Production of vinylidene olefins

• US 5,659,100 A
• Filed: 02/05/1996
• Issued: 08/19/1997
• Est. Priority Date: 02/05/1996
• Status: Expired due to Term

• Current Assignee: Monsanto Company (Bayer AG), Innovene USA LLC
• Original Assignee: Amoco Corporation (BP PLC)
• Inventors: Lin, Kaung-Far
• Primary Examiner(s): Howard, Jacqueline V.
• Application Number:
  US08/596,801
• Time in Patent Office: 561 Days
• Field of Search: 585/503, 585/511, 585/512
• US Class Current: 585/503
• CPC Class Codes: C07C 2/30 containing metal-to-carbon bond; Metal hydrides
• CPC Class Codes: C07C 2531/14 of aluminium or boron

Abstract

Vinylidene olefin can be formed in good yield and high selectivity in much shorter reaction periods than found critical heretofore. The process involves dimerizing vinyl olefin with at least one trialkylaluminum compound as the sole catalyst component charged to the reaction vessel. These materials are charged to the reactor so that it contains in the range of 0.001 to 0.5 mol of trialkylaluminum per mol of the initial vinyl olefin. The reaction is performed at a temperature in the range of 100° to 200° C. for a period of time sufficient to convert 10 to 99% by weight of the initial vinyl olefin to a different product and form a product mixture with at least 80 wt % vinylidene dimer selectivity. In conducting the process the liquid mixture in the reactor is maintained in direct contact with passivated ferrous metal such as low nickel ferrous metal or steel alloy interior surfaces during at least 90 percent of the total period of time during which the reactor contents are at a temperature above about 50° C.

Claims

1. A process for producing vinylidene olefin using a trialkylaluminum compound as the sole catalyst component charged to the reactor, which process comprises forming and heating a mixture of vinyl olefin and at least one trialkylaluminum compound as the catalyst in a ratio in the range of 0.001 to 0.5 mol of trialkylaluminum per mol of the initial vinyl olefin at a temperature in the range of about 100°

to about 200°

C. for a period of time sufficient to convert in the range of about 10 to about 99% by weight of the initial vinyl olefin to a different product with vinylidene dimer selectivity of at least 80%, with the proviso that said mixture is maintained in direct contact with passivated ferrous metal interior surfaces of and/or in said reactor for a total period of at least one hour during which the reaction mixture is at a temperature above about 50°

C.

2. A process of claim 1 wherein the reactor is a single reactor in which the reaction is conducted with agitation on a batch basis.

3. A process of claim 2 wherein during at least 50 percent of the time that the reaction mixture is at a temperature above about 110°

C.;

a) the vapor space in the reactor is in the range of 0 to 40 percent of the total interior free space of the reactor, and

b) the remainder of the free space in the reactor contains an inert atmosphere.

4. A process of claim 1 wherein the reactor comprises at least two vessels in which the reaction is conducted with agitation and continuous feed, said vessels being connected in series such that the feed rate to the first vessel, and the discharge rates from each vessel to the ensuing vessel, where there is an ensuing vessel, are substantially equal to each other.

5. A process of claim 4 wherein during at least 50 percent of the time that the reaction mixture is at a temperature above about 110°

C. in said vessels;

a) the vapor space in said vessels is in the range of 0 to 40 percent of the total interior free space of the vessels, and

b) the remainder of the free space in said vessels contains an inert atmosphere.

6. A process of claim 1 wherein the reactor is a single continuous elongated reactor in which the reaction is conducted with agitation on a continuous basis.

7. A process of claim 6 wherein during at least 50 percent of the time the reaction mixture is at a temperature above about 110°

C.;

a) the vapor space in the reactor is in the range of 0 to 40 percent of the total interior free space of the reactor, and

b) the remainder of the free space in the reactor contains an inert atmosphere.

8. A process of claim 1 wherein the trialkylaluminum as charged to the reaction vessel is one or more trialkylaluminum compounds in which substantially all of the alkyl groups are straight chain primary alkyl groups having in the range of from 2 to about 14 carbon atoms.

