A method for the alkoxylation of alkanols in the presence of strontium-containing catalysts and promoters

Claim 3

A method as described in claim 1 wherein a) the polyol promoters contain 2 or more adjacent or non-adjacent hydroxyl containing groups of the general formula wherein R1, R 2 , and R 3 ,are, independently, linear or branched acyclic groups, alicyclic groups, cyclic groups, aryl groups or hydrogen and wherein the R-designated groups in addition can contain one or more functional groups selected from the group consisting of ether, amine, carboxyl, halogen, nitro, carbonyl, and amide; b) the aldehyde and ketone promoters contain one or more adjacent or non-adjacent carbonyl containing groups of the general formula wherein R1, and R 2 are, independently, linear or branched acyclic groups, alicyclic groups, cyclic groups, aryl groups or hydrogen, and wherein the R-designated groups in addition can contain one or more functional groups selected from the group consisting of hydroxyl, ether, carboxyl, carbonyl, amine, nitro or halogen; c) the primary, secondary or tertiary amide promoters contain one or more amide containing groups of the general formula wherein R 1 , R 2 , and R 3 are, independently, hydrogen, linear or branched acyclic groups, alicyclic groups, cyclic groups or aryl groups and wherein the R-designated groups can in addition contain one or more functional groups selected from the group consisting of hydroxyl, ether, carboxyl, carbonyl, amine, nitro or halogen; d) the primary, secondary or tertiary amine promoters contain one or more amine containing groups of the general formula wherein R l , R 21 and R 3 are, independently, hydrogen, linear or branched acyclic groups, alicyclic groups, cyclic groups, or aryl groups, and wherein the R-designated groups can in addition contain one or more functional groups selected from the group consisting of hydroxyl, ether, carbonyl, halogen, carboxyl, nitro, or amide; e) the organic acid promoters contain one or more adjacent or non-adjacent carboxylic acid containing groups of the general formula wherein R 1 is a hydrogen, linear or branched acyclic group, alicylic group, cyclic group, or aryl group and wherein R can in addition contain one or more functional groups selected from the group consisting of carbonyl, hydroxyl, halogen, ether, nitro, amine, or amide; f) the phenol promoters have one or more functional groups of the general formula wherein R 1 , R 2 , R 3 , R 4 , and R 5 can be hydrogen and at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is from the group consisting of halogen, hydroxyl, nitro, ether, or carbonyl, linear or branched acyclic group, alicyclic group, cyclic group, aryl group or substituted aryl group and wherein at least one acyclic or alicyclic group contains at least 17 carbon atoms and wherein, in addition, the R-designated groups can contain one or more functional groups selected from the group consisting of halogen, ether, nitro, carboxyl, carbonyl, amine, amide, or hydroxyl.

Claim 4

A method as described in claim 2 wherein the alkoxylation is carried out using ethylene oxide, propylene oxide, or mixtures of these.

Claim 5

A method as described in claim 3 wherein the catalyst is selected from the group consisting of strontium metal, strontium hydride, strontium hydroxide, hydrated strontium hydroxide, or strontium oxide.

Claim 6

A method as described in claim 4 wherein the reaction is carried out at a pressure of up to about 100 pounds per square inch gauge.

Claim 7

A method as described in claim 5 wherein ethylene oxide is used as the alkoxylation agent and a mole adduct ratio ranges from about 30 weight percent to about 80 weight percent of the ethoxylated product.

Claim 8

A method as described in claim 6 wherein the strontium containing catalyst is present in an amount of at least about 0.1% by weight based upon the alcohol to be reacted.

Claim 9

A method as described in claim 7 wherein the alcohols to be ethoxylated contain from about 4 to about 20 carbon atoms.

Claim 10

A method as described in claim 8 wherein the alcohol is a primary alcohol.

Claim 11

A method as described in claim 8 wherein the alcohol is the product of a hydroformylation/hydrogenation reaction.

Claim 12

A method as described in claim 7 wherein the catalyst promoter is selected from the group consisting of heptanoic acid, ethylene glycol, benzoic acid, benzamide, adipic acid, phenol, stearic acid, bisphenol A (4,4'isopropylidene diphenol), triphenylmethanol, trimethylphenol, hexadecylamine, 1-naphthol, 2-naphthol, azelaic acid, fumaric acid, hydroquinone, salicylic acid, acetophenone, aniline, lauryl aldehyde, benzaldehyde, nonyl phenol, o-phenylphenol, benzylamine, citric acid, glycerine, acetylacetone, p-chlorophenol, formamide, 4-methyl-2-pentanone, pyridine, 1,4-butanediol, propylene glycol, p-methoxyphenol, p-nitrophenol, 2-undecanone, 2,2,2-trifluoroethanol, 2-ethylhexanoic acid, acetic acid, mixtures of 2-ethylhexanoic acid and benzamide, or 2-methoxyethanol.

Claim 13

A method as described in claim 11 when carried out in a continuous fashion.

Claim 14

A method as described in claim 12 wherein the promoter is alcohol having a pKa of less than 17.

Claim 15

A method as described in claim 13 wherein the alcohol is selected from the group consisting of triphenylmethanol, trichloroethanol, trifluoroethanol, 2-nitroethanol, 2-chloroethanol, 2,2-dichloroethanol, 2-methoxyethanol, 2-chlorocyclohexanol, ortho-chlorobenzyl alcohol.

