Patent GB-407997-A (GB)
Title: Improvements in the manufacture and production of condensation products from hydroxylated cyclic compounds and acetylene
IPC: C08G8/30
Filed: 1932-09-29
Abstract: Resinous products are obtained by treating noncarboxylated mono- or poly-hydroxy compounds of the mono- or poly-iso- or heterocyclic series in the liquid phase with acetylene at 100--300 DEG  C. in the presence of an organic salt of zinc or cadmium, e.g. zinc or cadmium acetate, propionate, butyrate, oleate or abietate.  Specified hydroxy compounds are phenol, cresols, xylenols, 4-oxydiphenyl, p-tert.-butylphenol, dioxydiphenyldimethylmethane, resorcinol, naphthols, tetrahydronaphthol, cyclohexanol, hydroxy derivatives of pyridine, quinoline, and methylquinoline, or halogen or sulpho derivatives of any of these, such as chlorophenols and phenolsulphonic acids.  The reaction may be effected in the presence of solvents, a number of which are specified; fillers and other substances required to remain in the products (see below) may also be present.  Pressure is preferably applied during the reaction. According to the conditions, the products may be soluble or insoluble in organic solvents and aqueous alkalies. The products may be purified by (1) an optional steam distillation, followed by treatment in solution in an organic solvent with a bleaching earth, active carbon, or a chemical bleaching agent such as hydrosulphite, followed by filtration and distillation, or (2) precipitation from alkaline solution, or (3) treatment in solid form with acids, alkalies, or alkali carbonates.  The products may be hardened by treatment with aldehydes or reagents yielding aldehydes, such as hexamethylene tetramine; the hardening may be effected in the presence of catalysts such as sulphuric acid, aliphatic or aromatic sulphonic acids, resinic acids, fatty acids, caustic alkalies or organic bases such as cyclohexylamine; solvents may also be present, as well as substances required to remain in the products, such as cellulose ethers and other cellulose derivatives, waxes, oils, resins, resin esters, polymerized vinyl esters, polymerized styrene, polymerized acrylic acid and its derivatives, and fillers such as asbestos, gypsum and wood meal.  The properties of the products may be further modified by the following after-treatments:--(1) esterification with saturated or unsaturated fatty acids, aromatic acids, hydroxy acids, ether acids such as diglycollic acid, amino acids, or polybasic acids such as phthalic succinic, adipic, suberic, citric or tartaric acid; esterification may be effected by treating the alkali salts of the resins with acid chlorides, viscous or waxy products or insoluble plastic masses are so obtained; (2) sulphonation, products having tanning properties being obtained; (3) nitration or chlorination, products being obtained which, like the initial condensation products, can be coupled with diazo compounds to form dyes; the nitrated products may also be reduced to amino compounds, which may be diazotized and combined with coupling components; (4) etherification, as by treating the products with ethylene oxide or by treating the alkali salts of the products with methyl iodide, chlorhydrins, dimethyl or diethyl sulphate, or chloracetic acid; the etherified products resemble the initial resins.  In the examples: (1) phenol is treated with acetylene at 180 DEG  C. under pressure in the presence of zinc acetate, and the resinous product is treated in benzene solution with bleaching earth, filtered, and the solution distilled in vacuo; the purified resin may be hardened by heating it to 200 DEG  C. with a subordinate amount of hexamethylene tetramine; an alkali-soluble product is obtained by heating the purified resin to 200 DEG  C. with linoleic acid, and an alkali-insoluble product is obtained by heating the purified resin in alcoholic caustic soda solution with ethylene chlorhydrin; (2) phenol is treated with acetylene as in example 1 in the presence of zinc acetate and cadmium acetate; (3) phenol is treated with acetylene as in example 1 in the presence of cadmium acetate; (4) commercial cresol or xylenol; (5) o- or p-chlorophenol; (6) 4-oxydiphenyl; (7) p-tert.-butylphenol; (8) resorcinol; (9) dioxydiphenyldimethylmethane; and (10) 8-oxyquinoline are treated with acetylene as in example 1 in the presence of zinc acetate.  The dioxydiphenyldimethylmethane used in example 9 may be a crude product prepared by condensing phenol with acetone in the presence of a strong acid such as hydrochloric, sulphuric or p-toluenesulphonic acid.  Specification 395,732 is referred to.ALSO:Resinous products are obtained by treating noncarboxylated mono- or polyhydroxy compounds of the mono- or poly-iso- or heterocyclic series in the liquid phase with acetylene at 100-300 DEG C. in the presence of an organic salt of zinc or cadmium, e.g. zinc or cadmium acetate, propionate, butyrate, oleate or abietate. Specified hydroxy compounds are phenol, cresols, xylenols, 4-oxydiphenyl, p-tert.-butylphenol, dioxydiphenyldimethylmethane, resorcinol, naphthols, tetrahydronaphthol, cyclohexanol, hydroxy derivatives of pyridine, quinoline, and methylquinoline, or halogen or sulpho derivatives of any of these, such as chlorophenols and phenolsulphonic acids.  The reaction may be effected in the presence of solvents, a number of which are specified; fillers and other substances required to remain in the products (see below) may also be present.  Pressure is preferably applied during the reaction.  The products may be hardened by treatment with aldehydes or reagents yielding aldehydes, such as hexamethylene tetramine; the hardening may be effected in the presence of catalysts such as sulphuric acid, aliphatic or aromatic sulphonic acids, resinic acids, fatty acids, caustic alkalies or organic bases such as cyclohexylamine; solvents may also be present, as well as substances required to remain in the products, such as cellulose ethers and other cellulose derivatives, waxes, oils, resins, resin esters, polymerized vinyl esters, polymerized styrene, polymerized acrylic acid and its derivatives, and fillers such as asbestos, gypsum and wood meal.  The properties of the products may be further modified by the following aftertreatments:-(1) esterification with saturated or unsaturated fatty acids, aromatic acids, hydroxy acids, ether acids such as diglycollic acid, amino acids, or polybasic acids such as phthalic, succinic, adipic, suberic, citric or tartaric acid; esterification may be effected by treating the alkali salts of the resins with acid chlorides; viscous or waxy products or insoluble plastic masses are so obtained; (2) etherification, as by treating the products with ethylene oxide or by treating the alkali salts of the products with methyl iodide, chlorhydrins, dimethyl or diethyl sulphate, or chloracetic acid; the etherified products resemble the initial resins.