# US 7,745,652 B2 · Integrated chemical processes for industrial utilization of seed oils

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- Number: US 7,745,652 B2
- Document ID: US7745652B2
- Status: Granted
- Kind: B2
- Application number: 12/328,868
- Filed: 2008-12-05
- Published: 2009-06-04
- Granted: 2010-06-29
- Earliest claimed: 2002-04-29
- Assignees: Dow Global Technologies LLC
- Inventors: Zenon Lysenko; Bob R. Maughon; Jozef Bicerano; Kenneth A. Burdett; Christopher P. Christenson; Clark H. Cummins; Marvin L. Dettloff; Alan K. Schrock; P. J. Thomas; Richard D. Varjian; Jerry E. White; John Michael Maher
- Web page: https://patentgrep.com/patent/US7745652B2

## CPC

- C07D 303/42: Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
- C07C 67/31: by introduction of functional groups containing oxygen only in singly bound form
- C07C 67/333: by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32)
- C07C 67/347: by addition to unsaturated carbon-to-carbon bonds
- C07C 67/56: by solid-liquid treatment; by chemisorption
- C07C 69/533: Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C 227/08: by reaction of ammonia or amines with acids containing functional groups
- C07C 227/18: by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
- C07C 229/08: the nitrogen atom of the amino group being further bound to hydrogen atoms
- Y02P 20/10: Process efficiency
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Integrated processes of preparing industrial chemicals starting from seed oil feedstock compositions containing one or more unsaturated fatty acids or unsaturated fatty acid esters, which are essentially free of metathesis catalyst poisons, particularly hydroperoxides; metathesis of the feedstock composition with a lower olefin, such as ethylene, to form a reduced chain olefin, preferably, a reduced chain α-olefin, and a reduced chain unsaturated acid or ester, preferably, a reduced chain α,ω-unsaturated acid or ester. The reduced chain unsaturated acid or ester may be (trans)esterified to form a polyester polyolefin, which may be epoxidized to form a polyester polyepoxide. The reduced chain unsaturated acid or ester may be hydroformylated with reduction to produce an α,ω-hydroxy acid or α,ω-hydroxy ester, which may be (trans)esterified with a polyol to form an α,ω-polyester polyol. Alternatively, the reduced chain unsaturated acid or ester may be hydroformylated with reductive amination to produce an α,ω-amino acid or α,ω-amino ester, which may be (trans)esterified to form an α,ω-polyester polyamine.

## Claims

### Claim 1

A fatty acid or fatty acid ester composition comprising one or more unsaturated fatty acids or one or more unsaturated fatty acid esters, characterized as comprising less than 1.5 milliequivalents of metathesis catalyst poison(s) per kilogram (meq/kg) of fatty acid or fatty acid ester composition, wherein the metathesis catalyst poison comprises one or more organic hydroperoxides; the feedstock composition being prepared by hydrolyzing a seed oil with water to obtain one or more unsaturated fatty acids or transesterifying a seed oil with a C1-8 alkanol to prepare one or more unsaturated fatty acid esters of the C1-8 alkanol, and thereafter contacting the one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with an adsorbent to remove the metathesis catalyst poison(s) to a concentration of less than 1.5 meq/kg.

### Claim 2 (depends on 1)

The fatty acid or fatty acid ester composition of claim 1 comprising less than about 1.0 meq/kg of metathesis catalyst poison(s).

### Claim 3 (depends on 1)

The fatty acid or fatty acid ester composition of claim 1 comprising greater than about 70 weight percent unsaturated fatty acid(s) and/or unsaturated fatty acid ester(s).

### Claim 4 (depends on 3)

The fatty acid or fatty acid ester composition of claim 3 wherein the unsaturated fatty acid is oleic acid, or the unsaturated fatty acid ester is an ester of oleic acid.

### Claim 5 (depends on 4)

The fatty acid ester composition of claim 4 wherein the unsaturated fatty acid ester is the methyl ester of oleic acid.

### Claim 6 (depends on 1)

The fatty acid or fatty acid ester composition of claim 1 wherein the adsorbent is selected from the group consisting of aluminas, silicas, activated carbons, clays, magnesias, aluminosilicates, molecular sieves, titanosilicates, and mixtures thereof.

