Patent GB-889321-A (GB)
Title: Stabilizing organic materials subject to oxidative deterioration
Inventor: MORRIS RUPERT C
IPC: C10L1/18
Filed: 1960-07-28
Abstract: Oleaginous materials and waxes, e.g. edible fats and oils of vegetable, animal or mineral origin, especially kerosene, gasoline and lubricating oil, linseed, menbaden, codliver, castor, olive, rapeseed, coconut, palm, corn, sesame, peanut and babassu oils, lard and beef tallow, petroleum wax and natural waxes contain as a stabilizer a minor proportion of a 3:5-dialkyl-4-hydroxybenzyl alcohol, the alkyl substituents preferably being branched groups of 3-8 carbon atoms; the preferred stabilizer is 3:5-di-tert.butyl-4-hydroxybenzyl alcohol.  In general the stabilizer is used in amounts of 0,00001-5% by weight of the material to be stabilized, but in distillate fuels are preferably used in amounts of 0,001-1%.  A second sulphur-containing stabilizer is generally also incorporated and the resulting compositions show an enhanced synergistic effect; such second stabilizers may be (a) a compound of formula <FORM:0889321/III/1> where R and R1 are hydrocarbon groups of 6-20 carbon atoms and n is 1-6, dilauryl thiodipropionate being preferred, (b) a compound of formula R1-CH2-CH2-Sx-R2 or R1-CH2-CH2-Sx-CH2-CH2-R2 where x is an integer and R1 and R2 are each an aromatic or, more preferably, an aliphatic group, e.g. di-dodecyl disulphide, (c) a thiuram disulphide, a tetraalkyl thiuram disulphide being preferred, (d) a compound of formula <FORM:0889321/III/2> where M is a metal of Group II of the Periodic System and R1 and R2 are each hydrocarbon groups of 1-6 carbon atoms, (e) a trialkyl trithiophosphite, (f) a polyalkoxyalkyl sulphide, (g) a polyalkoxyalkoxyalkyl sulphide, or (h) a polyhydroxyalkyl sulphide. Specification 834,291 is referred to.ALSO:Polyolefins, especially polyethylene and polypropylene, natural rubber, and synthetic rubbers such as polybutadiene and polyisoprene contain as a stabilizer a minor proportion of a 3:5-dialkyl-4-hydroxybenzyl alcohol, the alkyl substituents preferably being branched groups of 3-8 carbon atoms; the preferred stabilizer is 3:5-di-tert.butyl-4-hydroxybenzyl alcohol. In general the stabilizer is used in amounts of 0,00001-5% by weight of the material to be stabilized, but in rubber up to 10% by weight may be used.  A second sulphur-containing stabilizer is generally also incorporated and the resulting compositions show an enhanced synergistic effect; such second stabilizers may be (a) a compound of formula <FORM:0889321/IV (a)/1> where R and R1 are hydrocarbon groups of 6-20 carbon atoms and n is 1-6, dilauryl thiodipropionate being preferred, (b) a compound of formula R1-CH2-CH2-Sx-R2 or R1-CH2-CH2-Sx-CH2-CH2-R2 where x is an integer and R1 and R2 are each an aromatic or, more preferably, an aliphatic group, e.g. di-dodecyl disulphide, (c) a thiuram disulphide, a tetraalkyl thiuram disulphide being preferred, (d) a compound of formula <FORM:0889321/IV (a)/2> where M is a metal of Group II of the Periodic System and R1 and R2 are each hydrocarbon groups of 1-6 carbon atoms, (e) a trialkyl trithiophosphite, (f) a polyalkyoxyalkyl sulphide, (g) a polyalkoxyalkoxyalkyl sulphide, or (h) a polyhydroxyalkyl sulphide.  Specification 834,291 is referred to.ALSO:Organic material generally subject to oxidative deterioration and in particular esters such as methyl linoleate and palmitate and ethyl stearate, and aldehydes such as nona-aldehyde contains as a stabilizer a minor proportion of a 3 : 5-dialkyl-4-hydroxybenzyl alcohol, the alkyl substituents preferably being branched groups of 3-8 carbon atoms; the preferred stabilizer is 3 : 5-di-tert.butyl-4-hydroxy-benzyl alcohol.  In general the stabilizer is used in amounts of 0.00001%-5% by weight of the material to be stabilized.  