Patent GB-621104-A (GB)
Title: Non-ionic surface active agent
IPC: C11C3/00
Filed: 1943-08-06
Abstract: Non-ionic surface-active agents comprising esters containing free hydroxyl groups are prepared by heating a fatty acid polymer, as hereinafter defined, with more than one molecular proportion of a water-soluble polyalkylene oxide or polyalkylene glycol of molecular weight exceeding 300 in the presence of an acid catalyst.  The fatty acid polymers are those obtained by heating fatty acids containing more than 10 carbon atoms and two or more ethylene linkages to such a temperature and for such a time as to effect a high degree of conversion of the acid to the dimeric form and thereafter distilling in a vacuum to remove any unpolymerized materials; the polymerized product consists substantially of the dimeric acid with a small percentage, usually 2 to 10 per cent, of the trimeric acid; the unsaturated polymeric acids may be subsequently modified by catalytic hydrogenation.  Generally, reaction is effected at about 140 DEG  to 150 DEG  C.  The esters, stated to be novel, exert solubilizing action on many anionic- and cationic-organic compounds in the same water solution and possess wetting, emulsifying and dispersing properties.  The compounds may be reacted with monomeric unsaturated fatty acids to esterify the free hydroxyl groups and form products having similar properties. In examples: (1) unhydrogenated dibasic acids obtained by heat-treating the fatty acids of soya-bean oil, castor oil, linseed-oil and tung oil and vacuum distilling off the unpolymerized acid, and the unhydrogenated polymeric polybasic fatty acid comprising the still residues from the fractional distillation of the isomerized fatty acids obtained by autoclaving linseed oil with caustic soda, are each reacted with a polyethylene oxide (mol. weight 4000) in a 1 : 2 molar proportion at 140 DEG  C. for 2 hours to yield wax-like esters; in like manner, (2) linseed oil fatty acids obtained as in (1) above and a dimeric dibasic fatty acid obtained by catalytically hydrogenating the dimeric acids remaining after removal of monomeric acids from thermally polymerized castor oil acids are each reacted with a poly-ethylene oxide (mol. weight 1500) and (3) dimeric soyabean fatty acid obtained as in (1) is reacted with a polyethylene glycol (mol. weight 326); (4) dimeric linseed oil fatty acid is reacted with a product (mol. weight 1700) prepared by reacting 12 moles. propylene oxide with 1 mol. polyethylene oxide (mol. weight 1500) in presence of sulphuric acid; (5) the product of (1) derived from dimeric soya bean oil acids is further reacted with oleic acid.  Specifications 380,431 and 537,211 are referred to.  The Specification as open to inspection under Sect. 91 relates to the condensation of any polymeric long-chain fatty acid with a high molecular weight water-soluble polyalkylene oxide.  A mixture of polymeric and monomeric long-chain fatty acids may be used, the polymeric acid being obtained by heat-treatment of a portion of the monomeric acid.  In an additional example, a mixture of polymeric and monomeric acids obtained by heat-polymerizing the mixed fatty acids from soya bean oil is used as in (1) above. This subject-matter does not appear in the Specification as accepted.ALSO:Non-ionic surface-active agents comprising esters containing free hydroxyl groups are prepared by heating a fatty acid polymer, as hereinafter defined, with more than one molecular proportion of a water-soluble polyalkylene oxide or polyalkylene glycol of molecular weight exceeding 300 in the presence of an acid catalyst.  The fatty acid polymers are those obtained by heating fatty acids containing more than 10 carbon atoms and two or more ethylene linkages to such a temperature and for such a time as to effect a high degree of conversion of the acid to the dimeric form and thereafter distilling in a vacuum to remove any unpolymerized materials; the polymerized product consists substantially of the dimeric acid with a small percentage, usually 2 to 10 per cent, of the trimeric acid; the unsaturated polymeric acids may be subsequently modified by catalytic hydrogenation. Generally, reaction is effected at about 140 DEG  to 150 DEG  C.  The esters, stated to be novel, exert solubilizing action on many anionic- and cationic-organic compounds in the same water solution and possess wetting, emulsifying and dispersing properties.  The compounds may be reacted with monomeric unsaturated fatty acids to esterify the free hydroxyl groups and form products having similar properties.  