### Claim 7

An olefin metathesis process comprising contacting a feedstock composition derived from a seed oil and comprising one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with a lower olefin in the presence of a metathesis catalyst under metathesis process conditions sufficient to prepare a reduced chain olefin and a reduced chain unsaturated acid or unsaturated ester, the feedstock composition characterized as comprising less than 10 milliequivalents of metathesis catalyst poison(s) per kilogram (meq/kg) of feedstock composition wherein the metathesis catalyst poison comprises one or more organic hydroperoxides, and the feedstock composition is prepared by hydrolyzing a seed oil with water to obtain one or more unsaturated fatty acids or transesterifying a seed oil with a C1-8 alkanol to prepare one or more unsaturated fatty acid esters of the C1-8 alkanol, and thereafter contacting the one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with an adsorbent to remove the metathesis catalyst poison(s) to a concentration of less than 10 meq/kg.

### Claim 8 (depends on 7)

The process of claim 7 wherein the feedstock composition comprises less than about 3.0 meq organic hydroperoxides per kg feedstock composition.

### Claim 9 (depends on 8)

The process of claim 8 wherein the feedstock composition comprises less than about 1.0 meq organic hydroperoxides per kg feedstock composition.

### Claim 10 (depends on 7)

The process of claim 7 wherein the feedstock composition comprises greater than about 70 weight percent unsaturated fatty acid(s) or unsaturated fatty acid ester(s).

### Claim 11 (depends on 10)

The process of claim 10 wherein the feedstock composition comprises greater than about 70 weight percent oleic acid or oleic acid ester(s).

### Claim 12 (depends on 7)

The process of claim 7 wherein the metathesis is conducted in the presence of a transition metal organophosphorus complex catalyst.

### Claim 13 (depends on 12)

The process of claim 12 wherein the metathesis catalyst is selected from the group consisting of dichloro-3,3-diphenylvinylcarbene-bis(tricyclohexylphosphine)ruthenium (II), bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(tricyclohexylphosphine)benzylidene ruthenium dibromide, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium dichloride, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium dibromide, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium diiodide, and the chelated ruthenium complexes represented by the following formula:
wherein M is Ru; each L is independently selected from neutral and anionic ligands in any combination that balances the bonding and charge requirements of M; a is an integer from 1 to about 4; R′ is selected from hydrogen, straight-chain or branched alkyl, cycloalkyl, aryl, and substituted aryl radicals; Y is an electron donor group of an element from Group 15 or 16 of the Periodic Table; each R″ is independently selected from hydrogen, alkyl, cycloalkyl, aryl, and substituted aryl radicals sufficient to satisfy the valency of Y; b is an integer from 0 to about 2; and Z is an organic diradical that is bonded to both Y and the carbene carbon (C) so as to form a bidentate ligand, which ligand in connection with the M atom forms a ring of from about 4 to about 8 atoms.

### Claim 14 (depends on 7)

The process of claim 7 wherein the lower olefin is selected from C2-5 olefins.

### Claim 15 (depends on 7)

The process of claim 7 wherein the reduced chain olefin is a reduced chain α-olefin, and the reduced chain unsaturated ester is a reduced chain α,ω-unsaturated ester.

### Claim 16 (depends on 15)

The process of claim 15 wherein the reduced chain α-olefin is 1-decene, and the reduced chain α,ω-unsaturated ester is methyl 9-decenoate.

### Claim 17

A process of preparing a polyester polyepoxide comprising (1) contacting a feedstock composition derived from a seed oil comprising one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with a lower olefin in the presence of an olefin metathesis catalyst under metathesis process conditions sufficient to prepare a reduced chain unsaturated acid or reduced chain unsaturated ester; (2) (trans)esterifying the reduced chain unsaturated acid or ester with a polyol under (trans)esterification conditions sufficient to prepare a polyester polyolefin; and (3) epoxidizing the polyester polyolefin with an epoxidizing agent, optionally, in the presence of an epoxidation catalyst, under epoxidation conditions sufficient to prepare a polyester polyepoxide; the feedstock composition of step (1) comprising less than 10 milliequivalents of metathesis catalyst poison(s) per kilo ram (meq/kg) of feedstock composition, wherein the metathesis catalyst poison comprises one or more organic hydroperoxides, and the feedstock composition is prepared by hydrolyzing a seed oil with water to obtain one or more unsaturated fatty acids or transesterifying a seed oil with a C1-8 alkanol to prepare one or more unsaturated fatty acid esters of the C1-8 alkanol, and thereafter contacting the one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with an adsorbent to remove the metathesis catalyst poison(s) to a concentration of less than 10 meq/kg.