A second sulphur-containing stabilizer is generally also incorporated and the resulting compositions show an enhanced synergistic effect; such second stabilizers may be (a) a compound of the formula <FORM:0889321/IV (b)/1> where R and R1 are hydrocarbon groups of 6-20 carbon atoms and n is 1-6, dilauryl thiodipropionate being preferred, (b) a compound of formula R1-CH2-CH2-Sx-R2 or R2-CH2-CH2-Sx-CH2-CH2-R2 where x is an integer and R1 and R2 are each an aromatic or, more preferably, an aliphatic group, e.g. di-dodecyl disulphide, (c) a thiuram disulphide, a tetraalkyl thiuram disulphide being preferred, (d) a compound of formula <FORM:0889321/IV (b)/2> where M is a metal Group II of the Periodic System and R1 and R2 are each hydrocarbon groups of 1-6 carbon atoms, (e) a trialkyl trithiophosphite, (f) a polyalkyoxyalkyl sulphide, (g) a polyalkoxyalkoxyalkyl sulphide, or (h) a polyhydroxyalkyl sulphide. Specification 834,291 is referred to.ALSO:Butter and margarine contain as a stabilizer a minor proportion of a 3 : 5-dialkyl-4-hydroxybenzyl alcohol, the alkyl substituents preferably being branched groups of 3-8 carbon atoms; the preferred stabilizer is 3 : 5-di-tert. butyl-4-hydroxybenzyl alcohol.  In general the stabilizer is used in amounts of 0,00001-5% by weight of the material to be stabilized.  A second sulphur-containing stabilizer is generally also incorporated and the resulting compositions show an enhanced synergistic effect; such second stabilizers may be (a) a compound of formula <FORM:0889321/I/1> where R and R1 are hydrocarbon groups of 6-20 carbon atoms and n is 1-6, dilauryl thiodipropionate being preferred, (b) a compound of formula R1-CH2-CH2-Sx-R2 or R1-CH2-CH2-Sx-CH2 -CH2-R2 where x is an integer and R1 and R2 are each an aromatic or, more preferably, an aliphatic group, e.g. di-dodecyl disulphide, (c) a thiuram disulphide, a tetraalkyl thiuram disulphide being preferred, (d) a compound of formula <FORM:0889321/I/2> where M is a metal of Group II of the Periodic System and R1 and R2 are each hydrocarbon groups of 1-6 carbon atoms, (e) a trialkyl trithiophosphite, (f) a polyalkyoxyalkyl sulphide, (g) a polyalkoxyalkoxyalkyl sulphide, or (h) a polyhydroxyalkyl sulphide. Specification 834,291 is referred to.ALSO:Foodstuffs such as oranges, pineapples, bananas, eggplant, alfalfa, squash, avocados, milk, dried milk powder, chocolate, ice cream, cheese, chicken, duck, goose, turkey, bacon, other meat and fish contain as a stabilizer a minor proportion of a 3 : 5-dialkyl-4-hydroxybenzyl alcohol, the alkyl substituents preferably being branched groups of 3-8 carbon atoms; the preferred stabilizer is 3 : 5-di-tert. butyl-4-hydroxybenzyl alcohol.  In general the stabilizer is used in amounts of 0.00001-5% by weight of the material to be stabilized.  A second sulphur-containing stabilizer is generally also incorporated and the resulting compositions show an enhanced synergistic effect; such second stabilizers may be (a) a compound of formula <FORM:0889321/VI/1> where R and R1 are hydrocarbon groups of 6-20 carbon atoms and n is 1-6, dilauryl thiodipropionate being preferred; (b) a compound of formula <FORM:0889321/VI/2> or <FORM:0889321/VI/3> where x is an integer and R1 and R2 are each an aromatic or, more preferably, an aliphatic group, e.g. di-dodecyl disulphide; (c) a thiuram disulphide, a tetra-alkyl thiuram disulphide being preferred; (d) a compound of formula <FORM:0889321/VI/4> where M is a metal of Group II of the Periodic System and R1 and R2 are each hydrocarbon groups of 1-6 carbon atoms; (c) a trialkyl trithiophosphite; (f) a polyalkyoxyalkyl sulphide; (g) a polyalkoxyalkoxyalkyl sulphide; or (h) a polyhydroxyalkyl sulphide.  The stabilizer may be applied to the surface of the foodstuffs by spraying in the form of a dispersion or by dipping in a vegetable oil solution.  Specification 834,291 is referred to.