Synthesis of plasticizer and detergent alcohols

Claim 2

A process of preparing alcohols which comprises conducting an oxo reaction with hydrogen, carbon monoxide and olefins selected from those having 3 to 7 carbon atoms to obtain aldehydes having from 4 to 8 carbon atoms and comprised of a mixture of isomer containing at least 50% alkanals with no branching at the 2-position and subjecting the aldehydes to an aldol reaction to cause good conversion of the aldehydes to aldol product but with that produced from cross-aldol of 2-substituted aldehydes constituting no more than 20% of the product, and hydrogenating to obtain alcohols.

Claim 3

The process of claim 1 in which the aldehydes have content of alkanals with no branching at the 2-position from about 60 to about 80% and the conversions of aldehyde to aldol product are in the range of about 75% to about 90%.

Claim 4

The process of claim 1 in which the conversion of aldehyde other than 2-substituted aldehyde in the aldol reaction is at least about 95%.

Claim 5

The process of claim 1 in which the oxo reaction is conducted with hydrogen and carbon monoxide at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi, and the aldol reaction is conducted in aqueous alkaline medium at temperatures of 60° to 150° C.

Claim 6

The process of claim 4 in which a cobalt catalyst is employed for the oxo reaction.

Claim 9

A process of preparing a plasticizer alcohol comprised of 2-propylheptanol and no more than 15% of 2-propyl-4-methylhexanol which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi. with a mixture of normal butenes and hydrogen and carbon monoxide to obtain a mixture of amyl aldehydes with at least about 66% n-pentanal content and without separation of aldehyde isomers conducting an aldol reaction in aqueous alkaline medium at temperatures of 60° to 150° C. of the mixture to convert a high percentage of such aldehydes to ten-carbon aldol products but stopping the reaction short of complete conversion so that substantially all of the n-pentanal has formed aldol product but a portion of the branched aldehyde in the aldehyde mixture is not reacted, hydrogenating the resulting aldehyde mixture with hydrogen and obtaining a 2-propylheptanol product in which the 2-propyl-4-methylhexanol co-product constitutes no more than about 15% of the 10-carbon alcohol composition, in admixture with 2-methylbutanol.

Claim 10

A process of preparing a plasticizer alcohol comprised of 2-propylheptanol and no more than 15% of 2-propyl-4-methylhexanol which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi. with a mixture of normal butenes and hydrogen and carbon monoxide to obtain a mixture of amyl aldehydes with at least about 66% n-pentanal content and without separation of aldehyde isomers conducting an aldol reaction in aqueous alkaline medium at temperatures of 60° to 150° C. of the mixture to convert a high percentage of such aldehydes to ten-carbon aldol products but stopping the reaction short of complete conversion so that substantially all of the n-pentanal has formed aldol product but a portion of the branched aldehyde in the aldehyde mixture is not reacted, hydrogenating the resulting aldehyde mixture with hydrogen and obtaining a 2-propylheptanol product in which the 2-propyl-4-methylhexanol co-product constitutes no more than about 15% of the 10-carbon alcohol composition, in admixture with 2-methylbutanol.

Claim 11

The process of claim 7 in which the 2-propyl-4-methylhexanol constitutes about 11-12%.

Claim 12

The process of preparing ten-carbon plasticizer alcohols which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi. of normal butenes and hydrogen and carbon monoxide to obtain aldehydes which are at least about 70% n-pentanal and subjecting the aldehydes to an aldol reaction in aqueous alkali of about 1 to 10% concentration by weight to cause nearly all of the n-petanal to be condensed, producing ten-carbon enals comprised of at least about 85% of 2-propylheptenal, and hydrogenating the 10-carbon enals with hydrogen to obtain alcohols comprised of at least about 85% 2-propylheptanol, and a substantial portion up to about 15% of other ten-carbon atom isomeric alcohols.

