Claims
- 1. A continuous process for co-producing secondary alcohols of long-chain olefins and lower carboxylic acid esters, comprising the steps of:
- (A) passing a mixture of a long-chain .alpha.-olefin, and optionally the internal olefin isomers thereof, together with a lower carboxylic acid through a reaction zone in the presence of an amount sufficient to catalyze the conversion of said olefins and carboxylic acids to secondary alcohol carboxylates of an acidic heterogeneous catalyst under conditions at which the corresponding oxylation reaction will occur, thereby producing mixtures of isomeric secondary alcohol carboxylates;
- (B) recovering the mixture of isomeric carboxylates produced in step (A);
- (C) mixing the recovered carboxylates with a lower aliphatic alcohol in a pre-reaction zone in the presence of an amount sufficient to catalyze the pre-reaction of said carboxylates and lower aliphatic alcohol to said secondary alcohols of long-chain olefins and lower carboxylic acid esters of an ester exchange catalyst under conditions at which pre-reaction will occur;
- (D) after the pre-reaction, passing the recovered carboxylates and a lower aliphatic alcohol, wherein the molar concentration of lower aliphatic alcohol is greater than the molar concentration of said carboxylates, through a reactive distillation still in the presence of an amount sufficient to catalyze the conversion of said carboxylates and lower aliphatic alcohol to said secondary alcohols of long-chain olefins and lower carboxylic acid esters of an ester exchange catalyst under conditions at which the ester exchange will occur, thereby producing, as co-products, secondary alcohols of said long-chain olefins and carboxylates of said lower aliphatic alcohols; and
- (E) removing said carboxylates overhead and said secondary alcohols in the tails.
- 2. A process of claim 1 wherein the acidic heterogeneous catalyst comprises a copolymeric, high fluorine content aliphatic sulfonic acid, or a macroreticular, cross-linked sulfonated styrene/divinyl benzene copolymer.
- 3. A process of claim 1 wherein the olefin is a linear, unsubstituted .alpha.-olefin of from 8 to 14 carbon atoms.
- 4. A process of claim 3 wherein the .alpha.-olefin is a mixture of linear, unsubstituted olefins of from 8 to 14 carbon atoms.
- 5. A process of claim 4 wherein the .alpha.-olefin is a mixture of linear, unsubstituted olefins of from 12 to 14 carbon atoms.
- 6. A process of claim 3 wherein the linear, unsubstituted olefin comprises an .alpha.-olefin of from 8 to 14 carbon atoms and internal olefin isomers thereof.
- 7. A process of claim 1 wherein the lower carboxylic acid is a linear or branched alkyl or alkenyl carboxylic acid of from 1 to 5 carbon atoms in the non-carboxylic moiety.
- 8. A process of claim 1 wherein the lower carboxylic acid is selected from the group consisting of acetic acid, cyanoacetic acid, the mono-, di-, and tri-chloroacetic acids, methoxyacetic acid, trifluoroacetic acid, 3-mercaptomethyl propionic acid, acrylic acid, methacrylic acid, 2-cyanoacrylic acid, 2-chloroacrylic acid, and .beta.-acryloxypropionic acid.
- 9. A process of claim 1 wherein the lower aliphatic alcohol is a linear, branched, or cyclic, alcohol of 1 to 8 carbon atoms.
- 10. A process of claim 1 wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, allyl alcohol, 2-cyanoethanol, 2-chloroethanol, 2-ethoxyethanol, 3-chloropropanol, 2-fluoroethanol, methallyl alcohol, 2-butenol, and 2-ethylhexanol.
- 11. A process of claim 1 wherein the acidic heterogenous catalyst is (1) a copolymeric, high fluorine content aliphatic sulfonic acid, or (2) a macroreticular, cross-linked sulfonated styrene/divinyl benzene copolymer.
- 12. A process of claim 1 wherein the ester-exchange catalyst is a titanium alcoholate.
- 13. A continuous process for co-producing secondary alcohols of long-chain olefins and lower carboxylic acid esters, comprising the steps of:
- (A) passing a mixture of a long-chain .alpha.-olefin, and optionally the internal olefin isomers thereof, and a lower carboxylic acid through a reaction zone in the presence of an amount sufficient to catalyze the conversion of said olefins and carboxylic acids to secondary alcohol carboxylates of an acidic heterogeneous catalyst selected from the group consisting of copolymeric high fluorine content aliphatic sulfonic acids and macroreticular, cross-linked sulfonated styrene/divinyl benzene copolymers having a cross-link density of about 18 to 21% and a pore volume of from about 30 to 35% under conditions at which the corresponding oxylation reaction will occur, thereby producing mixtures of isomeric secondary alcohol carboxylates;
- (B) recovering the mixture of isomeric carboxylates produced in step (A);
- (C) mixing the recovered carboxylates with a lower aliphatic alcohol in a pre-reaction zone in the presence of an amount sufficient to catalyze the pre-reaction of said carboxylates and lower aliphatic alcohol to said secondary alcohols of long-chain olefins and lower carboxylic acid esters of an ester exchange catalyst under conditions at which pre-reaction will occur;
- (D) after the pre-reaction, passing the recovered carboxylates and a lower aliphatic alcohol, wherein the molar concentration of lower aliphatic alcohol is greater than the molar concentration of said carboxylates, through a reactive distillation still in the presence of an amount sufficient to catalyze the conversion of said carboxylates and lower aliphatic alcohol to said secondary alcohols of long-chain olefins and lower carboxylic acid esters of an ester exchange catalyst under conditions at which the ester exchange will occur, thereby producing, as co-products, secondary alcohols of said long-chain olefins and carboxylates of said lower aliphatic alcohols; and
- (E) removing said carboxylates overhead and said secondary alcohols in the tails.
- 14. The process of claim 1 in which the molar concentration of lower aliphatic alcohol is increased in an amount sufficient to increase the secondary alcohol carboxylate conversion.
- 15. The process of claim 13 in which the molar concentration of lower aliphatic alcohol is increased in an amount sufficient to increase the secondary alcohol carboxylate conversion.
Parent Case Info
This application is a Continuation of prior U.S. application Ser. No. 198,245 Filing Date May 25, 1988 now abandoned and/which is a continuation of application Ser. No. 508,561 Filing Date Jun. 28, 1983 now abandoned.
US Referenced Citations (13)
Foreign Referenced Citations (3)
Number |
Date |
Country |
2031421 |
Apr 1980 |
GBX |
2041364 |
Sep 1980 |
GBX |
8100846 |
Apr 1981 |
GBX |
Non-Patent Literature Citations (1)
Entry |
Rohm and Haas, "Amberlyst 15" Technical Bulletin No. IE-94-65/72/76, Sep. 1978, pp. 1-17. |
Continuations (2)
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Number |
Date |
Country |
Parent |
198245 |
May 1988 |
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Parent |
508561 |
Jun 1983 |
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