PROCESS FOR ACRYLATE PRODUCTION

• US 20150141693A1
• Filed: 07/02/2013
• Published: 05/21/2015
• Est. Priority Date: 07/02/2012
• Status: Abandoned Application

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Allen, Scott D., Coates, Geoffrey
• Application Number:
  US14/410,764
• Publication Number:
  US 20150141693A1
• Time in Patent Office: Days
• US Class Current: 560/204
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C07D 305/12 Beta-lactones
• CPC Class Codes: C08G 63/08 Lactones or lactides

Abstract

Disclosed are methods for the continuous flow production of acrylic acid and derivatives thereof from an epoxide feedstock. In one embodiment, the method includes the steps of: contacting a process stream comprising ethylene oxide and an organic solvent with a carbonylation catalyst and carbon monoxide to provide a reaction stream containing beta propiolactone; applying the reaction stream containing the beta propiolactone to a nanofiltration membrane to produce a permeate stream containing beta lactone and a retentate stream containing carbonylation catalyst; and treating the permeate stream under conditions to convert the beta propiolactone into an acrylate ester. In some embodiments, the retentate stream is returned to the first step of the process where it is recharged with additional epoxide and passed through the sequence again.

Claims

1. A method for the production of an acrylate ester from ethylene oxide in a continuous flow process, the method comprising the steps of:

a) contacting a process stream comprising ethylene oxide and an organic solvent with a carbonylation catalyst in the presence of carbon monoxide to provide a reaction stream containing beta propiolactone formed from the ethylene oxide;

b) applying the reaction stream containing the beta propiolactone to a nanofiltration membrane to produce;

i) a permeate stream comprising beta propiolactone and a first portion of the organic solvent, and

ii) a retentate stream comprising carbonylation catalyst and a second portion of the organic solvent; and

c) treating the permeate stream under conditions to convert the beta propiolactone into an acrylate ester.

3. The method of claim 1, further comprising the step of returning the retentate stream to step (a).

4. The method of claim 3, further comprising treating the retentate stream prior to returning it to step (a) where the step of treating is selected from the group consisting of:

adding fresh catalyst, removing spent catalyst;

adding solvent;

adding epoxide; and

any combination of two or more of these.

5. The method of claim 1, wherein the nanofiltration membrane is selected from the group consisting of a polyimide membrane, an integrally skinned asymmetric polyimide membrane, a polyamide-imide membrane, a silicone-coated polyamide composite membrane, a polyacrylonitrile membrane, a membrane comprising a polydimethylsiloxane film on a polyacrylonitrile support, a silicone membrane, a polyphosphazene membrane, a polyphenylene sulfide membrane, a polyetheretherketone membrane, a polybenzimidazol membrane, and combinations thereof.

6. The method of claim 1, wherein the carbonylation catalyst comprises a metal carbonyl compound.

7. The method of claim 6, wherein the metal carbonyl compound has the general formula [QM_y(CO)_w]^x,

where:

Q is any ligand and need not be present;

M is a metal atom;

y is an integer from 1 to 6 inclusive;

w is a number such as to provide the stable metal carbonyl; and

x is an integer from −

3 to +3 inclusive.

8. The method of claim 7, wherein M is selected from the group consisting of Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, In and combinations thereof;

or where M is Rh;

or where M is Co.

9. The method of claim 6, wherein the carbonylation catalyst further comprises a Lewis acidic co-catalyst.

10. The method of claim 9, wherein the metal carbonyl compound is anionic, and the Lewis acidic co-catalyst is cationic.

11. The method of claim 10, wherein the metal carbonyl compound comprises a carbonyl cobaltate and the Lewis acidic co-catalyst comprises a metal-centered Lewis acid.

12. The method of claim 11, wherein the metal-centered Lewis acid is a metal complex of formula [M′

(L)_b]^c+,

where, M′

is a metal;

each L is a ligand;

b is an integer from 1 to 6 inclusive;

c is 1, 2, or 3; and

where, if more than one L is present, each L may be the same or different.

13. The method of claim 12, where M′

is selected from the group consisting of aluminum, chromium, indium and gallium;

or where M′

is aluminum;

or where M′

is chromium.

14. The method of claim 12, where the metal-centered Lewis acid includes a dianionic tetradentate ligand;

or where the metal-centered Lewis acid includes a dianionic tetradentate ligand selected from the group consisting of;

a porphyrin derivative;

a salen derivative;

a dibenzotetramethyltetraaza[14]annulene (tmtaa) derivative;

a phthalocyaninate derivative; and

a derivative of the Trost ligand;

or where the metal-centered Lewis acid includes a porphyrin ligand.

15. The method of claim 1, wherein the permeate stream is fed to an esterification unit prior to step (c).

16. The method of claim 1 further comprising the step of vacuum distilling the permeate stream to separate the beta lactone from the first portion of the organic solvent prior to step (c).

17. The method of claim 1, wherein step (c) is mediated by a catalyst.

18. The method of claim 17, wherein the catalyst in step (c) is an acid catalyst;

or wherein the catalyst in step (c) is a basic catalyst.

19. The method of claim 1, wherein step (a) is performed at a CO pressure from about 50 psi to about 5000 psi.

20. The method of claim 1, wherein step (a) is performed at a temperature from about 0°

C. to about 125°

C.;

or

wherein step (a) is performed at a temperature from about 30°

C. to about 100°

C.;

or

wherein step (a) is performed at a temperature from about 40°

C. to about 80°

C.

2. A method for the production of poly(3-hydroxy propionic acid) from ethylene oxide in a continuous flow process, the method comprising the steps of:

a) contacting a process stream comprising ethylene oxide and an organic solvent with a carbonylation catalyst in the presence of carbon monoxide to provide a reaction stream containing beta propiolactone formed from the ethylene oxide;

b) applying the reaction stream containing the beta propiolactone to a nanofiltration membrane to produce;

i) a permeate stream comprising beta propiolactone and a first portion of the organic solvent, and

ii) a retentate stream comprising carbonylation catalyst and a second portion of the organic solvent; and

c) treating the permeate stream under conditions to convert the beta propiolactone into poly(3-hydroxy propionic acid).