Patent GB-710757-A (GB)
Title: Cation-exchanging synthetic resins
IPC: B01J39/19
Filed: 1951-02-28
Abstract: Cation-exchange synthetic resins are made by condensing in acid medium (1) an aldehyde e.g. formaldehyde, (2) a naphthalene monosulphonic acid, (3) a phenol containing one phenolic hydroxy group per aromatic nucleus and (4) an aromatic compound containing more hydrophilic groups than aromatic nuclei, at least one of these groups being a hydroxy or an amino group.  The aromatic nuclei may be benzene or naphthalene nuclei.  The naphthalene monosulphonic acid may be preliminarily condensed with the aldehyde.  Specified for reactant 2 are alpha- and beta-naphthalene sulphonic acids and their alkyl substitution products; for reactant (3) phenol, cresols, xylenols, dihydroxy diphenyl sulphones, dihydroxy diphenyls, and dihydroxy diphenyl ketones; for reactant (4) 1.3-dihydroxy benzene, 3.5-dihydroxybenzoic acid, 1.7-dihydroxynaphthalene, 1-aminobenzene-3-sulphonic acid, N-phenylamino acetic acid, 2.8-dihydroxynaphthalene-3-carboxylic acid, 1-hydroxynaphthalene-6 or -7-sulphonic acid, 1.6- or 1.7-dihydroxynaphthalene-3-sulphonic acid, 1.8-dihydroxynaphthalene-3-carboxylic acid-6-sulphonic acid, 2.8-dihydroxynaphthalene-6-sulphonic acid, 1.8-dihydroxynaphthalene-3.6-disulphonic acid, 1-amino-5-hydroxynaphthalene-7-sulphonic acid, 1-amino-8-hydroxynaphthalene-3.6-disulphonic acid, 1-aminonaphthalene-6-sulphonic acid, 2-aminonaphthalene-6.8-disulphonic acid; also condensation products of aromatic hydroxy compounds with oxo compounds containing sulphonic acid groups, e.g. benzaldehyde-2.4-disulphonic acid; also condensation products of aromatic hydroxy compounds with the reaction products of sulphurous acid and unsaturated aliphatic oxo compounds, e.g. aerolein or crotonaldehyde, one of such condensation products being <FORM:0710757/IV (a)/1> In examples: (1) A mixture of sulphonated naphthalene, phenol, 1.8-dihydroxynaphthalene-3.6-disulphonic acid and formalin are allowed to stand at 50 DEG C.  Then the mixture is heated at 50-60 DEG C. with further formalin and the resultant gel after-hardened in a stream of hot air.  (2) A mixture of sulphonated naphthalene, dihydroxy diphenyl sulphone and 1.8-dihydroxy-naphthalene-3.6-disulphonic acid is heated to 105-110 DEG C., formalin gradually added and the mixture allowed to stand. (3a) Sulphonated naphthalene is condensed with formalin at 130-135 DEG C. (3b), (4) and (5) Phenol, formalin and either resorcin or 1.7-dihydroxynaphthalene are heated together, added to the condensate of Ex. 3a and the mixture heated.  (6) To the condensate of Ex. 3a is added a phenol-cresol mixture, 1.8-dihydroxynaphthalene-3.6-disulphonic acid and formalin. After standing at 50-55 DEG C. further formalin is added.  (7)-(11) To a mixture of phenol and the condensate of Ex. 3 (a) is added (7) a solution of 1-amino-8-hydroxynaphthalene-3.6-disulphonic acid in caustic soda and the mixture heated to 60 DEG C., (8) a mixture of formalin and 1-hydroxynaphthalene-6- or -7-sulphonic acid or 1.6 or 1.7-dihydroxynaphthalene-3-sulphonic acid or 1.8-dihydroxynaphthalene-3.6-disulphonic acid: after standing the mixture is heated to 60-70 DEG C., (9) a mixture of 1-aminobenzene-3-sulphonic acid, caustic soda and formalin, the mixture being heated to 50-55 DEG C., further formalin added and the temperature raised to 75-80 DEG C., (10) and (11) a mixture of formalin, caustic soda and either 1-amino-5-hydroxynaphthalene-7 sulphonic acid or N-phenylamino acetic acid, the mixture being heated first alone and then with formalin.  (12) A mixture of phenol and 1-hydroxybutane-1.3-disulphonic acid is dissolved in the condensate of Ex. 3 (a) and the mixture heated first alone and then with formalin.  (12a), (12b) A mixture of 1-hydroxybutane-1.3-disulphonic acid and phenol is heated in presence of sulphuric acid and the product heated with either formalin alone or phenol and formalin and added to the condensate of Ex. 3 (a).  The mixture is then reacted with further formalin. (12c) The reaction product of 1-hydroxybutane-1.3-disulphonic acid and phenol is added to a mixture of phenol and the condensate of Ex. 3 (a) and the mixture reacted with formalin.  (13) A mixture of resorcin, benzaldehyde-2.4-sodium disulphonate and sulphuric acid is heated, the condensate of Ex. 3 (a) and phenol added and the mixture reacted with formalin in two steps.  (14) A mixture of phenol, the condensate of Ex. 3 (a) and either 2.8-dihydroxynaphthalene-3-carboxylic acid or 2.8-dihydroxynaphthalene-3-carboxylic acid is heated and the product reacted with formalin in two steps.  The resulting gels are treated as in Example 1.ALSO:A diphenylol derivative of butane sulphonic acid of formula <FORM:0710757/IV (b)/1> is made by condensing phenol with 1-hydroxybutane-1,3-disulphonic acid.