Patent GB-1058845-A (GB)
Title: Process for producing phosphate esters
IPC: C07F9/09
Filed: 1964-04-22
Abstract: Phosphate esters are obtained by reacting molecular oxygen or air with one or more phosphites selected from the group of phosphites having the general formula <FORM:1058845/C2/1> where R represents an alkyl, chloroalkyl, alkenyl, chloroaryl or aryl radical, A represents a C2-C4 alkylene group and n represents a number (including 0) of from 0 to 150, R1 and R2 each represent a hydrogen atom, alkyl, alkenyl or aryl radical or the group R(OA)n, in the presence of catalytic amounts of hydrogen peroxide or an organic peroxide, preferably at a temperature of from 25 DEG  to 200 DEG  C. Specified phosphites include various trialkyl phosphites, trialkaryl phosphites, a tricycloalkaryl phosphite, diaryl alkyl phosphites, triaryl phosphites, phosphites derived from hydroxy compounds obtained by condensing at least one mole of ethylene oxide with an alcohol or phenol, and various primary and secondary phosphites.  If desired, the organic compound may be condensed with at least one mole of a C3-C4 alkylene oxide prior to condensation with ethylene oxide; suitable compounds containing active hydrogen are alcohols and phenols.  A preferred group of phosphites are those derived from polyalkylene oxide derivatives of phenolic compounds containing one or more alkyl substituents.  Preferred compounds of this type are derivatives of alkyl phenolic compounds in which the total number of carbon atoms is from 1 to 24.  Another preferred group of phosphites are those derived from alcohols obtained by reaction of alkylene oxides with C1 to C22 aliphatic alcohols and from condensation products of at least one mole of ethylene oxide with one mole of a multi-branched chain primary aliphatic oxo alcohol derived from a polyolefin having at least 7 carbon atoms and phosphites derived from oleyl alcohol and its alkoxylates with ethylene oxide.  Phosphites derived from alcohols obtained from metal alkyls formed by the polymerization of ethylene using Ziegler-type catalysts.  Suitable peroxides include diacyl aromatic peroxides, diacyl aliphatic peroxides, acid peroxides, ketone peroxides, aldehyde peroxides, alkyl peroxy-esters and alkyl peroxides and hydro-peroxides.  In carrying out the reaction oxygen or air is suitably introduced at the beginning of the reaction and continued until the reaction is complete.  The examples given include examples for the oxidation of tri-(dichlorophenol + 10 ethylene oxide molecules) phosphite, monodocosyl phosphite and dioleyl phosphite.  For comparative purposes the oxidation of tri-(nonyl phenol + 9 ethylene oxide molecules) phosphite with oxygen in the absence of peroxide is given.ALSO:Phosphate esters are obtained by reacting molecular oxygen or air with one or more phosphites selected from the group of phosphites having the general formula <FORM:1058845/C3/1> where R represents an alkyl, chloroalkyl, alkenyl, chloroaryl or aryl radical, A represents a C2-C4 alkylene group and n represents a number up to 150, R1 and R2 each represent hydrogen, alkyl, alkenyl, or aryl radicals or the group R(OA)n, in the presence of catalytic amounts of hydrogen peroxide or an organic peroxide, preferably at a temperature of from 25 DEG  C. to 200 DEG  C.  Specified phosphites include various triaryl phosphites, phosphites derived from hydroxy compounds obtained by condensing at least one mole of ethylene oxide with an alcohol or phenol, and various primary and secondary phosphites.  If desired the organic compound may be condensed with at least one mole of a C3-C4 alkylene oxide prior to condensation with ethylene oxide; suitable compounds containing active hydrogen are alcohols and phenols.  A preferred group of phosphites are those derived from polyalkylene oxide derivatives of phenolic compounds containing one or more alkyl substituents. Preferred compounds of this type are derivatives of alkyl phenolic compounds in which the total number of carbon atoms is from 1 to 24. Another preferred group of phosphites are those derived from alcohols obtained by reaction of alkylene oxides with C1 to C22 aliphatic alcohols and from condensation products of at least one mole of ethylene oxide with one mole of a multi-branched chain primary aliphatic oxo alcohol derived from a polyolefin having at least 7 carbon atoms and phosphites derived from oleyl alcohol and its alkoxylates with ethylene oxide. Phosphites derived from alcohols obtained from metal alkyls formed by the polymerization of ethylene using Ziegler type catalyst.  Suitable peroxides include diacyl aromatic peroxides, diacyl aliphatic peroxides, acid peroxides, ketone peroxides, aldehyde peroxides, alkyl peroxy-esters and alkyl peroxides and hydro-peroxides.  In carrying out the reaction oxygen or air is suitably introduced at the beginning of the reaction and continued until the reaction is complete.  The examples given include an example for the oxidation of tri(dichlorophenol + 10 ethylene oxide molecules) phosphite.  For comparative purposes the oxidation of tri(nonyl phenol + 9 ethylene oxide molecules) phosphite with oxygen in the absence of peroxide is given.