Claim 13

The process of preparing ten-carbon plasticizer alcohols which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi. of normal butenes and hydrogen and carbon monoxide to obtain aldehydes which are at least about 70% n-pentanal and subjecting the aldehydes to an aldol reaction in aqueous alkali of about 1 to 10% concentration by weight to cause nearly all of the n-petanal to be condensed, producing ten-carbon enals comprised of at least about 85% of 2-propylheptenal, and hydrogenating the 10-carbon enals with hydrogen to obtain alcohols comprised of at least about 85% 2-propylheptanol, and a substantial portion up to about 15% of other ten-carbon atom isomeric alcohols.

Claim 14

The process of claim 9 in which the oxo process is conducted at 1000 to 4000 psi in the presence of cobalt catalyst, and the aldol reaction is conducted at about 90° to about 130° C.

Claim 15

The process of claim 9 in which the amyl aldehydes are comprised of 70 to 85% n-pentanal and the ten-carbon alcohols are 85 to 95% 2-propylheptanol.

Claim 16

The process of preparing ten-carbon plasticizer alcohols which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi of normal butenes and hydrogen and carbon monoxide and in which substantially linear butenes which are at least one-third 1-butene are hydroformylated by reaction with carbon monoxide and hydrogen over cobalt catalyst to obtain amyl aldehydes with n-pentanal:2-methylbutanal ratios in the range of about 2.8:1 to 3.1:1, and the aldehydes are subjected to an aldol reaction in the presence of aqueous alkali hydroxide of about 1 to 10% concentration by weight, constituting about 15% to 75% by volume of the aqueous alkali and aldehyde reactant, at temperatures of about 90° to about 130° C. to condense nearly all of the n-pentanal while leaving some 2-methylbutanal unreacted to obtain ten-carbon enals with at least about 85% of 2-propylheptanal from self-condensation of n-pentanal, followed by hydrogentating the ten-carbon enals over hydrogenation catalyst with hydrogen at elevated pressure to obtain alcohols by reduction of enals and remaining amyl aldehydes, the ten-carbon alcohols obtained being composed of about 85 to 95% 2-propylheptanol and a substantial portion up to about 15% of other ten-carbon atom isomeric alcohols, and separating five-carbon alcohols and 10-carbon alcohols by distillation.

Claim 17

The process of preparing ten-carbon plasticizer alcohols which comprises conducting an oxo reaction at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi of normal butenes and hydrogen and carbon monoxide and in which substantially linear butenes which are at least one-third 1-butene are hydroformylated by reaction with carbon monoxide and hydrogen over cobalt catalyst to obtain amyl aldehydes with n-pentanal:2-methylbutanal ratios in the range of about 2.8:1 to 3.1:1, and the aldehydes are subjected to an aldol reaction in the presence of aqueous alkali hydroxide of about 1 to 10% concentration by weight, constituting about 15% to 75% by volume of the aqueous alkali and aldehyde reactant, at temperatures of about 90° to about 130° C. to condense nearly all of the n-pentanal while leaving some 2-methylbutanal unreacted to obtain ten-carbon enals with at least about 85% of 2-propylheptanal from self-condensation of n-pentanal, followed by hydrogentating the ten-carbon enals over hydrogenation catalyst with hydrogen at elevated pressure to obtain alcohols by reduction of enals and remaining amyl aldehydes, the ten-carbon alcohols obtained being composed of about 85 to 95% 2-propylheptanol and a substantial portion up to about 15% of other ten-carbon atom isomeric alcohols, and separating five-carbon alcohols and 10-carbon alcohols by distillation.

Claim 18

The process of preparing aldol products which comprises subjecting an amyl aldehyde mixture containing at least about 70% n-pentanal and a substantial amount of 2-methylbutanal to an aldol reaction with strong alkaline catalyst at temperatures of 90° to 130° C. to cause substantially all of the n-pentaldehyde to react, stopping the reaction with unconverted 2-methylbutanal still present and producing ten-carbon enals composed of at least about 85% 2-propylheptenal.

