Method for preparing hydroxyethyl (meth) acrylate

Patent metadata

Field	Value
Publication number	US-9845281-B2
Application number	US-201415300566-A
Country	US
Kind code	B2
Filing date	Jul 29, 2014
Priority date	Jul 14, 2014
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

Hydroxyethyl (methyl)acrylate is prepared by a process of a combination of a three-stage tubular reactor and a tower reactor, wherein, firstly, a catalyst, a polymerization inhibitor and (methyl) acrylic acid are mixed until the solids are dissolved, then mixed with a part of ethylene oxide and thereafter enter into a first tubular reactor for a reaction, a reaction liquid flowing out from the first tubular reactor is mixed with a certain amount of ethylene oxide and enters into a second tubular reactor for a reaction, a reaction liquid flowing out from the second tubular reactor is then mixed with a certain amount of ethylene oxide and thereafter enters into a third tubular reactor, and a reaction liquid flowing out from the third tubular reactor is then passed through a stage of an adiabatic tower reactor and aged such that a product liquid is obtained from extraction.

First claim

The invention claimed is:

1. A method for preparing hydroxyethyl (meth)acrylate, conducted in a process using a combination of three-stage tubular reactors and a tower reactor, the process comprising the following steps:
firstly, mixing catalysts, polymerization inhibitors and (meth)acrylic acid until the solids are dissolved;
then mixing the mixture of the catalysts, polymerization inhibitors and (meth)acrylic acid with ethylene oxide in an amount of 30-80% of the total amount of the ethylene oxide in the whole reaction and thereafter entering a first tubular reactor to react;
mixing the reaction liquid from the first tubular reactor with ethylene oxide in an amount of 10-50% of the total amount of the ethylene oxide in the whole reaction and thereafter entering a second tubular reactor to react;
mixing the reaction liquid from the second tubular reactor with ethylene oxide in an amount of 1-30% of the total amount of the ethylene oxide in the whole reaction and thereafter entering a third tubular reactor; and
aging the reaction liquid from the third tubular reactor in a tower reactor to obtain hydroxyethyl (meth)acrylate liquid product.

2. The method according to claim 1 , wherein for the whole reaction, the molar ratio of the total amount of ethylene oxide to (meth)acrylic acid is 1.0-1.2:1.

3. The method according to claim 1 , wherein the polymerization inhibitors are selected from one or more of p-benzoquinone, p-phenylenediamine, phenothiazine, diisopropyl p-phenylene diamine, 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy and 4-carbonyl-2,2,6,6-tetramethyl-piperidinooxy; the amount of the polymerization inhibitors is 0.01-0.2% of the weight of (meth)acrylic acid.

4. The method according to claim 1 , wherein the catalysts are one or more of amine compounds, iron compounds and chromium compounds; the amine compound is selected from tetrabutyl ammonium bromide, tetramethyl ammonium bromide, tetramethyl ammonium chloride, tetrabutyl ammonium iodide, triethylamine and pyridine; the iron compound is selected from ferric trichloride, iron powder, ferric formate, ferric acetate, iron acrylate and iron methacrylate; the chromium compound is selected from chromium trichloride, chromium acrylate, chromium methacrylate, chromium acetylacetonate, chromium picolinate, chromium formate, chromium acetate; the amount of the catalysts is 0.1-2% of the weight of (meth)acrylic acid.

5. The method according to claim 1 , wherein the amount of the ethylene oxide added into the first tubular reactor is 50-70% of the total amount of the ethylene oxide in the whole reaction; the amount of the ethylene oxide added into the second tubular reactor is 20-40% of the total amount of the ethylene oxide in the whole reaction; the amount of the ethylene oxide added into the third tubular reactor is 5-20% of the total amount of the ethylene oxide in the whole reaction.

6. The method according to claim 1 , in the first tubular reactor, the reaction temperature is 80-120° C., the reaction pressure is 0.2-0.5 Mpa, and the residence time is 0.1-0.3 h.

7. The method according to claim 1 , in the second tubular reactor, the reaction temperature is 100-130° C., the reaction pressure is 0.4-0.8 Mpa and the residence time is 0.2-0.5 h.

8. The method according to claim 1 , in the third tubular reactor, the reaction temperature is 110-150° C., the reaction pressure is 0.5-1 Mpa, and the residence time is 0.25-0.6 h.