9. A process of claim 1 wherein the trialkylaluminum as charged to the reaction vessel contains, if any, a maximum of 0.10 wt % of aluminum hydride equivalent.

10. A process of claim 1 wherein the trialkylaluminum as charged to the reaction vessel is triethylaluminum.

11. A process of claim 10 wherein the triethylaluminum as charged to the reaction vessel contains, if any, a maximum of 0.10 wt % of aluminum hydride equivalent.

12. A process of claim 1 wherein the vinyl olefin charged to the reactor contains in the range of 3 to 20 carbon atoms per molecule.

13. A process of claim 1 wherein said vinyl olefin is a single vinyl olefin.

14. A process of claim 13 wherein said single vinyl olefin is in admixture with up to about 40 mol percent of internal and/or vinylidene olefins.

15. A process of claim 13 wherein said single vinyl olefin is in admixture with up to about 40 mol percent of one or more paraffinic hydrocarbons.

16. A process of claim 13 wherein said single vinyl olefin is in admixture with up to about 40 mol percent of a mixture of (a) internal and/or vinylidene olefins, and (b) one or more paraffinic hydrocarbons.

17. A process of claim 1 wherein said vinyl olefin is a mixture of two or more vinyl olefins.

18. A process of claim 17 wherein said mixture of vinyl olefins is in admixture with up to about 40 mol percent of internal and/or vinylidene olefins.

19. A process of claim 17 wherein said mixture of vinyl olefins is in admixture with up to about 40 mol percent of one or more paraffinic hydrocarbons.

20. A process of claim 17 wherein said mixture of vinyl olefins is in admixture with up to about 40 mol percent of a mixture of (a) internal and/or vinylidene olefins, and (b) one or more paraffinic hydrocarbons.

21. A process of claim 1 wherein the ratio of trialkylaluminum per mol of the initial vinyl olefin is in the range of about 0.005 to about 0.05 mol of trialkylaluminum per mol of the initial vinyl olefin.

22. A process of claim 1 wherein the ratio of trialkylaluminum per mol of the initial vinyl olefin is in the range of about 0.010 to about 0.05 mol of trialkylaluminum per mol of the initial vinyl olefin.

23. A process of claim 1 wherein the dimerization is conducted predominately at temperatures in the range of about 120°

to about 180°

C. with reaction periods in the range of 1 to 24 hours.

24. A process of claim 1 wherein the dimerization is conducted predominately at temperatures in the range of 145°

to 170°

C. with reaction periods in the range of 1 to 15 hours.

25. A process of claim 1 wherein the dimerization is conducted predominately at temperatures in the range of 160°

to 170°

C. with reaction periods in the range of about 6 to about 12 hours.

26. A process of claim 1 wherein at least 90 percent of the interior surfaces of the reactor that are in direct contact with the reaction mixture are composed of passivated carbon-steel alloy.

27. A process of claim 1 wherein the vinyl olefin charged to the reactor contains in the range of 4 to 20 carbon atoms per molecule, wherein the trialkylaluminum as charged to the reaction vessel is one or more trialkylaluminum compounds in which substantially all of the alkyl groups are straight chain primary alkyl groups having in the range of from 2 to about 20 carbon atoms, and wherein the trialkylaluminum as charged to the reaction vessel contains, if any, a maximum of 0.10 wt % of aluminum hydride equivalent.

28. A process of claim 27 wherein said ratio is in the range of about 0.005 to about 0.05 mol of trialkylaluminum per mol of the initial vinyl olefin, and wherein the dimerization is conducted predominately at temperatures in the range of 160°

to 170°

C. with reaction periods in the range of 6 to 15 hours.

29. A process of claim 28 wherein the trialkylaluminum as charged to the reaction vessel is triethylaluminum.

30. A process of claim 29 wherein the triethylaluminum as charged to the reaction vessel contains, if any, a maximum of 0.10 wt % of aluminum hydride equivalent.

