Process for preparing ethylene glycol esters

Claim 2

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene, with a hydrocarbon carboxylic acid having up to 30 carbon atoms, oxygen, an effective amount of a halogen selected form the group consisting of at least one of bromine and a bromine containing compound yielding bromide ions during reaction; and an effective amount of at least one of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn, V, Ga, As, Co, Cr, Cu and Ag; at temperatures from 80*C. to 200*C., to form the desired ester the amount of halogen, expressed as weight % halogen based on total weight of solution, being from 0.01% to 30% and the amount of variable valence metal cation, expressed as equivalents of cation to equivalent of halogen, being from 1:0.01 to 1:100.

Claim 3

The process of claim 1 wherein the halogen is selected from the group consisting of bromine, hydrobromic acid, and an alkali and alkaline earth metal bromide.

Claim 4

The process of claim 1 wherein the variable valence metal is Ce, Sb, Mn or V.

Claim 5

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with a hydrocarbon carboxylic acid having up to 30 carbon atoms, oxygen, an effective amount of at least one of a halogen selected from the group consisting of chlorine and a chlorine containing compound yielding chloride ions during reaction; and an effective amount of at least one of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn, V, Ga, As, Co, Cu, Ag and Cr; at temperatures from 80*C. to 200*C., to form the desired ester the amount of halogen, expressed as weight percent halogen based on total weight of solution, being from 0.01 percent to 30 percent and the amount of variable valence metal cation, expressed as equivalents of cation to equivalent of halogen, being from 1:0.01 to 1:100.

Claim 6

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with a hydrocarbon carboxylic acid having up to 30 carbon atoms, oxygen, an effective amount of at least one of a halogen selected from the group consisting of chlorine and a chlorine containing compound yielding chloride ions during reaction; and an effective amount of at least one of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn, V, Ga, As, Co, Cu, Ag and Cr; at temperatures from 80*C. to 200*C., to form the desired ester the amount of halogen, expressed as weight percent halogen based on total weight of solution, being from 0.01 percent to 30 percent and the amount of variable valence metal cation, expressed as equivalents of cation to equivalent of halogen, being from 1:0.01 to 1:100.

Claim 7

The process of claim 4 wherein the halogen is selected from the group consisting of chlorine, hydrochloric aciD, and an alkali and alkaline earth metal chloride.

Claim 8

The process of claim 4 wherein the variable valence metal is Ce, Mn, or Co.

Claim 9

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene, with oxygen, a hydrocarbon carboxylic acid having up to 30 carbon atoms an effective amount of a halogen selected from at least one member of the group consisting of bromine, hydrogen bromide, alkali metal bromides, alkaline earth metal bromides, lower alkyl bromides, and the bromides of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag and V; an effective amount of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag or V; at a temperature of 80*C. to 200*C., wherein the wt. % halogen is from 0.01 to 30 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:01 to 1:100 to form the desired ester.

Claim 10

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene, with oxygen, a hydrocarbon carboxylic acid having up to 30 carbon atoms an effective amount of a halogen selected from at least one member of the group consisting of bromine, hydrogen bromide, alkali metal bromides, alkaline earth metal bromides, lower alkyl bromides, and the bromides of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag and V; an effective amount of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag or V; at a temperature of 80*C. to 200*C., wherein the wt. % halogen is from 0.01 to 30 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:01 to 1:100 to form the desired ester.

Claim 11

The process of claim 7 wherein the variable valence metal cation is Ce, Sb, Mn or V, the wt. % of halogen is from 0.1 percent to 20 percent, based on the total weight of solution, the temperature of reaction is from 100* to 200*C. and the ratio of cation to halogen is 1:0.2 to 1:40.

Claim 12

A process in accordance with claim 7 wherein the carboxylic acid is acetic acid.

Claim 13

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene, with oxygen, a hydrocarbon carboxylic acid having up to 30 carbon atoms, an effective amount of a halogen selected from at least one member of the group consisting of chlorine, hydrogen chloride, alkali metal chlorides, alkaline earth metal chlorides, lower alkyl chlorides, and the chlorides of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag, and V; an effective amount of a variable valence metal cation selected form the group consisting of Ce, Mn, Sb, V, Ga, As, Cr, Cu, Ag and Co; at temperatures of 80*C. to 200*C., wherein the wt. % halogen is from 0.01 to 30 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:.01 to 1:100 to form the desired ester.

