Patent GB-681266-A (GB)
Title: Improvements in and relating to the manufacture of resinous condensation products and of leather
Inventor: WHITE THEODORE
IPC: C14C3/18
Filed: 1949-10-14
Abstract: Water-and acid-soluble resinous condensation products are made by condensing at least one aliphatic aldehyde with at least one aliphatic ketone in an alkaline medium and at least one sulphonic acid group is introduced during or after the condensation by treatment in an alkaline medium with a preferably water-inorganic sulphite, bisulphite, or sulphur dioxide, or is present in one of the aldehydes or ketones.  Normally the treatment with the sulphite, bisulphite or sulphur dioxide is effected in the same medium as that used for condensation but the product may be separated before the second alkaline treatment.  Preferably the products are derived from acetone and formaldehyde or methyl ethyl ketone and formaldehyde. Acetaldehyde, crotonaldehyde and methyl propyl ketone are also specified.  Two or more ketones may be condensed with one or more aldehydes or vice versa.  Alkali earth metal sulphites, e.g. calcium sulphite may be used and sodium sulphite and bisulphite are also specified.  The sulphonic acid groups may, in whole or in part, be introduced as bisulphite compounds of an aldehyde or ketone used in the condensation, e.g. formaldehyde and acetone bisulphites. Magnesium oxide may be used as an alkaline compound.  In an illustration, 4 mols. of acetone are condensed with 1 mol. of formaldehyde, excess acetone removed and the product resinified and made water-soluble by treatment with aqueous sodium sulphite. Products containing fewer sulphonic acid groups are obtained if the sodium sulphite is replaced by sodium metabisulphite followed by alkali.  The products are used in leather tanning.  In examples: (1) acetone (4 mols.) is condensed with formaldehyde (1 mol.), aqueous sodium sulphite added at below 20 DEG  C., the temperature raised to 80 DEG  C., and the product brought to pH 3 with acetic acid; (2) the product, similar to that of (1), is deionized by passage through a synthetic resin ion-exchange medium; (3) the initial condensation product of (1) is fractionated in butyl phthalate and a fraction reacted with sodium sulphite as in (1) and deionized as in (2); (4) instead of deionizing, the product of (3) is treated with sulphuric acid to pH 3.12; and in (5) with acetic acid to pH 3.55; (6) another fraction from (3) is dissolved in ethanol and aqueous sodium sulphite added, the product being deionized in (7) before pH adjustment to 2.92 with aqueous ammonia and acidified with sulphonic acid in (8); (9) and (10) the initial condensation product of (1) is treated with aqueous sodium metabisulphite and caustic soda reaction effected at 70 DEG  C. and the product acidified with sulphuric acid; (11) is a repeat of (10), the metabisulphite being reacted with the carbonization product at 70 DEG  C. before cooling and further reacting with the caustic soda at 80 DEG  C.; (12) the non-volatiles from the fractionation of (3) are treated with sodium metabisulphite in refluxing aqueous ethanol, the pH adjusted to 11.5 with caustic soda and refluxing continued before acidification with sulphuric acid; (in (13)-(23) formaldehyde is used as a 37 per cent aqueous solution) (13) formaldehyde (3 mols.) is condensed with acetone (1.5 mols.) in the presence of caustic soda solution at 50 DEG  C., neutralized with sulphuric acid, the product reacted with sodium sulphite at 70 DEG  C. and acidified with sulphuric acid; (14) the initial condensation product of (13) is stirred with sodium metabisulphite, caustic soda added to give a pH of 11.5, reaction effected at 50 DEG  C., and the product acidified with sulphuric acid; (15) the initial condensate is made using sodium carbonate instead of the hydroxide, the product is dissolved in aqueous ethanol, refluxed with sodium metabisulphite and neutralized and acidified with sulphuric acid; (16) a condensate similar to that of (15) is reacted at 70-75 DEG  C. in ethanol solution with sodium metabisulphite and aqueous caustic-soda, excess ethanol is removed and the product