GB1138308A - Process for the production of solid resins - Google Patents

Abstract

1,138,308. Resins and compositions. INSTITUT FRANCAISE DU PETROLE, DES CARBURANTS ET LUBRIFIANTS. 11 May, 1966 [11 May, 1965], No. 20961/66. Heading C3R. Solid resins are prepared by reacting an aldehyde with a " heavy residue " from the production of a conjugated diolefin by cracking an alkylmetadioxan, then reacting the product with a phenol. The heavy residue preferably derives from cracking of 4-methyl-, 4 :4-dimethyl-, 4:5-dimethyl-, and 4-ethyl-metadioxans, and may also contain similar residues from the preparation of the metadioxan. The chief characteristics of the heavy residues are: b.p. 140-250‹ C., M.W. 150-250, hydroxyl number 30-90, bromine number above 60, e.g. 90-180, flow point below 0‹ C., composition C = 75-86 %, H = 7-12%, O = 5-10%. Suitable aldehydes are C 1-3 saturated aliphatic aldehydes, e.g. formaldehyde, formalin, paraformaldehyde, acetaldehyde, and propionaldehyde. Suitable phenols may be substituted by alkyl, aryl, ether, carboxyl, sulphonic groups or halogen and are, e.g. phenol, o- and mcresol, 1:3 :5-xylenol, 2-butylphenol, 3-benzylphenol, 3:5 - diphenylphenol, 3 - cyclohexylphenol, resorcinol, the bisphenols, 3-chlorophenol, 3-methoxyphenol, salicylic acid, 3- phenolsulphonic acid. The reaction with aldehyde and the. reaction with phenol are both preferably conducted at 60-200‹ C., in the presence of Lewis acid and Friedel-Crafts type catalysts, e.g. phosphoric acid, sulphuric acid, hydrochloric acid, phenolsulphonic acid, SnCl 4 , FeBr 3 , SbF 3 , BF 3 , ZnCl 2 , AlCl 3 as such or in aqueous solutions which may be 0À1-7 N. Thus the first reaction may be conducted in 3-7 N aqueous acid, the second in 0À1-2 N acid, or both may be conducted in acid of less than 2 N. No catalyst is required when the phenol is phenolsulphonic acid. Preferred ratios of reactants are : to each p.b.w. of heavy residue, 0À1-10 p.b.w. of aldehyde and 0À1-10 p.b.w. of phenol. The resins may be cured by heating with an aldehyde. In examples a heavy residue of b.p. 150‹ C. and Br number 160 from the cracking of 4:4-dimethylmetadioxan is reacted with phenol i.p.o. sulphuric acid or 85% phosphoric acid. In Examples 5 and 6 heavy residues are used from the cracking of 4-methyl- and 4:5-dimethyl-metadioxan, of b.p. 140‹ and 180‹ C. and Br numbers 145 and 150 respectively. In Example 4 the phenol is phenol sulphonic acid. In Example 2 a moulding composition is prepared from the resin, hexamine, wood flour, zinc stearate, stearic acid, wax, lime and a colouring matter.