(Meth)Acrylic Acid Esterification With Alkene Recycle

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Solution Overview

Problem

Existing methods for producing (meth)acrylic acid esters using secondary alcohols face challenges in selectivity and yield due to intramolecular dehydration reactions and hydrolysis, leading to impurities and decomposition, which are not effectively addressed by current techniques.

Innovation Solution

Control the alkene concentration to secondary alcohol concentration ratio in the reactor to 0.001 or more during the esterification process, recycling alkenes to suppress intramolecular dehydration and enhance the selectivity and yield of (meth)acrylic acid esters.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If secondary alcohol is used in esterification reaction with acid catalyst, then esterification reaction proceeds, but intramolecular dehydration reaction occurs leading to alkene formation and reduced selectivity

Engineering Contradiction:
Improveesterification reaction rateVSAvoidselectivity of (meth)acrylic acid ester
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent applies preliminary anti-action by adding alkene at the beginning of the esterification reaction. This pre-added alkene suppresses the intramolecular dehydration reaction of secondary alcohol that would otherwise produce unwanted alkene impurities, thereby improving selectivity before the side reaction can occur significantly

Inventive Principle:
Principle #9Preliminary anti-action

Solution Approach 2:

The patent changes the chemical composition parameter by introducing alkene into the reaction system. This parameter change shifts the reaction equilibrium and suppresses the dehydration side reaction, allowing the esterification to proceed with high selectivity while maintaining productivity

Inventive Principle:
Principle #35Parameter changes

2Productivity

If water is removed to shift equilibrium toward ester formation, then yield improves, but hydrolysis decomposition of ester increases

Engineering Contradiction:
Improveyield of (meth)acrylic acid esterVSAvoidpurity of (meth)acrylic acid ester
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent applies preliminary anti-action by pre-adding alkene to suppress hydrolysis decomposition. The alkene acts in advance to prevent the reverse reaction that would decompose the ester, allowing water removal to proceed effectively for improving yield without significant loss to decomposition

Inventive Principle:
Principle #9Preliminary anti-action

Solution Approach 2:

The patent converts the potentially harmful effect of water (which causes hydrolysis) into a benefit by using alkene to suppress the hydrolysis reaction. This allows the water removal process to effectively shift equilibrium toward ester formation without the detrimental side effect of decomposition

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Manufacturing precision

If distillation is used for purification with long retention time, then purity improves, but decomposition of (meth)acrylic acid ester increases

Engineering Contradiction:
Improvepurity of (meth)acrylic acid esterVSAvoidselectivity of (meth)acrylic acid ester
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent applies preliminary anti-action by adding alkene before distillation to prevent decomposition during the purification process. This suppresses any decomposition reactions that might occur during long retention time distillation, maintaining both purity and selectivity

Inventive Principle:
Principle #9Preliminary anti-action

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The method improves the selectivity and yield of (meth)acrylic acid esters by shifting the equilibrium reaction towards forming the desired product, reducing impurities and enhancing productivity.

Implementation Method 1

reacting (meth)acrylic acid with a secondary alcohol in a reactor in the presence of an acid-type esterification catalyst

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

reacting (meth)acrylic acid with a secondary alcohol in a reactor in the presence of an acid-type esterification catalyst and a polymerization inhibitor

Methodology Applied
Scientific EffectPolymerization inhibition:

Data Source

PatentEP4620941A2(METH)acrylic acid ester production method
Publication Date: 2025.09.24 NIPPON SHOKUBAI CO LTD
  • EP4620941A2 patent drawingFigure 1
  • EP4620941A2 patent drawingFigure 2
  • EP4620941A2 patent drawingFigure 3

AI summary

The present invention provides a technique for improving the selectivity of a (meth)acrylic acid ester. The present invention relates to a method of producing a (meth)acrylic acid ester, the method including: reacting (meth)acrylic acid with a secondary alcohol in a reactor in the presence of an acid-type esterification catalyst and a polymerization inhibitor; and supplying an alkene-containing product obtained during production of the (meth)acrylic acid ester to the reactor so that a ratio of an alkene concentration to a secondary alcohol concentration in the reactor is 0.001 or more.