Claim 16

A method as described in claim 1 wherein the promoter is a phenol having one or more functional groups of the general formula wherein at least one but less than all of R 1 , R 2 , R 31 R 41 and R 5 is hydrogen, linear or branched acyclic groups or alicyclic groups having from 1 to 16 carbon atoms and wherein at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is halogen, hydroxyl, nitro, ether, carbonyl, linear or branched acyclic group, alicyclic group, cyclic group, aryl group, or substituted aryl group and wherein, in addition, the R-designated groups can contain one or more functional groups selected from the group consisting of halogen, ether, nitro, carboxyl, carbonyl, amine, amide, or hydroxyl.

Claim 19

A method as described in claim 1 wherein a) the polyol promoters contain 2 or more adjacent or non-adjacent hydroxyl containing groups of the general formula wherein R 1 , R 21 and R 3 are, independently, linear or branched acyclic groups, alicyclic groups, cyclic groups, aryl groups or hydrogen and wherein the R-designated groups in addition can contain one or more functional groups selected from the group consisting of ether, amine, carboxyl, halogen, nitro, carbonyl, and amide; b) the aldehyde and ketone promoters contain one or more adjacent or non-adjacent carbonyl containing groups of the general formula wherein R 1 , and R 2 are, independently, linear or branched acyclic groups, alicyclic groups, cyclic groups, aryl groups or hydrogen, and wherein the R-designated groups in addition can contain one or more functional groups selected from the group consisting of hydroxyl, ether, carboxyl, carbonyl, amine, nitro or halogen; c) the primary, secondary or tertiary amide promoters contain one or more amide containing groups of the general formula wherein R 1 , R 2 , and R 3 are, independently, hydrogen, linear or branched acyclic groups, alicyclic groups, cyclic groups or aryl groups and wherein the R-designated groups can in addition contain one or more functional groups selected from the group consisting of hydroxyl, ether, carboxyl, carbonyl, amine, nitro or halogen; d) the primary, secondary or tertiary amine promoters contain one or more amine containing groups of the general formula wherein R 1 , R 2 , and R 3 are, independently, hydrogen, linear or branched acyclic groups, alicyclic groups, cyclic groups, or aryl groups, and wherein the R-designated groups can in addition contain one or more functional groups selected from the group consisting of hydroxyl, ether, carbonyl, halogen, carboxyl, nitro, or amide; e) the organic acid promoters contain one or more adjacent or non-adjacent carboxylic acid containing groups of the general formula wherein R 1 is a hydrogen, linear or branched acyclic group, alicylic group, cyclic group, or aryl group and wherein R can in addition contain one or more functional groups selected from'the group consisting of carbonyl, hydroxyl, halogen, ether, nitro, amine, or amide.

Claim 20

A method as described in claim 2 wherein the .alkoxylation is carried out using ethylene oxide, propylene oxide, or mixtures of these.

Claim 21

A method as described in claim 3 wherein the catalyst is selected from the group consisting of strontium metal, strontium-hydride, strontium hydroxide, hydrated strontium hydroxide, or strontium oxide.

Claim 22

A method as described in claim 4 wherein the reaction is carried out at a pressure of up to about 100 pounds per square inch gauge.

Claim 23

A method as described in claim 5 wherein ethylene oxide is used as the alkoxylation agent and a mole adduct ratio ranges from about 30 weight percent to about 80 weight percent of the ethoxylated product.

Claim 24

A method as described in claim 6 wherein the strontium containing catalyst is present in an amount of at least about 0.1% by weight based upon the alcohol to be reacted.

Claim 25

A method as described in claim 7 wherein the alcohols to be ethoxylated contain from about 4 to about 20 carbon atoms.

Claim 26

A method as described in claim 8 wherein the alcohol is a primary alcohol.

Claim 27

A method as described in claim 8 wherein the alcohol is the product of a hydroformylation/hydrogenation reaction.

Claim 28

A method as described in claim 7 wherein the catalyst promoter is selected from the group consisting of heptanoic acid, ethylene glycol, benzoic acid, benzamide, adipic acid, phenol, stearic acid, bisphenol A (4,4' isopropylidene diphenol), triphenylmethanol, trimethylphenol, hexadecylamine, 1-naphthol, 2-naphthol, azelaic acid, fumaric acid, hydroquinone, salicylic acid, acetophenone, aniline, lauryl aldehyde, benzaldehyde, nonyl phenol, o-phenylphenol, benzylamine, citric acid, glycerine, acetylacetone, p-chlorophenol, formamide, 4-methyl-2-pentanone, pyridine, 1,4-butanediol, propylene glycol, p-methoxyphenol, p-nitrophenol, 2-undecanone, 2,2,2-trifluoroethanol, 2-ethylhexanoic acid, acetic acid, mixtures of 2-ethylhexanoic acid and benzamide, or 2-methoxyethanol.

Claim 29

A method as described in claim 11 when carried out in a continuous fashion.

Claim 30

A method as described in claim 12 wherein the promoter is alcohol having a pKa of less than 17.

Claim 31

A method as described in claim 13 wherein.the alcohol is selected from the group consisting of triphenylmethanol, trichloroethanol, trifluoroethanol, 2-nitroethanol, 2-chloroethanol, 2,2-dichloroethanol, 2-methoxyethanol, 2-chlorocyclohexanol, ortho-chlorobenzyl alcohol.