Methods of making (alk)acrylic esters in flow reactors

Patent metadata

Field	Value
Publication number	US-10308584-B2
Application number	US-201716079161-A
Country	US
Kind code	B2
Filing date	Feb 21, 2017
Priority date	Feb 25, 2016
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

Abstract

A method of making an (alk)acrylic ester in a microflow reactor.

First claim

What is claimed is:

1. A method of making an (alk)acrylic ester comprising
adding to a mixing chamber of a microflow reactor
an alcohol,
one or more bases that are sufficient to at least partially deprotonate the alcohol,
a polar solvent,
an (alk)acryloyl halide or a 3-haloalkylcarboxyl halide, and
an organic solvent that is immiscible with the polar solvent in sufficient quantity to dissolve the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide; wherein

the molar flow ratio of the alcohol to the sum of all of the one or more bases is 1 to at least 1.1; and
producing a product stream comprising one or more (alk)acrylic esters and one or more salts of the one or more bases; wherein
the polar solvent added to the mixing chamber is sufficient to dissolve substantially all of the at one or more salts; and
the product stream having an organic portion and a polar portion, the organic portion comprises the (alk)acrylic ester in an amount of at least 80 wt % based on the total weight of the solutes in the organic portion of the product stream.

2. The method of claim 1 , wherein
the polar solvent comprises water.

3. The method of claim 1 , wherein
the mixing chamber of the microflow reactor comprises an exit port;
wherein the method further comprises a step of removing the (alk)acrylic ester from the exit port simultaneously with the adding step.

4. The method of claim 1 , wherein
the one or more bases are soluble in the polar solvent, the alcohol, or both and are selected from amines, alkali metal hydroxides, alkali earth metal hydroxides, and combinations thereof.

5. The method of claim 4 , wherein the one or more bases comprises triethyl amine.

6. The method of claim 1 , wherein the mixing chamber of the microflow reactor comprises a first addition port and a second addition port, and wherein the adding step comprises
adding a mixture of the alcohol and the one or more bases through the first addition port; and
adding the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide through the second addition port.

7. The method of claim 6 , wherein
adding the mixture of the alcohol and the base through the first addition port comprises adding a mixture of the alcohol, the base, and the polar solvent through the first addition port; and
adding the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide through the second addition port comprises adding a mixture of the organic solvent and the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide through the second addition port.

8. The method of claim 1 , wherein the mixing chamber of the microflow reactor comprises a first addition port, a second addition port, a third addition port, and a fourth addition port, and wherein the adding step comprises
adding a mixture of the alcohol and base through the first addition port;
adding the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide through the second addition port;
adding the polar solvent through the third addition port; and
adding the organic solvent through the fourth addition port.

9. The method of claim 1 , wherein the molar flow ratio of the alcohol to the (alk)acryloyl halide or 3-haloalkylcarboxyl halide is 1 to at least 1.1.

10. The method of claim 1 , wherein the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide is 3-chloropropionylchloride.

11. The method of claim 1 , wherein the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide is an (alk)acrylyl halide.

12. The method of claim 1 , wherein the (alk)acryloyl halide or a 3-haloalkylcarboxyl halide is acryloyl chloride or methacryloyl chloride.

13. The method of claim 1 , wherein the organic solvent is selected from dichloromethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl butyl ketone.

14. The method of claim 1 , wherein the microflow reactor is not temperature controlled during the method.

15. The method of claim 1 , wherein the mixing chamber of the microflow reactor has an internal volume of no more than 1 mL.

Assignees

• 3M Innovative Properties Co

Inventors

• Dams Rudolf J
• Van Campenhout Rudy W

Classifications

• B01J19/0093

  Microreactors, e.g. miniaturised or microfabricated reactors (laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027) · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C67/14 Primary

  from carboxylic acid halides · CPC title

• B01J2219/0086

  Dimensions of the flow channels · CPC title

• B01J2219/00889

  Mixing · CPC title