In examples: (1) unhydrogenated dibasic acids obtained by heat-treating the fatty acids of soya-bean oil, castor oil, linseed-oil and tung oil and vacuum-distilling off the unpolymerized acid, and the unhydrogenated polymeric polybasic fatty acid comprising the still residues from the fractional distillation of the isomerized fatty acids obtained by autoclaving linseed oil with caustic soda, are each reacted with a polyethylene oxide (mol. weight 4000) in a 1 : 2 molar proportion at 140 DEG  C. for 2 hours to yield wax-like esters; in like manner, (2) linseed oil fatty acids obtained as in (1) above and a dimeric dibasic fatty acid obtained by catalytically hydrogenating the dimeric acids remaining after removal of monomeric acids from thermally polymerized castor oil acids are each reacted with a polyethylene oxide (mol. weight 1500) and (3) dimeric soya-bean fatty acid obtained as in (1) is reacted with a polyethylene glycol (mol. weight 326); (4) dimeric linseed oil fatty acid is reacted with a product (mol. weight 1700) prepared by reacting 12 moles. propylene oxide with 1 mole. polyethylene oxide (mol. weight 1500) in presence of sulphuric acid; (5) the product of (1) derived from dimeric soyabean oil acids is further reacted with oleic acid.  Specifications 380,431 and 537,211 are referred to.  The Specification as open to inspection under Sect. 91 relates to the condensation of any polymeric long-chain fatty acid with a high molecular weight water-soluble polyalkylene oxide.  A mixture of polymeric and monomeric long chain fatty acids may be used, the polymeric acid being obtained by heat-treatment of a portion of the monomeric acid.  In an additional example, a mixture of polymeric and monomeric acids, obtained by heat-polymerizing the mixed fatty acids from soyabean oil is used as in (1) above. This subject-matter does not appear in the Specification as accepted.ALSO:Non-ionic surface-active agents comprising esters containing free hydroxyl groups are prepared by heating a fatty acid polymer, as hereinafter defined, with more than one molecular proportion of a water-soluble polyalkylene oxide or polyalkylene glycol of molecular weight exceeding 300 in the presence of an acid catalyst (see Group IV (b)). The fatty acid polymers are those obtained by heating fatty acids containing more than 10 carbon atoms and two or more ethylene linkages to such a temperature and for such a time as to effect a high degree of conversion of the acid to the dimeric form and thereafter distilling in a vacuum to remove any unpolymerized materials; the polymerized product consists substantially of the dimeric acid with a small percentage, usually 2 to 10 per cent, of the trimeric acid; the unsaturated polymeric acids may be subsequently modified by catalytic hydrogenation. The esters, stated to be novel, exert solubilizing action on many anionic- and cationic-organic compounds in the same water solution and possess wetting, emulsifying and dispersing properties.  The compounds may be reacted with monomeric unsaturated fatty acids to esterify the free hydroxyl groups and form products having similar properties.  In examples: (1) unhydrogenated dibasic acids obtained by heat-treating the fatty acids of soya-bean oil, castor oil, linseed oil and tung oil and vacuum distilling off the unpolymerized acid, and the unhydrogenated polymeric polybasic fatty acid comprising the still residues from the fractional distillation of the isomerized fatty acids obtained by autoclaving linseed oil with caustic soda, are each reacted with a polyethylene oxide (mol. weight 4000) in a 1 : 2 molar proportion at 140 DEG  C. for 2 hours to yield wax-like esters; in like manner, (2) linseed oil fatty acids obtained as in (1) above and a dimeric dibasic fatty acid obtained by catalytically hydrogenating the dimeric acids remaining after removal of monomeric acids from thermally polymerized castor oil acids are each reacted with a polyethylene oxide (mol. weight 1500) and (3) dimeric soyabean fatty acid obtained as in (1) is reacted with a polyethylene glycol (mol. weight 326); (4) dimeric linseed oil fatty acid is reacted with a product (mol. weight 1700) prepared by reacting 12 moles. propylene oxide with 1 mol. polyethylene oxide (mol. weight 1500) in presence of sulphuric acid; (5) the product of (1) derived from dimeric soya bean oil acids is further reacted with oleic acid.  Specifications 380,431 and 537,211 are referred to.  The Specification as open to inspection under Sect. 91 describes surface-active agents obtained by the condensation of any polymeric long-chain fatty acid with a high molecular weight water-soluble polyalkylene oxide.  A mixture of polymeric and monomeric long-chain fatty acids may be used, the polymeric acid being obtained by heat-treatment of a portion of the monomeric acid.  In an additional example, a mixture of polymeric and monomeric acids obtained by heat-polymerizing the mixed fatty acids from soya bean oil is used as in (1) above.  This subject-matter does not appear in the Specification as accepted.