Process for the preparation of linear polyethylenepolyamines by reacting monoethanolamine with ethylenediamine in the presence of an intercalatively active catalyst

Claim 2

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process which comprises: (a) using, as the catalyst, an intercalatively catalytically active tetravalent zirconium polymeric reaction product of an organo phosphonic acid or an ester thereof with a compound of tetravalent zirconium reactive therewith; and (b) contacting a mixture of ethylenediamine and monoethanolamine in the molar ratio of about 1 to about 5 moles of ethylenediamine per mole of monoethanolamine with said catalyst at a temperature of about 250° to about 400° C.

Claim 3

A method as in claim 1 wherein the tetravalent zirconium compound is zirconyl chloride and wherein the organo phosphonic acid is trimethylenediphosphonic acid.

Claim 4

A method as in claim 1 wherein the zirconium compound is zirconyl chloride and wherein the organo phosphonic acid is carboxymethyl phosphonic acid.

Claim 5

A method as in claim 1 wherein the zirconium compound is zirconyl chloride and wherein the organo phosphonic acid is phenylphosphonic acid.

Claim 6

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a catalyst to provide an essentially noncyclic reaction product comprising polyethylenepolyamines, the improvement for conducting said process which comprises: (a) using, as the catalyst, an intercalatively catalytically active tetravalent zirconium polymeric reaction product of an organo phosphonic acid with a tetravalent zirconium halide, said polymeric reaction product containing a molar ratio of phosphorous to zirconium of about 2 to 1; the organo groups of said polymeric reaction product being covalently bonded to phosphorous through a carbon linkage and the phosphorous being bonded to the zirconium through an oxygen linkage; and (b) contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to about 5 moles of ethylenediamine per mole of monoethanolamine with said catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

Claim 7

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a catalyst to provide an essentially noncyclic reaction product comprising polyethylenepolyamines, the improvement for conducting said process which comprises: (a) using, as the catalyst, an intercalatively catalytically active tetravalent zirconium polymeric reaction product of an organo phosphonic acid with a tetravalent zirconium halide, said polymeric reaction product containing a molar ratio of phosphorous to zirconium of about 2 to 1; the organo groups of said polymeric reaction product being covalently bonded to phosphorous through a carbon linkage and the phosphorous being bonded to the zirconium through an oxygen linkage; and (b) contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to about 5 moles of ethylenediamine per mole of monoethanolamine with said catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

Claim 8

A method as in claim 5 wherein the zirconyl halide is zirconyl chloride.

Claim 9

A method as in claim 6 wherein the phosphonic acid is trimethylene diphosphonic acid.

Claim 10

A method as in claim 6 wherein the phosphonic acid is carboxymethyl phosphonic acid.

Claim 11

A process as in claim 6 wherein the phosphonic acid is phenyl phosphonic acid.

Claim 12

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a catalyst to provide an essentially noncyclic reaction product comprising polyethylenepolyamines, the improvement for conducting said process which comprises: a. using a catalyst consisting essentially of an intercalatively catalytically active tetravalent zirconium polymeric reaction product prepared by reacting an alkylenediphosphonic acid, a carboxymethylphosphonic acid or a phenylphosphonic acid with an amount of a tetravalent zirconium halide sufficient to provide a polymeric reaction product having a molar ratio of phosphorous to zirconium of about 2 to 1; the organo groups of said polymeric reaction product being covalently bonded to phosphorous through a carbon linkage and the phosphorous being bonded to the zirconium through an oxygen linkage; and b. contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole of monoethanolamine with said catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig to obtain an essentially noncyclic reaction product comprising diethylenetriamine.

Claim 13

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a catalyst to provide an essentially noncyclic reaction product comprising polyethylenepolyamines, the improvement for conducting said process which comprises: a. using a catalyst consisting essentially of an intercalatively catalytically active tetravalent zirconium polymeric reaction product prepared by reacting an alkylenediphosphonic acid, a carboxymethylphosphonic acid or a phenylphosphonic acid with an amount of a tetravalent zirconium halide sufficient to provide a polymeric reaction product having a molar ratio of phosphorous to zirconium of about 2 to 1; the organo groups of said polymeric reaction product being covalently bonded to phosphorous through a carbon linkage and the phosphorous being bonded to the zirconium through an oxygen linkage; and b. contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole of monoethanolamine with said catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig to obtain an essentially noncyclic reaction product comprising diethylenetriamine.

Claim 14

A method as in claim 10, wherein the zirconyl halide is zirconyl chloride.

Claim 15

A method as in claim 11, wherein the phosphonic acid is trimethylenediphosphonic acid.

Claim 16

A method as in claim 11, wherein the phosphonic acid is carboxymethyl phosphonic acid.

Claim 17

A method as in claim 11, wherein the phosphonic acid is phenyl phosphonic acid.