Neo-acids and process for making the same

Patent metadata

Field	Value
Publication number	US-10597347-B2
Application number	US-201816033298-A
Country	US
Kind code	B2
Filing date	Jul 12, 2018
Priority date	Sep 29, 2017
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

This disclosure relates to neo-acids and processes for making neo-acids from a vinylidene olefin.

First claim

What is claimed is:

1. A compound having a formula (F-I) below:

wherein R 1 and R 2 are a C6 to C30 linear or branched alkyl group and R 1 and R 2 are identical.

2. The compound of claim 1 , wherein R 1 and R 2 are a linear alkyl group.

3. The compound of claim 1 , wherein R 1 and R 2 are selected from n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl, n-docosyl, n-tetracosyl, n-hexacosyl, and n-octacosyl.

4. The compound of claim 2 , wherein R 1 and R 2 are selected from n-hexyl, n-octyl, n-decyl, and n-dodecyl.

5. The compound of claim 1 , which is selected from: 2-hexyl-2-methyldecanoic acid; 2-methyl-2-octyldodecanoic acid; 2-decyl-2-methylhexadecanoic acid; 2-decyl-2-methyldecanoic acid; 2-dodecyl-2-methyldecanoic acid; 2-methyl-2-tetradecylocotadecanoic acid; and 2-hexadecyl-2-methylicosanoic acid.

6. A process for making a neo-acid product comprising a neo-acid compound having a formula (F-I) below:

wherein R 1 and R 2 are each independently a hydrocarbyl group comprising at least two carbon atoms, the process comprising:
(I) providing a vinylidene olefin feed comprising a vinylidene olefin having a formula (F-II) below:

 where R 1 and R 2 correspond to the R 1 and R 2 in formula (F-I) above, respectively;
(II) contacting the vinylidene olefin with carbon monoxide in a reactor in the presence of an active acid catalyst to obtain a reaction mixture; wherein the active acid catalyst is not added into the reactor until after the partial pressure of carbon monoxide (CO) in the reactor has reached 2.0 MPa;
(III) contacting the reaction mixture with water to obtain an acid product mixture; and
(IV) obtaining the neo-acid product from the acid product mixture.

7. The process of claim 6 , wherein in step (II), the active acid catalyst is not added into the reactor until after the partial pressure of carbon monoxide in the reactor reaches at least 3.5 MPa.

8. The process of claim 6 , wherein in step (II), the active acid catalyst is not added into the reactor until after the partial pressure of CO in the reactor has reached 5.0 MPa.

9. The process of claim 6 , wherein steps (II) and (III) combined have a selectivity of the vinylidene olefin toward the neo-acid compound of at least 90% after removal of vinylidene and heavy components.

10. The process of claim 6 , wherein R 1 and R 2 are each independently a C2to C30linear or branched alkyl group.

11. The process of claim 6 , wherein R 1 and R 2 are each independently a linear alkyl group.

12. The process of claim 6 , wherein R 1 and R 2 are identical.

13. The process of claim 6 , wherein in step (I), the vinylidene olefin feed consists essentially of a single vinylidene olefin having a formula (F-II).

14. The process of claim 6 , wherein in step (I), the vinylidene olefin feed comprises multiple vinylidene olefins each having a different formula (F-II), and the multiple vinylidene olefins differ in terms of molecular weight thereof by no more than 150 grams per mole.

15. The process of claim 6 , wherein in step (I), the vinylidene olefin is selected from: 4-methylenenonane; 3-methylenenonane; 5-methyleneundecane; 5-methylenetridecane; 7-methylenetridecane; 7-methylenepentadecane; 9-methyleneheptadecane; 7-methyleneheptadecane; 9-methylenenonadecane; 11-methylenehenicosane ; 11-methylenetricosane; 9-methylenehenicosane; 13-methylenepentaco sane ; 13-methyleneheptaco sane; 11-methylenepentacosane; 15-methylenenonaco sane ; 15-methylenehentriacontane; 13-methylenenonacosane; 15-methylenetritriacontane; 17-methylenepentatriacontane; 17-methylenetritriacontane; and any mixtures of two or more of the foregoing differing in number of carbon atoms contained therein no greater than 8.

