# US 10,308,584 B2 · Methods of making (alk)acrylic esters in flow reactors

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- Number: US 10,308,584 B2
- Document ID: US10308584B2
- Status: Granted
- Kind: B2
- Application number: 16/079,161
- Filed: 2017-02-21
- Published: 2019-02-28
- Granted: 2019-06-04
- Earliest claimed: 2016-02-25
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Rudolf J. Dams; Rudy W. Van Campenhout
- Web page: https://patentgrep.com/patent/US10308584B2

## CPC

- C07C 67/14: from carboxylic acid halides
- B01J 19/0093: {Microreactors, e.g. miniaturised or microfabricated reactors (laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027)}
- B01J 19/248: {Reactors comprising multiple separated flow channels}
- B01J 2219/0086: Dimensions of the flow channels
- B01J 2219/00889: Mixing
- C07C 69/54: Acrylic acid esters; Methacrylic acid esters
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

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

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 4)

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

### Claim 6 (depends on 1)

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.

### Claim 7 (depends on 6)

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.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

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.

### Claim 10 (depends on 1)

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

### Claim 11 (depends on 1)

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

### Claim 12 (depends on 1)

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

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 1)

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

### Claim 15 (depends on 1)

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