Patent GB-665474-A (GB)
Title: Cation modified clay
IPC: C09C1/42
Filed: 1948-12-31
Abstract: Clays having base exchange properties are reacted first with "onium" compounds and then with organic compounds having radicals reactable with the organic radical of the onium compound. "Onium" compounds specified are ammonium, phosphonium, and arsenoniom, sulphonium, oxonium, selenonium, stannonium, and iodonium compounds.  Clays specified are montmorilonites, e.g. bentonites, hectorite, and nontronite; illite, attapulgite, fuller's earth and the synthetic permutites.  Reactable organic compounds are those used in condensation, polymerization and esterification reactions, e.g. aldehydes, ketones, polycarboxylic acids and their anhydrides, dyes and dye intermediates; synthetic resins, natural and synthetic rubbers.  The products are thermoplastic and thermosetting resins, pigments, and synthetic rubbers.  In examples: (1) 26.3 gs. octadecadienylamine was dissolved in hot water and 10 gs. 37 per cent HCl.  An aqueous slurry of 100 gs.  Wyoming bentonite was added to the solution with agitation.  The flocculent precipitate of octadecadienylammonium bentonite was filtered, washed and dried and mixed with 1 gm. benzoyl peroxide.  On moulding at 150 DEG  C. under pressure a plastic product was obtained; (2) aniline bentonite, formed by interaction of bentonite, aniline and hydrochloric acid was reacted with formaldehyde to give a yellow precipitate which in admixture with zinc stearate was moulded to give a thermosetting solid; (3) the reaction product of bentonite, triethylene tetramine and acetic acid was mixed with dimethylol urea and zinc stearate on hot differential rolls and the sheet obtained cooled, ground and moulded at 165 DEG  C.; (4) a pigment was obtained by reacting alpha-naphthylamine hydrochloride with the tetrazonium bentonite obtained by reacting bentonite, and benzidine in HCl solution; (5) a pigment was similarly obtained from bentonite, melamine hydrochloride and Ponceau red.  In examples (6)-(9) the bentonite was replaced by fuller's earth, synthetic zeolite, magnesium bentonite and nontronite; (10) an alkyd resin was obtained by reacting glycine bentonite with glycerol and phthalic anhydride; (11) a similar resin was obtained by reacting triethanolamine bentonite, phthalic anhydride, soya bean fatty acids, fumaric acid and glycerine; (12) the triethanol amine bentonite of (11) was reacted with stearic acid at 280 DEG  C., and (13) with adipic acid, (14) with stearic acid; (15) triethylenetriamine was reacted with illite; (16) and (17) trithenol ethyl arsonium and stibonium iodide were used to replace the triethanol amine of example (11).ALSO:Clays having base exchange properties are reacted first with "onium" compounds and then with organic compounds having radicals reactable with the organic radical of the onium compound (see Group IV (a)).  "Onium" compounds specified are ammonium, phosphonium arsonium, sulphonium, oxonium, selenonium, stannonium and iodonium compounds.  Clays specified are montmorilonites, e.g. bentonites, hectorite, and nontronite, illite, attapulgite, fuller's earth and the synthetic permutites.  In examples, bentonite is reacted with (1) octadecadienylamine and hydrochloric acid to give octadecadienylammonium bentonite; (2) aniline and hydrochloric acid to give phenyl ammonium bentonite; (3) triethylene tetramine and acetic acid; (4) benzidine and hydrochloric acid, followed by tetrazotization of the benzidene bentonite, and coupling with a -naphthylamine to give a pigment; (5) melamine and hydrochloric acid, followed by reacting the melamine bentonite with Ponceau Red; (6) glycine and hydrochloric acid; (7) triethanolamine and hydrochloric acid, and the triethanolamine bentonite is reacted with stearic or adipic acids; (8) triethanolethyl arsonium or stibonium iodide and hydrochloric acid.  In (5) above, the bentonite may be replaced by fuller's earth (attapulgite), a synthetic zeolite, a magnesium bentonite, or nontronite.ALSO:Products suitable for use as dyes or pigments are obtained by reacting clays, having base exchange capacity, with an onium compound and with an organic compound having affinity to the organic portion of the onium radical, e.g. dyes and dye intermediates.  In examples: (4) a pigment is obtained by reacting alphanaphthylamine hydrochloride with tetrazonium bentonite obtained by reacting bentonite and benzidine in HCl solution; (5) a pigment is similarly obtained from bentonite, melamine HCl, and Ponceau red.  Bentonite may be replaced by other montmorilonites, illite, attapulgite, fuller's earth and synthetic permutites.