16. The process of claim 6 , wherein step (I) comprises the following steps:
(Ia) providing a monomer feed comprising a terminal olefin having a formula (F-III) below and optionally a terminal olefin having a formula (F-IV) below: R 1 -CH═CH 2 (F-III), R 2 —CH═CH 2 (F-IV), where R 1 and R 2 correspond to the R 1 and R 2 in formula (F-I), respectively;
(Ib) oligomerizing the monomer feed in an oligomerization reactor in the presence of a catalyst system comprising a metallocene compound to obtain an oligomerization product mixture; and
(Ic) obtaining at least a portion of the vinylidene olefin feed from the oligomerization product mixture.

17. The process of claim 16 , wherein in step (Ia), the monomer feed comprises a single terminal olefin having a formula (F-III).

18. The process of claim 16 , wherein in step (Ia), the monomer feed comprises both the terminal olefin having formula (F-III) and the terminal olefin having formula (F-IV), and the two terminal olefins differ in terms of molecular weight thereof by no more than 100 grams per mole.

19. The process of claim 16 , wherein:
in step (Ib), the metallocene compound has a formula Cp(Bg) n MX 2 Cp′, wherein M is selected from Hf and Zr; each X is independently a halogen or a hydrocarbyl group; Cp and Cp′, the same or different, independently represents a cyclopentadienyl, alkyl-substituted cyclopentadienyl, indenyl, alkyl-substituted indenyl, 4,5,6,7-tetrahydro-2H-indenyl, alkyl-substituted 4,5,6,7-tetrahydro-2H-indenyl, 9H-fluorenyl, and alkyl-substituted 9H-fluorenyl; each Bg is a bridging group covalently linking Cp and Cp′; and n is 0, 1, or 2; and the catalyst system further comprises an alumoxane.

20. The process of claim 19 , wherein:
step (Ib) is carried out in a continuous process at a temperature in the range from 50 to 90° C.; and in step (Ib):
the metallocene compound is fed into the oligomerization reactor at a feeding rate of R(mc) moles per hour, the alumoxane is fed into the oligomerization reactor at a feeding rate of R(Al) moles per hour, the monomer is fed into the oligomerization reactor at a feeding rate of R(to) moles per hour, 350≤R(to)/R(mc)≤750, 2≤R(Al)/R(mc)≤10, an oligomer mixture comprising the vinylidene olefin and a trimer of the terminal olefin is produced, and the selectivity toward the trimer is less than 5%.

21. The process of claim 6 , wherein the active acid catalyst in step (II) is selected from a Brϕnsted acid, a solid acid, an acidic resin, a Lewis acid, and mixtures and combinations thereof.

22. The process of claim 6 , wherein the active acid catalyst comprises BF 3 ·1.1H 2 O.

23. The process of claim 6 , wherein in step (II), the molar ratio of the active acid catalyst to the vinylidene olefin is in the range from 0.01 to 50.

24. The process of claim 6 , wherein in step (II), the vinylidene olefin is admixed with BF 3 ·1.2H 2 O before the partial pressure of CO in the reactor has reached 2.0 MPa, and afterwards BF 3 is added into the reactor to form active acid catalyst BF 3 ·1.1H 2 O.

25. The process of claim 6 , wherein step (II) further comprises raising the reaction pressure to at least 7 MPa after adding the active acid catalyst.

26. The process of claim 6 , wherein step (II) further comprises raising the reaction temperature to at least 50° C. after

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Lewis Kyle G

Classifications

• B01J2531/48

  Zirconium · CPC title

• C07C53/128 Primary

  the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids · CPC title

• B01J21/02

  Boron or aluminium; Oxides or hydroxides thereof · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• C07C51/14

  on a carbon-to-carbon unsaturated bond in organic compounds · CPC title