Lanthanide Catalyst Esterification for Cyanoacrylate Monomers

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Solution Overview

Problem

The commercial production of cyanoacrylate monomers typically relies on thermally induced depolymerization of a prepolymer formed under base-catalyzed Knoevenagel condensation reaction conditions, which is inefficient and unsuitable for sensitive precursors like glycidyl cyanoacetate, and lacks the use of lanthanide element-containing acid catalysts in esterification reactions for electron deficient olefin precursors.

Innovation Solution

Employing a lanthanide element catalyst, such as ytterbium trifluoromethane sulfonate, in an acid-catalyzed esterification reaction between cyanoacetic acid and an alcohol to produce high yields of electron deficient olefin precursors like cyanoacetates, which can then be used to synthesize cyanoacrylates without the need for thermal depolymerization.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If base-catalyzed Knoevenagel condensation reaction is used to produce cyanoacrylate monomers, then high yields of monofunctional cyanoacrylates can be achieved, but thermal depolymerization is required which is inefficient and unsuitable for sensitive precursors like glycidyl cyanoacetate

Engineering Contradiction:
Improveyield of cyanoacrylate monomersVSAvoidsuitability for sensitive precursors
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent changes the fundamental reaction parameters by switching from base-catalyzed to acid-catalyzed conditions, and from condensation to esterification reaction type. This allows the use of sensitive precursors like glycidyl cyanoacetate that would decompose under traditional basic and thermal conditions, while still achieving high yields of cyanoacrylate monomers through the acid-catalyzed esterification of cyanoacetates with formaldehyde

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces cyanoacetates as stable intermediate compounds that can be prepared in advance under mild acid-catalyzed esterification conditions, then converted to cyanoacrylate monomers without requiring thermal depolymerization. This intermediary approach decouples the synthesis of the active monomer from the formation of the prepolymer, enabling better control over sensitive functional groups

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of manufacture

If traditional Knoevenagel condensation reaction conditions are used, then cyanoacrylate monomers can be produced, but the process requires thermal depolymerization which reduces efficiency and increases complexity

Engineering Contradiction:
Improveprocess simplicityVSAvoidmanufacturing efficiency
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The patent extracts and eliminates the thermal depolymerization step from the traditional Knoevenagel condensation process. By using acid-catalyzed esterification to directly produce cyanoacrylate monomers from cyanoacetates and formaldehyde, the method removes the inefficient thermal cracking step while simplifying the overall manufacturing process

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Instead of following the traditional route of condensation then depolymerization, the patent inverts the approach by using esterification to directly form the monomer. This reverse engineering of the synthetic pathway eliminates the need for prepolymer formation and subsequent thermal breakdown, streamlining the manufacturing process

Inventive Principle:
Principle #13The other way round (Inversion)

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

This method achieves yields greater than 70%, desirably 80%, and more desirably 90% of electron deficient olefin precursors, enabling the synthesis of cyanoacrylates with improved purity and avoiding the limitations of traditional Knoevenagel condensation reactions.

Implementation Method 1

reacting cyanoacetic acid and an alcohol, in the presence of a catalyst comprising a lanthanide element, under appropriate conditions and for a time sufficient to yield a cyanoacetate

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3558933B1Process for preparing electron deficient olefin precursors
Publication Date: 2022.11.23 HENKEL KGAA
  • EP3558933B1 patent drawingFigure 1

AI summary

This invention relates to a process for producing electron deficient olefin precursors, such as 2-cyanoacetates, using an acid catalyzed esterification reaction.