Patent GB-1011118-A (GB)
Title: Phosphate, phosphite, thiophosphate and phosphonate esters
IPC: C08G63/692
Filed: 1962-07-19
Abstract: The invention comprises (a) secondary and tertiary phosphite esters of alkaneetherpolyols, said polyols having 3 to 6 hydroxyl groups and being the ethers of C3 to C6 alkane-polyols having 3 to 6 hydroxyl groups and alkylene glycols or polyalkyleneglycols, said esters having a plurality of free alcoholic hydroxyl groups; (b) phosphate esters corresponding to said phosphite esters; (c) thiophosphate esters corresponding to said phosphite esters; (d) phosphonate esters isomeric with said phosphite esters; (e) condensation polymers of said phosphite esters, having up to 7 phosphorus atoms; and (f) polyphosphonates isomeric with said condensation polymers.  The phosphites and polymers thereof have the general formulae <FORM:1011118/C3/1> and <FORM:1011118/C3/2> wherein R1 is an alkaneetherpolyol from which one hydroxyl group has been removed, R2 is an alkaneetherpolyol from which two hydroxyl groups have been removed and n is a whole number from 0 to 6.  Phosphite esters of Formula (I) wherein n = 0 may be prepared by heating, preferably in a vacuum, the appropriate alkaneetherpolyol with a trihydrocarbon or trihaloaryl phosphite in the molar ratio of at least 3 to 1 in the presence of a dihydrocarbon or dihaloaryl phosphite or an alkali metal alcoholate or phenolate as catalyst.  Those compounds of Formula II wherein n = 0 may be prepared by heating the appropriate alkaneetherpolyol with a dihydrocarbon phosphite in the molar ratio of at least 2 to 1, preferably under vacuum.  The phosphates (b) and thiophosphates (c) may be prepared from the compounds of Formula (I) wherein n = o by oxidation with, for example, a stoichiometric amount of aqueous hydrogen peroxide or other peroxide and by heating at 110 DEG  to 130 DEG  C. with sulphur, respectively.  Polymers (e) may be obtained by those processes used to produce the compounds of Formulae (I) and (II) wherein n = 0 when less than 3 moles and less than 2 moles, respectively, of polyol are employed per mole of phosphite reactant.  The phosphonates (d) and (f) may be prepared by heating the compounds of Formula (I) with a catalytic amount, e.g. 0.5 to 10%, of an alkyl halide.  Numerous polyol reactants and ester products are specified including those products derived from polyethers. Specification 1,011,119 is referred to.ALSO:The invention comprises (a) secondary and tertiary phosphite esters of alkane-ether polyols, said polyols having 3 to 6 hydroxyl groups and being the ethers of C3 to C6 alkanepolyols having 3 to 6 hydroxyl groups and alkylene glycols or polyalkylene glycols, said esters having a plurality of free alcoholic hydroxyl groups; (b) phosphate esters corresponding to said phosphite esters; (c) thiophosphate esters corresponding to said phosphite esters; (d) phosphonate esters isomeric with said phosphite esters; (e) condensation polymers of said phosphite esters, having up to 7 phosphorus atoms; and (f) polyphosphonates isomeric with said condensation polymers.  The phosphites and polymers thereof have the general formulae <FORM:1011118/C2/1> and <FORM:1011118/C2/2> wherein R1 is an alkane-etherpolyol from which one hydroxyl group has been removed, R2 is an alkane-etherpolyol from which two hydroxyl groups have been removed and n is a whole number from 0 to 6.  Phosphite esters of formula (I) wherein n=0 may be prepared by heating, preferably under vacuum, the appropriate alkane-etherpolyol with a trihydrocarbon or trihaloaryl phosphite in the molar ratio of at least 3 to 1 in the presence of a dihydrocarbon or dihaloaryl phosphite or an alkali metal alcoholate or phenolate as catalyst.  Those compounds of Formula (II) wherein n=O may be prepared by heating the appropriate alkaneetherpolyol with a dihydrocarbon phosphite in the molar ratio of at least 2 to 1, preferably under vacuum.  The phosphates (b) and thiophosphates (c) may be prepared from the compounds of Formula (I) wherein n=O by oxidation with, for example, a stoichiometric amount of aqueous hydrogen peroxide or other peroxide and by heating at 110 DEG  to 130 DEG  C. with sulphur, respectively.  Polymers (e) may be obtained by those processes used to produce the compounds of Formulae (I) and (II), wherein n=O when less than 3 moles and less than 2 moles, respectively, of polyol are employed per mole of phosphite reactant.  The phosphonates (d) and (f) may be prepared by heating the compounds of Formula (I) with a catalytic amount, e.g. 0.5 to 10%, of an alkyl halide.  Numerous polyol reactants and ester products are specified and the products of the invention may be employed to produce polymethanes by reaction with polyisocyanates. Specification 1,011,119 is referred to.