Invented by Bernard Miles Malofsky, Adam Gregg Malofsky, Jeffrey M. Sullivan, Philip B. Kisanga, John Joseph Anderson, Michael Charles Milner Cockrem, Philip Jay Carlberg, Nippon Shokubai Co Ltd

The market for the method of obtaining methylene malonate by the bis(hydroxymethylmalonate) pathway is gaining significant attention in the chemical industry. Methylene malonate is a versatile compound that finds applications in various sectors, including pharmaceuticals, polymers, and agrochemicals. The bis(hydroxymethylmalonate) pathway offers a promising approach to produce methylene malonate efficiently and sustainably. Methylene malonate is a compound with two ester groups and a methylene bridge in between. It is a valuable building block for the synthesis of complex molecules due to its unique reactivity and structural features. Traditionally, methylene malonate has been synthesized using the Knoevenagel condensation reaction, which involves the reaction of malonic acid with formaldehyde. However, this method suffers from several drawbacks, including low yields, the use of toxic reagents, and the generation of hazardous waste. The bis(hydroxymethylmalonate) pathway offers an alternative and more environmentally friendly route to produce methylene malonate. This pathway involves the condensation of glyoxal with malonic acid, followed by a decarboxylation step to form bis(hydroxymethylmalonate). This intermediate compound can then be easily converted into methylene malonate through a simple acid-catalyzed reaction. One of the key advantages of the bis(hydroxymethylmalonate) pathway is its high atom economy. The reaction sequence involves the use of readily available starting materials, and almost all the atoms present in the reactants are incorporated into the final product. This results in minimal waste generation and a more sustainable production process compared to traditional methods. Furthermore, the bis(hydroxymethylmalonate) pathway offers improved reaction kinetics and higher yields compared to the Knoevenagel condensation method. The reaction conditions are milder, and the reaction proceeds smoothly without the need for harsh conditions or toxic catalysts. This not only reduces the overall cost of production but also enhances the safety and environmental profile of the process. The market potential for methylene malonate is vast, considering its diverse applications in various industries. In the pharmaceutical sector, methylene malonate can be used as a building block for the synthesis of drug candidates with improved pharmacokinetic properties. Its unique structural features enable the introduction of functional groups that enhance drug efficacy and reduce side effects. In the polymer industry, methylene malonate can be utilized as a monomer for the production of high-performance polymers. Its reactivity allows for the formation of polymers with tailored properties, such as enhanced thermal stability, mechanical strength, and chemical resistance. These polymers find applications in coatings, adhesives, and engineering plastics. Additionally, methylene malonate has potential applications in the agrochemical sector. It can be used as a precursor for the synthesis of herbicides and insecticides, providing an alternative to traditional chemical compounds that may have adverse environmental impacts. As the demand for sustainable and environmentally friendly chemical processes continues to grow, the market for the method of obtaining methylene malonate by the bis(hydroxymethylmalonate) pathway is expected to expand. The advantages of this pathway, such as high atom economy, improved reaction kinetics, and higher yields, make it an attractive option for chemical manufacturers. Moreover, the versatility of methylene malonate and its applications in various industries further contribute to its market potential. In conclusion, the bis(hydroxymethylmalonate) pathway offers a promising method for obtaining methylene malonate. Its sustainable and efficient production process, coupled with the compound’s diverse applications, make it an attractive option for chemical manufacturers. As the demand for sustainable chemical processes and innovative compounds continues to rise, the market for methylene malonate is expected to grow significantly in the coming years.

The Nippon Shokubai Co Ltd invention works as follows

Method for obtaining methylene malonate, and related monomers using a bis(hydroxymethyl), malonate pathway.” Thermolysis is used to react a bis(hydroxymethyl malonate) intermediary to produce a methylene monomer. In the presence of an acidic catalyst (e.g. calcium hydroxide), a source of formaldehyde is supplied (e.g. formalin), and a malonate is then added (e.g. diethylmalonate) under appropriate reaction conditions in order to obtain the intermediate (e.g. dialkylbis(hydroxymethyl), for example). The intermediate is subjected (i.e. to thermolysis) in suitable conditions, and in the presence a suitable catalyst (e.g. a Zeolite), to obtain a monomer of methylene malonate. In one embodiment, the thermolysis includes adding the bis(hydroxymethyl-malonate) intermediary to a heated catalyst. The reaction product can be collected and purified. The disclosed methods can be carried out in continuous operation. Modular units can be used to perform discrete steps within an entire plant.

Background for Method of obtaining methylene malonate by bis(hydroxymethylmalonate) pathway

1. “1.

The invention is a method for producing methylene malonate using a bis (hydroxymethyl) malonate intermediate. The intermediate is then cracked to produce a monomer.

2. Background

Methylene malonates are compounds with the general formula (I): “Methylene malonates” are compounds with the general formula I:

Wherein R and R?” The substituents or side-chains can be different or the same. Since 1886, W. H. Perkin Jr. first demonstrated the formation of Diethyl Methylene Malonate (Perkin Ber. 19, 1053 (1886)).

The monomers of methylene malonate and the polymeric products derived from them would be useful for industrial (including household and medical) applications.

However, although earlier methods of producing methylene-malonates have existed for many years, they suffer from significant deficiencies which prevent their use to obtain commercially viable monomers. These deficiencies include undesirable polymerization (e.g. formation of polymers, oligomers, or alternative complexes), the formation of unwanted side products (e.g. ketals, or other latent acids-forming species that impede rapid polymerization), the degradation of the product and/or the low yields. “The overall lower yield, chemical performance, and quality of monomer products produced by previous methods has affected their practical use for the production of commercial and industrial products.

The co-inventors have submitted patent applications for improved methods of synthesizing methylene malonates. These include WO2012/054616, Synthesis Methylene Malonates Substantially free of Impurities and WO2012/054633, Synthesis Methylene Malonates using Rapid Recovery in Presence of Heat Transfer Agent. The synthesis methods described therein lead to improved yields of high-quality methylene malonates, and other polymerizable compounds.

The improved methods described in the patent applications above are capable of providing the desired methylene-malonate monomers. However, improvements are needed, especially in developing methods for commercial production. There is a need for better and/or simpler processes to obtain methylene-malonate and other monomers.

The following description will make clear the purpose and benefits of the invention. The written description, claims and drawings will reveal additional advantages that can be achieved by the invention.

The present invention provides novel method for the preparation of monomers of methylene-malonate from a bis(hydroxymethyl), malonate reagent, in the presence a catalyst. It also provides polymers of said monomers as well as products using the monomers and polymers.

In one aspect, this invention provides a process for making a monomer of methylene malonate that includes:

(a), reacting a dialkylbis(hydroxymethyl)malonate composition with a suitable catalyst to form a monomer of methylene malonate; and

(b), isolating methylene-malonate monomer.

In certain embodiments, step (a) of the reaction is performed in a continuous procedure.

In certain embodiments, step (a), the reaction, is performed without adding a solvent.

In certain embodiments the reaction step (a), is performed under atmospheric pressure.

In certain embodiments, the alkyl group of the dialkylbis(hydroxymethyl), malonate can be straight or branched and has between 1 and 16 carbons.

In one embodiment, the dialkylbis(hydroxymethyl), malonate is prepared using a method that includes:

(i), reacting a formaldehyde source with a dialkyl-malonate ester, in the presence a catalyst for the reaction to form a product diol reaction containing the dialkyl bis (hydroxymethyl) malonate.

In certain embodiments, step i (reacting) is performed in a process that is continuous.

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