Patent GB-433452-A (GB)
Title: Synthetic resins and method of production thereof
IPC: C08G65/40
Filed: 1934-01-10
Abstract: Resinous substances are prepared by reacting at elevated temperature and in the presence of alkali one or more dihalogeno derivatives of the general formula Hal--X--Hal wherein X represents CH2 or an aliphatic hydrocarbon chain which is preferably broken by an ether linkage with one or more dinuclear phenols of the general formula <FORM:0433452/IV/1> wherein Ar and Ar<1> are phenylenes which may carry alkyl, alkoxy or halogen substituents or, preferably a secondary or tertiary alkyl groups in a p-position to the phenolic hydroxyl group and R and R<1> represent hydrogen, alkyl, or aryl groups.  A portion of the phenol may be replaced by an equivalent amount of a dihydroxydiarylsulphone or by one or more monohydric phenols and a proportion of the dihalogeno compound may be replaced by a monohalogen compound.  Suitable phenols include di(4-hydroxyphenyl)methylmethane, di(4 - hydroxyphenyl) dimethylmethane, di(4-hydroxyphenyl)methylethylmethane, di(4-hydroxyphenyl)propylmethane, di(4-hydroxyphenyl)dipropylmethane, 1 - 1 - di(4 - hydroxyphenyl) cyclohexane, di(4 - hydroxy) phenylmethane, di(4 - hydroxy - 3 - chlorophenyl)-dimethylmethane, di(4 - hydroxy - 3 - methylphenyl) dimethylmethane, di (4 - hydroxy - 3-methyl-5-chlorophenyl)dimethylmethane, di(4-hydroxy-3-5-dimethylphenyl)-dimethylmethane and di(4 - hydroxy - 3 - 5 - dichlorophenyl)-dimethylmethane.  Suitable dihalogen compounds which include chlorides, bromides and iodides are ethylene dichloride, propylene dichloride, amylene dichloride, p  iso-amylene dichloride, b  - b <1> - dichlorodiethylether, b  - b <1>-dichlorodiamylether, methyl - b  - g  - dibromo-m-butyl ether, and g -g <1>-dichlorodipropyl ether. Suitable monohalides include benzyl chloride, stearyl chloride, oleyl chloride, amyl bromide, and mixtures of monochlorinated aliphatic hydrocarbons.  Suitable sulphones include di(4 - hydroxyphenyl)sulphone, di(4-hydroxy - 3 - methylphenyl) sulphone, di(4-hydroxy - 3 - methyl - 5 - chlorophenyl) sulphone, di(4 - hydroxy - 3 - 5 - dimethylphenyl) sulphone, di(4 - hydroxy - 3 - chlorophenyl) sulphone and di(4 - hydroxy - 3 - 5 - dichlorophenyl) sulphone.  The condensation may take place in aqueous medium or in the presence of an inert solvent such as toluene, xylene or chlorobenzene or alcohols such as butyl alcohol, glycerol or glycol with or without the addition of water. In examples resins are prepared by condensing in the presence of water and sodium hydroxide dichlorodiethyl ether and (1) di(4-hydroxyphenyl)dimethylmethane with or without the addition of di(4-hydroxyphenyl)sulphone; (4) di(4 - hydroxy - 3 - methylphenyl)dimethylmethane; (5) di(4 - hydroxy - 3 - 5 - dichlorophenyl) dimethylmethane; or (6) o-cresol and di(4-hydroxyphenyl)dimethylmethane or by condensing di(4 - hydroxyphenyl)dimethyl - methane in the presence of water and sodium hydroxide with ethylene or amylene dichlorides.  The resins may be used in various compositions in conjunction with solvents, pigments; fillers; lakes; plasticizers; cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose propionate, cellulose acetobutyrate, ethyl cellulose and benzyl cellulose; natural resins or derivatives thereof such as rosin, kauri, damar, ethyl abietate, ester gum, congo glycollide, and hydrogenated rosin; drying oils such as linseed and chinawood oils; synthetic resins such as polyhydric alcoholpolybasic acid, amine-aldehyde and phenolaldehyde condensation products and polyvinyl resins; and bitumens such as asphalt.  The products may be used in the paint industry as undercoats, primers, surfacers and top coats; as moulding plastics; as bonding agents for mica; as adhesives in the manufacture of laminated glass; as binding agents for sheets of cellulose acetate or paper in the manufacture of laminated sheet and tubes; as cements and sealing waxes; as impregnating, coating, sizing, glazing or water-proofing agents for linoleum, rubber, regenerated cellulose, cellulose ethers and esters, fabrics, paper, porous stone, leather, artificial leather, rubber-coated fabrics, wood or wood pulp; as binders for linoleum plastics; in the manufacture of printing inks; as glass substitutes such as photographic films or plates or motion picture films; as fire retardants (when the resin contains excess chlorine); as transparent sheet material; as impregnating agents, with or without waxes, for milk bottle tops; as