neutralized and acidified with sulphuric acid; (17) acetone (1 mol.) and formaldehyde (1.5 mols.) are condensed at 35-40 DEG  C. with sodium carbonate and the product treated with formaldehyde bisulphite at 50-70 DEG  C., the pH being adjusted to 11.5 with sodium hydroxide and neutralized and acidified with sulphuric acid; (18) acetone (1 mol.) and formaldehyde (2 mols.) are condensed with methanolic caustic potash at 50-60 DEG  C. and the product treated similarly to that of (17); (19) acetone (1 mol.) p as its bisulphite is condensed with formaldehyde (2.5 mols.) at 50-60 DEG  C.), the pH being kept at 11.5 with caustic soda and the product neutralized and acidified with sulphuric acid; (20) formaldehyde (2.5 mols.) as its bisulphite is condensed with acetone (1 mol.) at 40-50 DEG  C. with sodium carbonate and at 90 DEG  C. whilst the pH is raised to 10.5 with caustic soda, neutralization and acidification then being effected as previously; (21) acetone (1 mol.) is condensed at 45-50 DEG  C. with formaldehyde (2.5 mols.) and sodium carbonate and at 70 DEG  C. at pH 10.5, the necessary adjustment being made with caustic soda, the product is treated with sodium metabisulphite at 75-85 DEG  C. and pH 10-10.5 before neutralization and acidification as above; (22) formaldehyde (4 mols.) and acetone (1 mol.) are condensed at 50 DEG  C. with caustic soda at pH 10.5 and the product which does not react with sodium metabisulphite at room temperatures is reacted with sodium sulphite at 70 DEG  C. before acidification with sulphuric acid; (23) an initial condensation product similar to that of (22) is treated in aqueous ethanol at 70-75 DEG  C. and pH 11-11.5 (adjustment being made with caustic soda) with sodium metabisulphite with neutralisation and acidification as before; (24) methyl ethyl ketone (3 mols.) is condensed with paraformaldehyde as in Specification 551,219, warmed with sodium metabisulphite solution and heated at 40 DEG  and 80 DEG C. with pH adjustment to 11.5 with caustic soda, the product being acidified with sulphuric acid; (25) the initial product of (24) is treated at 50 DEG  C. with aqueous sodium sulphite and subsequently acidified as before and it is stated that free formaldehyde may be present; (26) mixed acet- and croton-aldehydes are condensed with acetone in the presence of methanolic caustic potash at below 5 DEG C., neutralized by passing CO2 and excess acetone removed, the product, in ethanol, being reacted with aqueous sodium metabisulphite at 50 DEG  C., cooled, the pH adjusted to 11.5 with caustic soda and heated at 80 DEG  C. before acidification; (27) aqueous formaldehyde mixed with crotonaldehyde is condensed with acetone and sodium carbonate at below 10 DEG  C., the pH being maintained at 10.5-11 with caustic soda, heated at 35-40 DEG  C., neutralized with sulphuric acid, filtered and the resultant aqueous solution reacted with sodium metabisulphite at 50 DEG  C., cooled and the pH adjusted to 11.5 with caustic soda and the mixture heated at 80 DEG  C. before neutralization and acidification; (28) acetaldehyde and aqueous formaldehyde are condensed with acetone and methyl ethyl ketone in the presence of sodium carbonate at below 10 DEG  C., pH being kept at 10.5-11 with caustic soda, then further reacted at about 40 DEG C., neutralized and the product treated with sodium metabisulphite as in (27); (29) acetaldehyde, crotonaldehyde and aqueous formaldehyde are condensed with acetone and methyl ethyl ketone with sodium carbonate below 10 DEG  C., pH being kept at 10.5-11 with caustic soda and further reacted in a similar fashion to (27); (30) aqueous formaldehyde is condensed with acetone and methyl ethyl ketone at 35-40 DEG  C. in the presence of caustic soda, cooled, heated at about 40 DEG  C. with pH at 10.5-11 by the addition of caustic soda and neutralized, the product being reacted with sodium metabisulphite similarly to (27), and in (31) acetone (4 mols.) and formaldehyde (1 mol.) are condensed and treated with calcium sulphite initially at room temperature but then at 50 DEG  C., and finally at 90 DEG  C., the cooled product being acidified as previously.