31. A process of claim 27 wherein the reactor is a single reactor in which the reaction is conducted with agitation on a batch basis;

and wherein during at least 50 percent of the time that the reaction mixture is at a temperature above about 110°

C.;

a) the vapor space in the reactor is in the range of 0 to 40 percent of the total interior free space of the reactor, and

b) the remainder of the free space in the reactor contains an inert atmosphere.

32. A process of claim 27 wherein the reactor comprises at least two vessels in which the reaction is conducted with agitation and continuous feed, said vessels being connected in series such that the feed rate to the first vessel, and the discharge rates from each vessel to the ensuing vessel, where there is an ensuing vessel, are substantially equal to each other;

and wherein during at least 50 percent of the time that the reaction mixture is at a temperature above about 110°

C. in one or more of said vessels;

a) the vapor space in said vessels is in the range of 0 to 40 percent of the total interior free space of the vessels, and

b) the remainder of the free space in said vessels contains an inert atmosphere.

33. A process of claim 27 wherein the reactor is a single continuous elongated reactor in which the reaction is conducted with agitation on a continuous basis;

and wherein during at least 50 percent of the time the reaction mixture is at a temperature above about 110°

C.;

a) the vapor space in the reactor is in the range of 0 to 40 percent of the total interior free space of the reactor, and

b) the remainder of the free space in the reactor contains an inert atmosphere.

34. A process of dimerizing vinyl olefin to produce vinylidene olefin which comprises:

a) introducing into a reactor having low nickel ferrous metal alloy interior surfaces (i) vinyl olefin to be dimerized and (ii) a trialkylaluminum compound as the sole catalyst component charged to the reactor, (i) and (ii) being proportioned to result in a ratio in the range of 0.001 to 0.05 mol of trialkylaluminum per mol of the initial vinyl olefin, thereby forming a reaction mixture;

b) maintaining the reaction mixture (i) in direct contact with passivated ferrous metal alloy interior surfaces, and substantially free of contact with metallic non-passivated nickel-containing surfaces in said reactor, for a the total period of time of at least one hour during which the reaction mixture is at a temperature above about 50°

C., and (ii) under substantially anhydrous oxygen-free conditions and at one or more temperatures in the range of 100°

to 200°

C. for a period of time in the range of 1 to 24 hours.

35. A process of claim 34 wherein the passivated metal alloy interior surfaces of said reactor are composed of a carbon steel.

36. A process of claim 35 wherein the reaction mixture is maintained under substantially anhydrous oxygen-free conditions at one or more temperatures in the range of about 120°

to about 180°

C. for a period of time in the range of 1 to 24 hours.

37. A process of claim 35 wherein the vinyl olefin to be dimerized has in the range of 4 to 20 carbon atoms, wherein the trialkylaluminum compound charged to the reactor is triethylaluminum, and wherein the reaction mixture is maintained under substantially anhydrous oxygen-free conditions at one or more temperatures in the range of 145°

to 170°

C. for a period of time in the range of 1 to 24 hours.

38. A process of claim 35 wherein the reactor is a single reactor in which the reaction is conducted with agitation on a batch basis, wherein during at least 50 percent of the time that the reaction mixture is at a temperature above about 110°

C.;

a) the vapor space in the reactor is in the range of 0 to 10 percent of the total interior free space of the reactor, and

b) the remainder of the free space in the reactor contains an inert atmosphere.

39. A process of claim 38 wherein the vinyl olefin to be dimerized has in the range of 3 to 20 carbon atoms, wherein the trialkylaluminum compound charged to the reactor is triethylaluminum, and wherein the reaction mixture is maintained under substantially anhydrous oxygen-free conditions at one or more temperatures in the range of about 160°

to about 180°

C. for a period of time in the range of 1 to 24 hours.

40. A process of claim 34 wherein the passivated metal alloy interior surfaces of said reactor are composed of a low-nickel stainless steel.