boot or shoe stiffeners or water-proofing agents for sole leather; as adhesive, preservative and transparency-producing agents for parchment paper; impregnating agents for highly absorptive papers, thin papers, or wall papers; impregnating agents for tyre cord, cotton for use in making canvas or tenting material, hemp ropes, linen, duck, flannel, woollen fabrics, aeroplane fabrics and balloon cloth; binders for artificial fibre board; as varnishes for electric cables or wires; as flexible finishes for tin or galvanized containers which are stamped into shape; as binders for sandpaper and emery cloth; as impregnating and delustring agents for artificial silk; as impregnating or coating agents for currency paper; as impregnating agents for paper containers for milk, oil or other liquids; as clear varnishes for golf balls or tennis rackets; as impregnating agents for hose; as cementing agents for architectural slabs, sheets or blocks of glass or as a chide substitute for making chewing gum.  Di(4 - hydroxy - 3 - 5 - dichlorophenyl) - dimethyl - methane is obtained by chlorinating the parent body in glacial acetic acid solution.  The Specification as open to inspection under Sect. 91 refers in general to the condensation of a polyhydric alcohol or an alkali or alkaline earth metal salt thereof with polyhalides having at least two reactive halogen atoms.  Examples of phenols include resorcinol, p-p<1>-dihydroxydiphenyl, 1-methyl-3-5-dihydroxybenzene, 1-3-dimethyl - 4 - 6 - dihydroxybenzene, ditertiaryamylresorcinol, hexylresorcinol, cyclohexylresorcinol, pyrocatechol, hydroquinone, hydrocumoquinone (1-2-4-trimethyl-3-6-dihydroxybenzene), 2-5-dichloroquinone, iso-propylpyrocatechol, a  - a <1> - dihydroxypyridine, 2 - 6 - dihydroxynapthalene, anthrahydroquinone, p - p<1> - dihydroxybenzophenone, di(4 - hydroxyphenyl)-sulphone, polynuclear phenols containing as groups between the nuclei --S--, --CH2--, --S--S--, --O--, --CO--CO--, --CH2--CH2-- groups, phenols obtained by condensing acids or anhydrides such as succinic acid or phthalic anhydride with phenol, chlorophenol, resorcinol, thymol and known as succineins, phenolphthalein, fluorescein, thymolphthalein, dichlorophenolphthalein, eosin and erythrosin, 2 - phenyl - 1 - 3 - dihydroxynaphthalene, pyrogallol, phloroglucinol, trihydroxynaphthalenes, tetrahydroxybenzenes, biresorcin, tetrahydroxydiphenyl, hydroxyanthrones (obtained from salicylic acid and resorcinol) gallic acid, dihydroxyphthalic acid and dihydroxynaphthalenesulphonamide.  Suitable halogen compounds include xyxylene dibromide, b -b <1>-dichlorodiethylsulphide, b -b <1>-dichlorodiethyldisulphide hexamethylene dibromide, rubber chloride, chlorinated fatty oils, halogen alkyl ethers of polyhydric alcohols such as b -b <1>-dichloroethyl ether of diethylene glycol, g -g <1>-g <11>-trichloropropyl ether of glycerol, dichloromethyl ether of ethylene glycol, dipentenehydrochloride, 1 - 4 - dichlorocyclohexane, pentamethylene dichloride, 2-3-dichloropentane, tetramethylene dichloride, 1-4-7-trichloropentane, trichloromethyl ether of glycerol, 1-3-5-chloromethylbenzene, 1-3-5-methylene trichloride. Phenols or halogen compounds containing other groups such as --NO2--, --NH, --NH2, --COOH, --CONH2, --CONHR, --COOR, RCOO--, aliphatic --SH or --OH, --SO2H, --SO2NHR may also be used and products obtained therefrom may be further reacted.  Suitable substances include trichlorotriethylamine, dichlorodiethylamine, gallic acid, dioxyphthalic acid, the product from which may be further reacted with polyhydric alcohols or derivatives thereof such as glycerol or mono- or di-linseed oil glycerides), dihydroxynaphthalenesulphonamide (the product may be further reacted with aldehydes) or glycerol-a -a <1>-dichlorhydrin (the product may be further reacted with carboxylic acids), 2-4-dihydroxy-phenylethyl alcohol (the product may be further reacted with carboxylic acids such as benzoic, stearic, oleic, butyric, acids or mixtures of fatty acids such as linseed oil, chinawood or cottonseed oil fatty acids). The resinous products may be sulphonated to yield wetting, flotation and tanning agents or they may be acetylated with keten or nitrated. The resins may also be obtained by intramolecular reaction of an organic compound containing both a phenolic hydroxyl and a reactive halogen.  Such compounds include the mono-chloroethyl or the mono-chlorethoxyethyl ether of dihydroxydiphenyldimethylmethane. This subject-matter does not appear in the Specification as accepted.