Patent GB-580247-A (GB)
Title: A process for the plasticisation of rubber
IPC: C08K11/00
Filed: 1943-06-24
Abstract: Rubber, including unvulcanised or vulcanised rubber, whether natural, reclaimed or synthetic, is plasticized by incorporating therein a minor proportion of a compound produced by reducing a product of sulphurisation, e.g., by the action of sulphur, a polysulphide or sulphur monochloride, of a compound containing the acylradicle R-CO-, wherein R represents an aliphatic chain of more than nine carbon atoms.  The compound containing the radicle R-CO- may be a fatty acid or a metal salt, amide or ester thereof, e.g., ricinoleic or oleic acid or their salts, or castor, tung, linseed, rape or cotton seed oil, or a marine animal oil. In examples, rubber is plasticised with agents prepared by (1) heating oleic acid with sulphur at 180 DEG -200 DEG  C. for 20 hours, heating the addition product so obtained for six hours with granulated zinc and aqueous sodium hydroxide solution, isolating an oil by precipitation with hydrochloric acid and drying the washed product in vacuo at 40 DEG  C.; (2) heating a mixture of oleic acid and sulphur monochloride to 100 DEG  C. for 15 minutes, refluxing the product for six hours with aqueous sodium hydroxide and excess granulated zinc and isolating the resultant oil as in (1); (3) heating a mixture of ricinoleic acid and sulphur monochloride to 100 DEG  C. for 15 minutes, refluxing the product for four hours with aqueous sodium hydroxide and excess granulated zinc and isolating an oil as in (2); (4) and (5) adding sulphur monochloride to (4) linseed oil and (5) rape seed oil, refluxing the resulting gels for 24 hours with aqueous sodium hydroxide and excess granulated zinc, water being added at intervals, and isolating the oily product as in (1); (6) adding sulphur monochloride to castor oil, heating the resulting gel with iron filings and glacial acetic acid, with gradual addition of aqueous hydrochloric acid, refluxing the mixture for six hours, and isolating the oil product by ether extraction; (7) heating an aqueous emulsion containing castor oil, oleic acid, ammonium hydroxide, zinc oxide and zinc isopropyl xanthate with aqueous sodium polysulphide for 72 hours, coagulating the resultant emulsion by addition of dilute hydrochloric acid and heating the resultant oil for 16 hours with alcoholic sodium hydroxide, diluting, acidifying with hydrochloric acid and isolating the oily product by benzene-extraction.ALSO:Rubber, including unvulcanized or vulcanized rubber, whether natural, reclaimed or synthetic, is plasticised by incorporating therein a minor proportion of a compound produced by reducing a product of sulphurisation, e.g. by the action of sulphur, polysulphide or sulphur monochloride, of a compound containing the acyl radicle R-CO-, wherein R represents an aliphatic chain of more than 9 carbon atoms.  The compound containing the radicle R-CO- may be a fatty acid or a metal salt, amide or ester thereof, e.g. ricinoleic or oleic acid or their salts, or castor, tung, linseed, rape or cotton seed oil or a marine animal oil. Reduction may be effected by such reducing-agents as zinc dust with aqueous sodium hydroxide, iron with aqueous hydrochloric acid, alcohol with an alkali metal, alcoholic alkali or sodium hydrosulphite.  In examples, rubber is plasticised with agents prepared by (1) heating oleic acid with sulphur, heating the addition product so obtained with granulated zinc and aqueous sodium hydroxide solution, isolating an oil by precipitation with hydrochloric acid and drying the washed product in vacuo at 40 DEG  C.; (2) heating a mixture of oleic acid and sulphur monochloride, refluxing the product with aqueous sodium hydroxide and excess granulated zinc and isolating the resultant oil as in (1); (3) heating a mixture of ricinoleic acid and sulphur monochloride, p  refluxing the product with aqueous sodium hydroxide and excess granulated zinc and isolating an oil as in (2); (4) and (5) adding sulphur monochloride to (4) linseed oil and (5) rape seed oil, refluxing the resulting gels for 24 hours with aqueous sodium hydroxide and excess granulated zinc, water being added at intervals and isolating the oily product as in (1); (6) adding sulphur monochloride to castor oil, heating the resulting gel with iron filings and glacial acetic acid, with gradual addition of aqueous hydrochloric acid, refluxing the mixture for 6 hours, and isolating the oily product by ether extraction; (7) heating an aqueous emulsion containing castor oil, oleic acid, ammonium hydroxide, zinc oxide and zinc isopropyl xanthate with aqueous sodium polysulphide for 72 hours, coagulating the resultant emulsion by addition of dilute hydrochloric acid and heating the resultant oil for 16 hours with alcoholic sodium hydroxide, diluting, acidifying with hydrochloric acid and isolating the oily product by benzene-extraction.ALSO:Rubber, including unvulcanized or vulcanized rubber whether natural, reclaimed or synthetic, is plasticized by incorporating therein a minor proportion of a compound produced by reducing a product of sulphurization, e.g., by the action of sulphur, polysulphide or sulphur monochloride, of a compound containing the acylradicle R-CO-, wherein R represents an aliphatic chain of more than 9 carbon atoms and subjecting such rubber to mechanical working. The compound containing the radicle R-CO- may be a fatty acid or a metal salt, amide or ester thereof, e.g., ricinoleic or oleic acid or their salts, or castor, tung, linseed, rape- or cotton-seed oil, or a marine animal oil.  The plasticizers may be used with other known plasticizing agents, e.g., mercaptobenzthiazole.  In examples, rubber is plasticized with agents prepared by (1) heating oleic acid with sulphur at 180-200 DEG C. for 20 hours, heating the addition product so obtained for 6 hours with granulated zinc and aqueous sodium hydroxide solution, isolating an oil by precipitation with hydrochloric acid and drying the washed product in vacuo at 40 DEG C.; (2) heating a mixture of oleic acid and sulphur monochloride to 100 DEG C. for 15 minutes, refluxing the product for 6 hours with aqueous sodium hydroxide and excess granulated zinc and isolating the resultant oil as in (1): (3) heating a mixture of ricinoleic acid and sulphur monochloride to 100 DEG C. for 15 minutes, refluxing the product for 4 hours with aqueous sodium hydroxide and excess granulated zinc and isolating an oil as in (2); (4) and (5) adding sulphur monochloride to (4) linseed oil and (5) rape seed oil, refluxing the resulting gels for 24 hours with aqueous sodium hydroxide and excess granulated zinc, water being added at intervals and isolating the oily product as in (1); (6) adding sulphur monochloride to castor oil, heating the resulting gel with iron filings and glacial acetic acid with gradual addition of aqueous hydrochloric acid, refluxing the mixture for 6 hours, and isolating the oily product by ether extraction; (7) heating an aqueous emulsion containing castor oil, oleic acid, ammonium hydroxide, zinc oxide and zinc isopropyl xanthate with aqueous sodium polysulphide for 72 hours coagulating the resultant emulsion by addition of dilute hydrochloric acid and heating the resultant oil for 16 hours with alcoholic sodium hydroxide, diluting, acidifying with hydrochloric acid and isolating the oily product by benzene-extraction.  In all the examples mercaptobenzthiazole may be used as an auxiliary plasticizer.