Patent GB-1011117-A (GB)
Title: Phosphite, phosphate and thiophosphate esters
IPC: C07F9/40
Filed: 1962-07-13
Abstract: The invention comprises compounds of the general formula <FORM:1011117/C3/1> wherein R1, R2, R5, R6 and R7 are residues of polypropylene glycol from which one of the hydroxyl groups has been removed; R3 and R4 are residues of polyethylene or polypropylene glycol from which the two hydroxyl groups have been removed; n is zero or an integer; and X1, X11 and X111 are nothing, oxygen or sulphur. Phosphites of the above general formula may be prepared by heating, preferably in a vacuum, a tri-hydrocarbon phosphite or trishaloarylphosphite with a polypropylene glycol, or a mixture of at least 55% polypropylene glycol with polyethylene glycol, in the presence of an alkali metal alcoholate or phenate, dihydrocarbon phosphite or dihaloarylphosphite as catalyst at a molar ratio of glycol to phosphite reactant of greater than 2: 1 but less than 3: 1 and removing the monohydroxy compound formed. Polymeric phosphites of dipropylene and/or tripropylene glycol can also be prepared by distilling out the appropriate amount of dipropylene and/or tripropylene glycol or heating tris-dipropylene and/or tris-tripropylene glycol phosphite or mixed tripropylene bis-dipropylene glycol in a vacuum, preferably in the presence of one of the above specified catalysts. Phosphates and thiophosphates of the above general formula may be prepared by oxidation of the corresponding phosphites with a stoichiometric amount of, for example, hydrogen peroxide or other peroxides, and addition of the stoichiometric quantity of sulphur to the corresponding phosphite and subsequent heating to 110 DEG  to 130 DEG  C., respectively.  The polymeric dipropylene and/or tripropylene phosphates and thiophosphates may also be obtained by distillation of the corresponding phosphates and thiophosphates in analogous manner to that of the polymeric phosphite.  The compounds of the invention are usually prepared as mixtures and generally are 50%, usually about 90%, of the free hydroxyl groups are secondary; R1, R2, R5, R6 and R7 usually having the structure HO.CH(CH3)CH2O[CH2CH(CH3)O]x-where is an integer.  Specifications 942,776 and 1,011,119 are referred to.ALSO:The invention comprises compounds of the general formula <FORM:1011117/C2/1> wherein R1, R2, R5, R6 and R7 are residues of polypropylene glycol from which one of the hydroxyl groups has been removed; R3 and R4 are residues of polyethylene or polypropylene glycol from which the two hydroxyl groups have been removed; n is zero or an integer; and X1, X11 and X111 are nothing, oxygen or sulphur. Phosphites of the above general formula may be prepared by heating, preferably in a vacuum, a trishydrocarbon phosphite or a trishaloaryl phosphite with a propylene glycol, or a mixture of at least 55% polypropylene glycol with polyethylene glycol, in the presence of an alkali metal alcoholate or phenate, dihydrocarbon phosphite, or dihaloaryl phosphite as catalyst at a molar ratio of glycol to phosphite reactant of greater than 2 : 1 but less than 3 : 1, and removing the monohydroxy compound formed.  Polymeric phosphites of dipropylene and/or tripropylene glycol can also be prepared by distilling out the appropriate amount of dipropylene and/or tripropylene glycol on heating trisdipropylene or tristripropylene glycol phosphite or mixed tripropylene bisdipropylene glycol phosphite in a vacuum, preferably in the presence of one of the above specified catalysts.  Phosphates and thiophosphates of the above general formula may be prepared by oxidation of the corresponding phosphites with a stoichiometric amount of, for example, hydrogen peroxide or other peroxy compound, and addition of a stoichiometric quantity of sulphur to the corresponding phosphite and subsequent heating of the mixture to 110 DEG  to 130 DEG  C., respectively.  The polymeric dipropylene and/or tripropylene phosphates and thiophosphates can also be obtained by distillation of the corresponding phosphates and thiophosphates in analogous manner to that of the polymeric phosphites.  The compounds of the invention are usually prepared as mixtures and generally over 50%, usually about 90%, of the free hydroxyl groups are secondary; R1, R2, R5, R6 and R7 usually having the structure <FORM:1011117/C2/2> where x is an integer.  Specifications 942,776 and 1,001,119 are referred to.