Synthesis of N-vinyl carboxylic acid amides

Patent metadata

Field	Value
Publication number	US-10696622-B2
Application number	US-201715669989-A
Country	US
Kind code	B2
Filing date	Aug 7, 2017
Priority date	Aug 29, 2016
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

Processes and systems for producing N-vinyl carboxylic acid amides are provided herein. According to some aspects of the present invention, a process for producing an N-vinyl carboxylic acid amide is described that eliminates interim solids handling steps during formation of the intermediate compounds, thereby increasing efficiency and reducing cost. The processes and system described herein may be used for the synthesis of N-vinylformamide and its intermediates, including 1-hydroxyethylformamide and 1-alkoxyethylformamide, or for the synthesis of N-methyl,N-vinylformamide and its intermediates, including N-methyl,1-hydroxyethylformamide and N-methyl,1alkoxyethylformamide.

First claim

The invention claimed is:

1. A process for making 1-hydroxyethylformamide or N-methyl, 1-hydroxylethylformamide, said process comprising:
(a) introducing formamide or N-methylformamide and acetaldehyde into a first reaction zone, wherein the molar ratio of formamide or N-methylformamide to acetaldehyde added to said first reaction zone is at least 1.5:1; and
(b) reacting at least a portion of said formamide or said N-methylformamide with at least a portion of said acetaldehyde in the presence of a basic catalyst in said first reaction zone to thereby form a reaction mixture comprising 1-hydroxyethylformamide or N-methyl,1-hydroxyethylformamide
wherein said introducing further comprises introducing at least one solvent into said first reaction zone and wherein said reacting is performed in the presence of said solvent, wherein the solubility of said 1-hydroxyethylformamide or said N-methyl,1-hydroxethylformamide in said solvent is at least 40 weight percent as determined at 20° C. using CIPAC Method MT 181.

2. The process of claim 1 , wherein at least 90 weight percent of said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide formed during said reacting is maintained in solution in said reaction mixture and wherein the total solids content of said reaction mixture is not more than 10 weight percent.

3. The process of claim 1 , further comprising subsequent to said reacting, combining said reaction mixture with at least one alcohol and an acid catalyst; and alkoxylating at least a portion of said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide with said alcohol to thereby form another reaction mixture comprising 1-alkoxyethylformamide or N-methyl,1-alkoxyethylformamide, and wherein said reacting, said combining, and said alkoxylating are performed in sequence without an intervening solids handling step.

4. The process of claim 1 , wherein said reacting is performed in a continuous reaction vessel and said reaction mixture is a single-phase liquid reaction mixture.

5. The process of claim 1 , wherein said solvent is present in said first reaction zone in an amount of at least 40 weight percent, based on the total weight of said reaction mixture.

6. The process of claim 1 , wherein said reaction mixture comprises not more than 10 weight percent of said solvent, based on the total weight of said reaction mixture.

7. The process of claim 1 , wherein said reacting is carried out at an average reaction temperature of not more than 45° C. for a total reaction time of not more than 45 minutes and wherein said reacting is performed in a continuous plug flow reactor.

8. A process for making 1-hydroxyethylformamide or N-methyl, 1-hydroxyethylformamide, said process comprising:
(a) introducing formamide or N-methylformamide and acetaldehyde into a first reaction zone; and
(b) reacting at least a portion of said formamide or said N-methylformamide with at least a portion of said acetaldehyde in the presence of a basic catalyst in said first reaction zone to form a first reaction mixture comprising 1-hydroxyethylformamide or N-methyl,1-hydroxyethylformamide, wherein said first reaction mixture further comprises at least one solvent, wherein said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide has a solubility of at least 20 weight percent in said solvent as determined at 20° C. using CIPAC Method MT 181, and wherein at least 90 weight percent of said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide formed during said reacting is maintained in solution in said first reaction mixture, wherein the molar ratio of formamide to acetaldehyde or the molar ratio of N-methylformamide to acetaldehyde introduced into said first reaction zone is at least 1.1:1.

9. The process of claim 8 , wherein said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide has a solubility of at least 40 weight percent in said solvent as determined at 20° C. using CIPAC Method MT 181 and wherein said solvent comprises at least one C 1 to C 8 alcohol or water.

10. The process of claim 8 , further comprising alkoxylating at least a portion of said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide in said first reaction mixture with an alcohol in the presence of an acid catalyst in a second reaction zone to thereby form a second reaction mixture comprising 1-alkoxyethylformamide or N-methyl,1-alkoxyethylformamide, wherein said reacting and alkoxylating are performed in sequence without an intervening solids handling step.

11. The process of claim 10 , wherein said reacting is carried out at a temperature of not more than 25° C. for a time of not more than 1 hour, wherein the yield of said 1-hydroxyethylformamide or said N-methyl,1-hydroxyethylformamide from said first reaction zone is at least 90 percent, wherein said alkoxylating is carried out at a temperature of at least 20° C. and not more than 45° C. and wherein the yield of said 1-alkoxyethylformamide or said N-methyl,1-alkoxyethylformamide from said second reaction zone is at least 85 percent.

12. The process of claim 8 , wherein the molar ratio of formamide to 1-hydroxyethylformamide or the molar ratio of N-methylformamide to N-methyl,1-hydroxyethylformamide in said first reaction mixture is greater than 1.1:1.

13. The process of claim 8 , wherein said reacting is performed in a continuous reaction vessel and wherein said first reaction mixture is a single phase reaction mixture.

14. The process of claim 1 , wherein the yield of 1-hydroxyethylformamide or N-methyl,1-hydroxyethylformamide in said reaction mixture is at least 90%.

15. The process of claim 1 , wherein the yield of 1-hydroxyethylformamide or N-methyl,1-hydroxyethylformamide in said reaction mixture is at least 95%.

Assignees

• Taminco Bvba
• Eastman Chem Co

Inventors

• Dumoleijn Kim
• Moonen Kristof
• Henricot Alexis
• Han Cai Xing Simon

Classifications

• C07C231/08

  from amides by reaction at nitrogen atoms of carboxamide groups · CPC title

• C07C233/18

  having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton · CPC title

• C07C233/03

  with carbon atoms of carboxamide groups bound to hydrogen atoms · CPC title

• C07C233/17

  with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom · CPC title

• C07C231/12 Primary

  by reactions not involving the formation of carboxamide groups · CPC title