Method for producing 2-octyl acrylate by direct esterification

Patent metadata

Field	Value
Publication number	US-9403750-B2
Application number	US-201214354986-A
Country	US
Kind code	B2
Filing date	Oct 30, 2012
Priority date	Nov 4, 2011
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

The invention relates to a process for continuously producing 2-octyl acrylate by reacting acrylic acid and 2-octanol in the presence of a sulfonic acid esterification catalyst and at least one polymerization inhibitor. The water formed by the esterification reaction is entrained by distillation in a column surmounting the reactor in the form of a heteroazeotropic mixture with the 2-octanol which is then subjected, after condensation, to separation in a decanter so as to give an upper organic phase and a lower aqueous phase. The reaction mixture containing the reaction product and residual by-products are purified by separation means in order to obtain: (1) pure 2-octyl acrylate and (2) unreacted 2-octanol and acrylic acid compounds that will be recycled along with the catalyst.

First claim

The invention claimed is:

1. A process for continuously producing 2-octyl acrylate, the process comprising the steps of (1) reacting acrylic acid and a branched secondary alcohol which is 2-octanol in the presence of a sulfuric acid esterification catalyst and at least one polymerization inhibitor in a reactor, (2) entraining water formed by the esterification reaction by distillation in a column surmounting the reactor in the form of a heteroazeotropic mixture with the 2-octanol which is condensed and then separated in a decanter to produce an upper organic phase and a lower aqueous phase, (3) purifying by separation a reaction mixture comprising reaction product and residual by-products to obtain, pure 2-octyl acrylate, unreacted 2-octanol, acrylic acid compounds, and catalyst, wherein said unreacted 2-octanol, acrylic acid compounds and catalyst are recyclable and wherein:
the aqueous phase derived from the decanter is continuously removed and not returned to the reactor;
the organic phase derived from the decanter is continuously recycled at the bottom of the distillation column surmounting the reactor; and
the treatment for purification of the reaction mixture comprises the steps of (i) separating a catalyst-rich stream which is at least partly recycled to the reaction step, (ii) separating a stream rich in unreacted 2-octanol which is at least partly recycled to the reaction step, and (iii) recovering pure 2-octyl acrylate.

2. The process as claimed in claim 1 , wherein the treatment for purification of the reaction mixture comprises steps of:
first separating the catalyst using a film evaporator, at the end of which are separated, at the bottom, a stream rich in catalyst and polymerization inhibitors, said stream being at least partly recycled to the reaction, and, at the top, a stream rich in 2-octyl acrylate; and
second, sending the stream rich in 2-octyl acrylate to a first distillation column to recover, at the top, a stream rich in 2-octanol which is recycled to the reaction and, at the bottom, a stream rich in 2-octyl acrylate which is sent to a second distillation column to separate, at the top, the pure 2-octyl acrylate and, at the bottom, a fraction containing heavy impurities and polymerization inhibitors which is either recycled to the first distillation column, or removed.

3. The process as claimed in claim 1 , wherein the treatment for purification of the reaction mixture comprises steps of:
flash evaporating the reaction mixture resulting in separation of a first stream rich in 2-octyl acrylate reaction product and of a reaction mixture residue;
bringing, with stirring, the reaction mixture residue into contact with water or an aqueous stream so as to form a two-phase system consisting of an aqueous phase comprising the catalyst, and an organic phase rich in heavy by-products resulting from the reaction;
separating said aqueous phase and recycling thereof to the reaction;
separating said organic phase which is sent to a film evaporator to separate a second stream of reaction products and unreacted reagents which is mixed with the first stream;
sending the first stream rich in 2-octyl acrylate to a distillation column to recover:
at the top, a third stream rich in 2-octanol which is recycled to the reaction,
pure 2-octyl acrylate via side take-off, and
at the bottom, a fourth stream rich in heavy by-products and containing 2-octyl acrylate which is sent to the film evaporator from which a fraction containing the heavy by-products is separated from reaction products and unreacted reagents and removed.

4. The process as claimed in claim 1 , wherein the treatment for purification of the reaction mixture comprises steps of:
bringing the reaction mixture into contact with water or an aqueous stream so as to form a two-phase system consisting of an aqueous phase comprising the catalyst, and of an organic phase rich in reaction product;
separating said aqueous phase and recycling thereof to the reaction;
separating said organic phase which is sent to a first distillation column to obtain:
at the top, a stream rich in reaction product; and
at the bottom, a stream rich in heavy by-products and containing 2-octyl acrylate, said stream being sent to a film evaporator from which a fraction containing the heavy by-products is separated and removed from reaction products and unreacted reagents which are recycled to the first distillation column;
sending the stream rich in reaction product to a second distillation column to recover:
at the top, a stream rich in 2-octanol which is recycled to the reaction;
the pure 2-octyl acrylate via a side take-off; and
at the bottom, a stream rich in 2-octyl acrylate with polymerization inhibitors, which is at least partly recycled to the first distillation column.

5. The process of claim 1 wherein the catalyst is methanesulfonic acid.

6. The process of claim 1 wherein the reaction is carried out in a single reactor, the 2-octanol being introduced partly directly into the reactor and partly by means of the distillation column surmounting the reactor.

7. The process of claim 1 wherein the aqueous phase from the decanter is subjected to a distillation whereby any 2-octanol present is recovered before the aqueous phase is removed.

8. The process of claim 2 wherein the film evaporator is a falling film or wiped film evaporator operating under the conditions of the first distillation column.

9. The process of claim 1 wherein the acrylic acid is of renewable origin.

Assignees

• Arkema France

Inventors

• Riondel Alain
• Graire Coralie
• Levray Andre
• Linemann Reinhard

Classifications

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C67/08 Primary

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C67/54

  by distillation · CPC title

• Y02P20/584

  Recycling of catalysts · CPC title

• C07C67/58

  by liquid-liquid treatment · CPC title