a long list is given.  A list of diazine derivatives falling within the above general formula is also given.  It also includes the use of the corresponding 1,2- or 1,4-diazines.  The reaction may be prepared under neutral or acid conditions, a list of acid substances suitable for adjusting the reaction of the mixture being given. The list of modifying agents is larger and includes reference to Specifications 554,195 and 1458/42 (as open to inspection under Sect. 91).  The list of curing catalysts given includes reference to Specifications 9244/41 and 10917/41 (as open to inspection under Sect. 91).  Various other aldehyde addition products which may be employed are also mentioned.  This matter forms no part of the Specification as accepted.