### Claim 18 (depends on 17)

The process of claim 17 wherein the lower olefin is ethylene.

### Claim 19 (depends on 17)

The process of claim 17 wherein the olefin product is an α-olefin, and the unsaturated ester is an α,ω-unsaturated ester.

### Claim 20

A process of preparing a reduced chain α,ω-hydroxy acid, α,ω-hydroxy ester, and/or α,ω-diol comprising (1) contacting a feedstock composition comprising one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with a lower olefin in the presence of an olefin metathesis catalyst under process conditions sufficient to prepare a reduced chain unsaturated acid or ester; and (2) subjecting the reduced chain unsaturated acid or ester to hydroformylation with reduction in the presence of a hydroformylation/reduction catalyst under hydroformylation/reduction conditions sufficient to produce an α,ω-hydroxy acid, an α,ω-hydroxy ester, and/or an α,ω-diol; the feedstock composition of step (1) comprising less than 10 milliequivalents of metathesis catalyst poison(s) per kilogram (meq/kg) of feedstock composition, wherein the metathesis catalyst poison comprises one or more organic hydroperoxides, and the feedstock composition is prepared by hydrolyzing a seed oil with water to obtain one or more unsaturated fatty acids or transesterifying a seed oil with a C1-8 alkanol to prepare one or more unsaturated fatty acid esters of the C1-8 alkanol, and thereafter contacting the one or more unsaturated fatty acids or the one or more unsaturated fatty acid esters with an adsorbent to remove the metathesis catalyst poison(s) to a concentration of less than 10 meq/kg.

### Claim 21 (depends on 20)

The process of claim 20 wherein the lower olefin is ethylene.

### Claim 22 (depends on 20)

The process of claim 20 wherein the α,ω-hydroxy acid or α,ω-hydroxy ester is (trans)esterified by contact with a polyol under (trans)esterification conditions sufficient to prepare an α,ω-polyester polyol.

### Claim 23

A process of preparing a reduced chain α,ω-amino acid, α,ω-amino ester, and/or α,ω-amino alcohol comprising (1) contacting a feedstock composition comprising one or more unsaturated fatty acids or one or more unsaturated fatty acid esters with a lower olefin in the presence of an olefin metathesis catalyst under process conditions sufficient to prepare a reduced chain unsaturated acid or ester; and thereafter (2) subjecting the reduced chain unsaturated acid or ester to hydroformylation with reductive amination in the presence of a hydroformylation catalyst under hydroformylation/reductive amination conditions sufficient to produce an α,ω-amino acid, an α,ω-amino ester, and/or an α,ω-amino alcohol; the feedstock composition of step (1) comprising less than 10 milliequivalents of metathesis catalyst poison(s) per kilogram (meq/kg) of feedstock composition, wherein the metathesis catalyst poison comprises one or more organic hydroperoxides, and the feedstock composition is prepared by hydrolyzing a seed oil with water to obtain one or more unsaturated fatty acids or transesterifying a seed oil with a C1-8 alkanol to prepare one or more unsaturated fatty acid esters of the C1-8 alkanol, and thereafter contacting the one or more unsaturated fatty acids or the one or more unsaturated fatty acid esters with an adsorbent to remove the metathesis catalyst poison(s) to a concentration of less than 10 meq/kg.

### Claim 24 (depends on 23)

The process of claim 23 wherein the lower olefin is ethylene.

### Claim 25 (depends on 23)

The process of claim 23 wherein the α,ω-amino acid or α,ω-amino ester is (trans)esterified by contacting the α,ω-amino acid or ester with a polyol under (trans)esterification conditions sufficient to prepare an α,ω-polyester polyamine.