9. The method according to claim 1 , during the reaction, each of the tubular reactors is under the protection of N 2 .

10. The method according to claim 1 , wherein the tower reactor is an adiabatic tower reactor.

11. The method according to claim 1 , wherein the theoretical plate number of the tower reactor is 4-20; the reaction pressure is 0.8-1.2 Mpa; the residence time is 0.3-1 h.

12. The method according to claim 2 , wherein the polymerization inhibitors are selected from one or more of p-benzoquinone, p-phenylenediamine, phenothiazine, diisopropyl p-phenylene diamine, p-hydroxy tetramethyl piperidine nitrogen oxygen free radical and p-carbonyl tetramethyl piperidine nitrogen oxygen free radical; the amount of the polymerization inhibitors is 0.01-0.2% of the weight of (meth)acrylic acid.

13. The method according to claim 2 , wherein the catalysts are one or more of amine compounds, iron compounds and chromium compounds; the amine compound is selected from tetrabutyl ammonium bromide, tetramethyl ammonium bromide, tetramethyl ammonium chloride, tetrabutyl ammonium iodide, triethylamine and pyridine; the iron compound is selected from ferric trichloride, iron powder, ferric formate, ferric acetate, iron acrylate and iron methacrylate; the chromium compound is selected from chromium trichloride, chromium acrylate, chromium methacrylate, chromium acetylacetonate, chromium picolinate, chromium formate, chromium acetate; the amount of the catalysts is 0.1-2% of the weight of (meth)acrylic acid.

14. The method according to claim 2 , wherein the amount of the ethylene oxide added into the first tubular reactor is 50-70% of the total amount of the ethylene oxide in the whole reaction; the amount of the ethylene oxide added into the second tubular reactor is 20-40% of the total amount of the ethylene oxide in the whole reaction; the amount of the ethylene oxide added into the third tubular reactor is 5-20% of the total amount of the ethylene oxide in the whole reaction.

15. The method according to claim 2 , in the first tubular reactor, the reaction temperature is 80-120° C., the reaction pressure is 0.2-0.5 Mpa, and the residence time is 0.1-0.3 h.

16. The method according to claim 2 , in the second tubular reactor, the reaction temperature is 100-130° C., the reaction pressure is 0.4-0.8 Mpa, and the residence time is 0.2-0.5 h.

17. The method according to claim 2 , in the third tubular reactor, the reaction temperature is 110-150° C., the reaction pressure is 0.5-1 Mpa, and the residence time is 0.25-0.6 h.

18. The method according to claim 5 , in the first tubular reactor, the reaction temperature is 80-120° C., the reaction pressure is 0.2-0.5 Mpa, and the residence time is 0.1-0.3 h.

19. The method according to claim 5 , in the second tubular reactor, the reaction temperature is 100-130° C., the reaction pressure is 0.4-0.8 Mpa, and the residence time is 0.2-0.5 h.

20. The method according to claim 5 , in the third tubular reactor, the reaction temperature is 110-150° C., the reaction pressure is 0.5-1 Mpa, and the residence time is 0.25-0.6 h.

21. The method according to claim 2 , wherein for the whole reaction, the molar ratio of the total amount of ethylene oxide to (meth)acrylic acid is 1.03-1.1:1.

22. The method according to claim 6 , in the first tubular reactor, the reaction temperature is 90-110° C., the reaction pressure is 0.3-0.4 Mpa and the residence time is 0.15-0.25 h.

23. The method according to claim 7 , in the second tubular reactor, the reaction temperature is 110-120° C., the reaction pressure is 0.5-0.7 Mpa and the residence time is 0.25-0.4 h.

24. The method according to claim 8 , in the third tubular reactor, the reaction temperature is 120-130° C., the reaction pressure is 0.6-0.9 Mpa and the residence time is 0.3-0.5 h.

Assignees

• Wanhua Chemical Group Co Ltd

Inventors

• Li Junping
• Chen Haibo
• Zhang Lichang
• Cui Chunxian
• Li Yuan
• Hua Weiqi
• Ding Jiansheng
• Zhang Junhua
• Cheng Zhaokun

Classifications

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C07C67/26 Primary

  with an oxirane ring · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title