Claim 19

The process of preparing aldol products which comprises subjecting an amyl aldehyde mixture containing at least about 70% n-pentanal and a substantial amount of 2-methylbutanal to an aldol reaction with strong alkaline catalyst at temperatures of 90° to 130° C. to cause substantially all of the n-pentaldehyde to react, stopping the reaction with unconverted 2-methylbutanal still present and producing ten-carbon enals composed of at least about 85% 2-propylheptenal.

Claim 20

The process of claim 12 in which the hydrogenation is conducted at pressures above 500 psi. and temperatures above about 130° C.

Claim 21

A process of preparing alcohols which comprises conducting an oxo reaction with hydrogen carbon monoxide and a hexene mixture comprised mainly of methylpentenes with internal unsaturation with no more than 30% linear hexenes, so as to obtain C 7 aldehydes with less than 30% 2-substituted aldehydes subjecting the aldehydes to an aldol reaction to obtain aldol product with conversion of at least 70% and hydrogenation with hydrogen to obtain alcohols.

Claim 22

A process of preparing alcohols which comprises conducting an oxo reaction with hydrogen carbon monoxide and a hexene mixture comprised mainly of methylpentenes with internal unsaturation with no more than 30% linear hexenes, so as to obtain C 7 aldehydes with less than 30% 2-substituted aldehydes subjecting the aldehydes to an aldol reaction to obtain aldol product with conversion of at least 70% and hydrogenation with hydrogen to obtain alcohols.

Claim 23

The process of claim 15 in which no more than one-third of the 2-substituted aldehydes are converted to aldol product.

Claim 24

The process of claim 15 in which the hexene mixture comprises substantially the hexenes mixture from a dimerization of propylene over a nickel and aluminum alkyl catalyst.

Claim 25

The process of claim 15 in which C 14 alcohols are produced with 2-pentyl-7-methyloctanol being the isomer present in largest amount.

Claim 26

The process of claim 15 in which more than 75% of the C 14 alcohol product has double branching but has practically no branches located on adjacent carbon atoms.

Claim 27

The process of claim 15 in which the oxo reaction is conducted with cobalt catalyst and hydrogen and carbon monoxide at temperatures in the range of 80° to 150° C. and pressures sufficient to maintain catalyst stability but not over 5000 psi, and the aldol reaction is conducted in aqueous alkaline medium at temperatures of 60° to 150° C.

Claim 28

The process of preparing alcohols in which substantially linear hexenes are separated from a propylene dimerization mixture and subjected to an oxo reaction with hydrogen and carbon monoxide to obtain better than 50% selectivity to alkanals with no branching at the 2-position and subjecting the oxo reaction product to an aldol reaction to produce an aldol product with no more than about 15% content from cross aldol of 2-substituted aldehydes, and hydrogenating with hydrogen to produce alcohols.

Claim 29

The process of preparing alcohols in which substantially linear hexenes are separated from a propylene dimerization mixture and subjected to an oxo reaction with hydrogen and carbon monoxide to obtain better than 50% selectivity to alkanals with no branching at the 2-position and subjecting the oxo reaction product to an aldol reaction to produce an aldol product with no more than about 15% content from cross aldol of 2-substituted aldehydes, and hydrogenating with hydrogen to produce alcohols.

Claim 30

The process of claim 21 in which the product contains at least 85% 2-pentylnonanol and no more than about 15% 2-pentyl-4-methyloctanol.

Claim 31

The process of preparing aldol products which comprises subjecting a C 7 aldehyde mixture of isomers comprising at least 50% methylhexanals but no more than 30% of 2-substituted aldehydes to an aldol reaction with strong alkaline catalyst to effect high conversion of the methylhexanals to aldol product but with no more than one-half of the 2-substituted aldehydes being converted to aldol product.

Claim 32

The process of preparing aldol products which comprises subjecting a C 7 aldehyde mixture of isomers comprising at least 50% methylhexanals but no more than 30% of 2-substituted aldehydes to an aldol reaction with strong alkaline catalyst to effect high conversion of the methylhexanals to aldol product but with no more than one-half of the 2-substituted aldehydes being converted to aldol product.