Claim 14

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene, with oxygen, a hydrocarbon carboxylic acid having up to 30 carbon atoms, an effective amount of a halogen selected from at least one member of the group consisting of chlorine, hydrogen chloride, alkali metal chlorides, alkaline earth metal chlorides, lower alkyl chlorides, and the chlorides of Ce, Sb, Mn, Ga, As, Co, Cr, Cu, Ag, and V; an effective amount of a variable valence metal cation selected form the group consisting of Ce, Mn, Sb, V, Ga, As, Cr, Cu, Ag and Co; at temperatures of 80*C. to 200*C., wherein the wt. % halogen is from 0.01 to 30 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:.01 to 1:100 to form the desired ester.

Claim 15

The process of claim 10 wherein the variable valence metal cation is Ce, Mn, Cu or Co; the wt. % halogen is from 0.1 to 20 percent, based on the total weight of solution; the temperature of reaction is from 100* to 200*C. and the ratio of cation to halogen is 1:0.2 to 1:40.

Claim 16

A process in accordance with claim 10 wherein the carboxylic acid is acetic acid.

Claim 17

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with oxygen, a monobasic lower aliphatic hydrocarbon carboxylic acid; a halogen selected form the group consisting of bromine, alkali metal or alkaline earth metal bromide and hydrobromic acid; an effective amount of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn and V; at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol ester.

Claim 18

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with oxygen, a monobasic lower aliphatic hydrocarbon carboxylic acid; a halogen selected form the group consisting of bromine, alkali metal or alkaline earth metal bromide and hydrobromic acid; an effective amount of a variable valence metal cation selected from the group consisting of Ce, Sb, Mn and V; at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol ester.

Claim 19

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with oxygen, a monobasic lower aliphatic hydrocarbon carboxylic acid; a halogen selected from the group consisting of chlorine, hydrochloric acid and alkali and alkaline earth metal chloride; an effective amount of a variable valence metal cation selected form the group consisting Of Ce, Mn, and Co; at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol ester.

Claim 20

A process for preparing an ethylene glycol ester which comprises intimately contacting ethylene with oxygen, a monobasic lower aliphatic hydrocarbon carboxylic acid; a halogen selected from the group consisting of chlorine, hydrochloric acid and alkali and alkaline earth metal chloride; an effective amount of a variable valence metal cation selected form the group consisting Of Ce, Mn, and Co; at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol ester.

Claim 21

A process for preparing ethylene glycol diacetate which comprises intimately contacting ethylene, with oxygen, acetic acid, a halogen selected from the group consisting of bromine, and hydrobromic acid; a variable valence metal cation selected from the group consisting of Ce, Sb and Mn at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol diacetate.

Claim 22

A process for preparing ethylene glycol diacetate which comprises intimately contacting ethylene, with oxygen, acetic acid, a halogen selected from the group consisting of bromine, and hydrobromic acid; a variable valence metal cation selected from the group consisting of Ce, Sb and Mn at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalents of cation to equivalents of halogen is from 1:1 to 1:20, to form the desired ethylene glycol diacetate.

Claim 23

A process for preparing ethylene glycol diacetate which comprises intimately contacting ethylene, with oxygen, acetic acid, a halogen selected from the group consisting of chlorine and hydrochloric acid; a variable valence metal cation selected form the group consisting of Ce, Mn or Co at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalence of cation to equivalence of halogen is from 1:1 to 1:20, to form the desired ethylene glycol diacetate.

Claim 24

A process for preparing ethylene glycol diacetate which comprises intimately contacting ethylene, with oxygen, acetic acid, a halogen selected from the group consisting of chlorine and hydrochloric acid; a variable valence metal cation selected form the group consisting of Ce, Mn or Co at a temperature of 120* to 180*C., wherein the wt. % halogen is from 0.05 to 10 percent, based on the total weight of solution, and the amount of variable valence metal cation expressed in terms of equivalence of cation to equivalence of halogen is from 1:1 to 1:20, to form the desired ethylene glycol diacetate.