USE OF SOLUBLE METAL SALTS IN METATHESIS REACTIONS

• US 20160039737A1
• Filed: 03/14/2014
• Published: 02/11/2016
• Est. Priority Date: 03/14/2013
• Status: Abandoned Application

• Current Assignee: Materia Incorporated (Exxon Mobil Corporation)
• Original Assignee: Materia Incorporated (Exxon Mobil Corporation)
• Inventors: CHAMPAGNE, Timothy M., UNG, Thay A.
• Application Number:
  US14/775,173
• Publication Number:
  US 20160039737A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 13/44 with a bicyclo ring system containing eight carbon atoms
• CPC Class Codes: C07C 13/61 with a bridged indene ring, e.g. dicyclopentadiene
• CPC Class Codes: C07C 5/54 with an acceptor system containing at least two compounds provided for in more than one of the sub-groups C07C5/44 - C07C5/50
• CPC Class Codes: C07C 6/04 at a carbon-to-carbon double bond
• CPC Class Codes: C07C 6/06 at a cyclic carbon-to-carbon double bond
• CPC Class Codes: C07C 67/333 by isomerisation; by change of size of the carbon skeleton introduction or elimination of carboxyl groups C07C67/313, C07C67/32
• CPC Class Codes: C07C 67/343 by increase in the number of carbon atoms
• CPC Class Codes: C07C 67/475 by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
• CPC Class Codes: C07C 67/60 by treatment giving rise to chemical modification by chemisorption C07C67/56
• CPC Class Codes: C07C 69/533 Monocarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/58 Esters of straight chain acids with eighteen carbon atoms in the acid moiety
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 7/173 with the aid of organo-metallic compounds
• CPC Class Codes: C10G 2300/1088 Olefins
• CPC Class Codes: C10G 2300/1092 C2-C4 olefins
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 29/06 Metal salts, or metal salts deposited on a carrier
• CPC Class Codes: C10G 29/205 : by reaction with hydrocarbons added to the hydrocarbon oil
• CPC Class Codes: C11B 3/10 : by adsorption

Abstract

The present invention describes the use of soluble metal salts to reduce impurities and metathesis catalysts poisons from olefinic feedstocks to improve olefin metathesis efficiency. The soluble metal salts were added to the olefinic feedstocks to prevent peroxides and catalyst poisons from inhibiting the metathesis catalyst. The soluble metal salts remain in the olefinic feedstocks and are used without further purification in the olefin metathesis reactions. The key to this invention is the soluble metal salt compounds do not inhibit the olefin metathesis catalysts but unexpectedly increase olefin metathesis catalyst efficiency while prior art heterogeneous metal complexes sequester the olefin metathesis catalyst, preventing olefin metathesis.

Claims

1. A method for improving the olefin metathesis of an olefinic feedstock, comprising:

providing an olefinic feedstock;

combining the olefinic feedstock with at least one soluble metal salt to form an olefinic feedstock composition;

subjecting the olefinic feedstock composition to conditions effective to reduce the concentration of at least one impurity in the olefinic feedstock;

combining the olefinic feedstock composition with at least one olefin metathesis catalyst; and

subjecting the olefinic feedstock composition to conditions effective to promote an olefin metathesis reaction.

2. The method of claim 1, wherein the olefinic feedstock comprises at least one olefin metathesis active compound derived from petroleum sources, fermentation sources, or natural sources such as oils extracted from plants or animals.

3. The method of claim 2, wherein the at least one olefin metatheis active compound is selected from alpha-olefins, internal olefins, cyclic olefins, polycyclic olefins, fumarates, isobutylene, fatty acids, fatty esters, terpenes, isoprenoids, citronellene, linalool, myrcene, β

-pinenespyrethrins, steroids, estolides, alkylresourcinols, cardanol, fatty alcohols, unsaturated triglyceride-based oils, polyunsaturated triglyceride-based oils, or combinations thereof.

4. The method of claim 1, wherein the olefinic feedstock comprises at least one natural seed oil.

5. The method of claim 4, wherein the at least one natural seed oil is selected from soybean oil, camelina oil, sunflower oil, canola oil, safflower oil, cottonseed oil, castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil, sesame oil, grape seed oil, fatty acid methyl esters of natural seed oil, or combinations thereof.

6. The method of claim 1, wherein the at least one soluble metal salt is selected from aluminum isopropoxide (Al(OⁱPr)₃), magnesium aluminum isopropoxide (MgAl₂(OⁱPr)₈), titanium (IV) isopropoxide (Ti(OⁱPr)₄), and methylaluminoxane (MAO), bismuth neodecanoate (Bi(Neodec)₃), cerium acetate hydrate (Ce(OAc)₃×

H₂O), or combinations thereof.

7. The method of claim 1, wherein the at least one impurity is a peroxide.

8. The method of claim 1, wherein the olefin metathesis reaction is selected from ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP), cross metathesis (CM), ring-opening cross metathesis (ROCM), self-metathesis, alkenolysis, acyclic diene metathesis polymerization, or combinations thereof.

9. The method of claim 1, wherein the at least one olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I)

10. The method of claim 9, wherein at least one of L¹, L², and L³ is an N-heterocyclic carbene ligand.

11. The method of claim 1, wherein the at least one olefin metathesis catalyst has the structure

12. The method of claim 11, wherein M is ruthenium, w, x, y, and z are zero, X and Y are N, and R^3A and R^4A are linked to-form -Q-, such that the complex has the structure

13. A composition, comprising:

an olefinic feedstock;

at least one soluble metal salt; and

at least one olefin metathesis catalyst, wherein the olefinic feedstock comprises at least one olefin metathesis active compound derived from petroleum sources, fermentation sources, or natural sources such as oils extracted from plants or animals.

14. The composition of claim 13, wherein the at least one olefin metathesis active compound derived from natural sources is at least one natural seed oil.

15. The composition of claim 14, wherein the at least one natural seed oil is selected from soybean oil, camelina oil, sunflower oil, canola oil, safflower oil, cottonseed oil, castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil, sesame oil, grape seed oil, fatty acid methyl esters of natural seed oil, or combinations thereof.

16. The composition of claim 13, wherein the at least one soluble metal salt is selected from aluminum isopropoxide (Al(OⁱPr)₃), magnesium aluminum isopropoxide (MgAl₂(OⁱPr)₈), titanium (IV) isopropoxide (Ti(OⁱPr)₄), and methylaluminoxane (MAO), bismuth neodecanoate (Bi(Neodec)₃), cerium acetate hydrate (Ce(OAc)₃ xH₂O), or combinations thereof.

17. The composition of claim 13, wherein the at least one olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I)

18. The composition of claim 17, wherein at least one of L¹, L², and L³ is an N-heterocyclic carbene ligand.

19. The composition of claim 13, wherein the at least one olefin metathesis catalyst has the structure

20. The method of claim 19, wherein M is ruthenium, w, x, y, and z are zero, X and Y are N, and R^3A and R^4A are linked to-form -Q-, such that the complex has the structure