Patent GB-683884-A (GB)
Title: Improvements in or relating to methods of making oxyalkylene condensation products
Filed: 1948-11-10
Abstract: <PICT:0683884/IV (a)/1> Alkylene oxide condensation products are prepared from water-insoluble organic compounds containing an hydroxyl, carboxyl, amino or mercapto group by a process comprising continuously introducing an alkylene oxide which boils below 200 DEG C. into a reaction zone at such a rate that the pressure is maintained substantially constant and the alkylene oxide is present in the gaseous state, spraying into the zone, in a finely divided liquid form, the said water-insoluble organic compound to react with the alkylene oxide, cooling to maintain a temperature at which substantial decomposition of the reaction products is avoided and continuously recycling and spraying the resulting products into the zone for further reaction until a predetermined number of alkylene oxide groups have been introduced into the said organic compound. The required cooling is preferably effected by withdrawing the products, cooling and then recycling for further reaction.  For safe operation, an inert atmosphere, for example of nitrogen, methane or butane, is maintained in the reaction zone.  Reaction temperatures of the order of 125-200 DEG  C. are normally employed.  Condensation catalysts may be employed such as bleaching earths, active charcoal, sulphuric or phosphoric acid, sodium or potassium bisulphate, sodium or potassium hydroxide or alkali metal alcopolates.  The reaction using ethylene oxide may be carried out under an ethylene oxide pressure of about 6 to 55 lbs./sq. inch and an inert gas pressure of an atmosphere; the reaction may proceed until from 1 to 50 ethenoxy groups have been introduced into the molecule of water - insoluble organic reactant.  Specified water-insoluble organic compounds having an hydroxyl, carboxyl, amino or mercapto group and containing in general at least 6 carbon atoms, are abietic acid or products containing the same such as rosin, rosin oil and tall oil, branched chain mercaptans having from 6 to 18 carbon atoms, and N-methylol amides of the general formula R.CONH.CH2OH, where R is an aliphatic radical having from 11 to 27 carbon atoms; U.S.A. Specification 1,970,578 is referred to for further examples.  In addition to ethylene oxide, propylene and butylene oxides are mentioned as suitable alkylene oxide reactants.  The products derived from ethylene oxide and abietic acid or products containing the same may be used in electrolytic plating baths, cosmetics or ointments or as detergents alone or with alkali metal phosphates; those obtained from the branched chain mercaptans and N-methylol amides may also be used as or in detergents.  Examples illustrate the reaction of ethylene oxide with tall oil and tertiary dodecyl mercaptan, respectively, employing the apparatus shown wherein a reactor 11 is charged with, say, tall oil from a feed tank 14 via line 16 and then ethylene oxide is introduced via line 7, valve 8 and inlet 10 from feed tank 2, the latter being maintained under inert gas pressure and connected by a pressure balancing line 6 to the reactor 11.  The liquid mixture in the reactor is continuously withdrawn via line 18 and pumped through a cooler 30 and/or its by-pass line 22 and thereafter sprayed back into the reactor via nozzle 25; meanwhile, ethylene oxide is fed into the reactor at a rate governed by a pressure controller 12 operating valve 8 to maintain the pressure in the reactor; the finished product is finally pumped from the system via line 33.  The bulk of the reaction occurs in the liquid mixture in the bottom of the reactor, but by lengthening the absorption or reaction zone and adjusting other reaction conditions the reaction may be carried out while the water-insoluble compound is substantially wholly in the atomized state.  Specifications 643,456 and 675,993 are referred to.  The Specification as open to inspection under Sect. 91 refers to the use of alkylene oxides and organic compounds having at least one reactive hydrogen atom in general as reagents in the above process and does not stipulate as essential a feed rate of alkylene oxide such that the reaction pressure is maintained substantially constant.  This subject-matter does not appear in the Specification as accepted.ALSO:Alkylene oxide condensation products are prepared from water-insoluble organic compounds containing an hydroxyl, carboxyl, amino or mercapto group by a process comprising continuously introducing an alkylene oxide which boils below 200 DEG  C. into a reaction zone at such a rate that the pressure is maintained substantially constant and the alkylene oxide is present in the gaseous state, spraying in a finely-divided liquid form into the zone the said water-insoluble organic compound to react with the alkylene oxide, cooling to maintain a temperature at which substantial decomposition of the reaction products is avoided and continuously recycling and spraying the resulting products into the zone for further reaction until a predetermined number of alkylene oxide groups have been introduced into the said organic compound.  The required cooling is preferably effected by withdrawing the products, cooling and then recycling for further reaction.  For safe operation, an inert atmosphere for example of nitrogen, methane or butane, is maintained in the reaction zone. Reaction temperatures of the order of 125-200 DEG  C. are normally employed.  Condensation catalysts may be employed such as bleaching earths, active charcoal, sulphuric or phosphoric acid, sodium or potassium bisulphate, sodium or potassium hydroxide or alkali metal alcoholates.  The reaction using ethylene oxide may be carried out under an ethylene oxide pressure of about 6 to 55 lbs./square inch and an inert gas pressure of an atmosphere; the reaction may proceed until from one to 50 ethenoxy groups have been introduced into the molecule of water-insoluble organic reactant.  Specified water-insoluble organic compounds having an hydroxyl, carboxyl, amino or mercapto group and containing in general at least 6 carbon atoms, are abietic acid or products containing the same such as rosin, rosin oil and tall oil, branched chain mercaptans having from 6 to 18 carbon atoms, and N-methylol amides of the general formula R.CONH.CH2OH, where R is an aliphatic radical having from 11 to 27 carbon atoms; U.S.A.  Specification 1,970,578 is referred to for further examples.  In addition to ethylene oxide, propylene and butylene oxides are mentioned as suitable alkylene oxide reactants.  The products derived from ethylene oxide and abietic acid or products containing the same may be used in eletrolytic plating baths, cosmetics or ointments or as detergents alone or with alkali metal phosphates; those obtained from the branched chain mercaptans and N-methylol amides may also be used as or in detergents.  Examples illustrate the reaction of ethylene oxide with tall oil and tertiary dodecyl mercaptan, respectively, employing the apparatus shown wherein, a reactor 11 is charged with, say, tall oil from a feed tank 14 via line 16 and then ethylene oxide is introduced via line 7, valve 8 and inlet 10 from feed tank 2, the latter being maintained under inert gas pressure and connected by a pressure balancing line 6 to the reactor 11.  The liquid mixture in the reactor is continuously withdrawn via line 18 and pumped through a cooler 30 and/or its by-pass line 22 and thereafter sprayed back into the reactor via nozzle 25; meanwhile ethylene oxide is fed into the reactor at a rate governed by a pressure controller 12 operating valve 8 to maintain the pressure in the reactor; the finished product is finally pumped from the <PICT:0683884/IV (b)/1> system via line 33.  The bulk of the reaction occurs in the liquid mixture in the bottom of the reactor but by lengthening the absorption or reaction zone and adjusting other reaction conditions the reaction may be carried out while the water-insoluble compound is substantially wholly in the atomized state.  Specifications 643,456 and 675,993 are referred to.  The Specification as open to inspection under Sect. 91, refers to the use of alkylene oxides and organic compounds having at least one reactive hydrogen atom in general as reagents in the above process and does not stipulate as essential a feed rate of alkylene oxide such that the reaction pressure is maintained substantially constant.  This subject-matter does not appear in the Specification as accepted.