The present invention provides a method of making a methylene malonate monomer that includes the steps of reacting a malonic acid ester with a source of formaldehyde optionally in the presence of an acidic or basic catalyst and optionally in the presence of an acidic or non-acidic solvent to form reaction complex. The reaction is optionally performed in the presence of or contacted with an energy transfer means such as a heat transfer agent, a heat transfer surface, a source of radiation or a laser such that reaction complex is substantially vaporized to produce a vapor phase comprising methylene malonate monomer which may be isolated. The present invention further provides methylene malonate monomers prepared by the method of the invention, as well as compositions and products formed from the methylene malonate monomers, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

Synthesis of methylene malonates using rapid recovery in the presence of a heat transfer agent

The exemplary embodiments disclosed herein relate to activating methods for initiation polymerization of methylene malonates and other polymerizable compositions. The polymerization may be activated by anionic or free radical mechanisms. Because the polymerization may occur very quickly upon contact between the activating agent and the polymerizable composition, methods are provide herein for separating or otherwise rendering the activating agent ineffective to initiate polymerization, until such a reaction is desired. The separation may be physical (separate packaging, separate application steps, encapsulation) or it may be based on latent- activation methods (activation precursors, UV activation). Products formed from the methods disclosed herein may include inks, adhesives, coatings, sealants, reactive moldings, fibers, films, sheets, medical polymers, composites, laminates and the like. Exemplary polymerizable compositions and products formed therefrom are environmentally sustainable, environmentally benign and/or biologically benign.

Methods for activating polymerizable compositions, polymerizable systems, and products formed thereby

The present invention provides multifunctional monomers, including, but not limited to include multifunctional methylene malonate and methylene beta-ketoester monomers; methods for producing the same; and compositions and products formed therefrom. The multifunctional monomers of the invention may be produced by transesterification or by direct synthesis from monofunctional methylene malonate monomers or methylene beta-ketoester monomers. The present invention further compositions and products formed from methylene beta-ketoester monomers of the invention, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom

Method to obtain methylene malonate and related monomers following a bis(hydroxymethyl) malonate pathway. A bis(hydroxymethyl) malonate intermediary is subsequently reacted (i.e., subjected to thermolysis) to provide a methylene malonate monomer species. A source of formaldehyde (e.g., formalin) is provided in the presence of a basic catalyst (e.g., calcium hydroxide), to which a malonate (e.g., diethyl malonate) is added under suitable reaction conditions to obtain the desired intermediary (e.g., dialkyl bis(hydroxymethyl) malonate). The intermediary is reacted (i.e., subjected to thermolysis) under suitable conditions in the presence of a suitable catalyst (e.g., a zeolite) to obtain a methylene malonate monomer. In an exemplary embodiment, the thermolysis reaction includes the addition of the bis(hydroxymethyl) malonate intermediary onto a heated catalyst. The reaction product is collected and purified. The disclosed methods may be performed in a continuous operation. Discrete steps may be performed by using modular units within a plant.

Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway

The present invention provides methylene beta-diketone monomers, methods for producing the same, and compositions and products formed therefrom. In the method for producing the methylene beta-diketones of the invention, a beta-diketone is reacted with a source of formaldehyde in a modified Knoevenagel reaction optionally in the presence of an acidic or basic catalyst, and optionally in the presence of an acidic or non-acidic solvent, to form reaction complex. The reaction complex may be an oligomeric complex. The reaction complex is subjected to further processing, which may be vaporization by contact with an energy transfer means in order to isolate the beta-diketone monomer. The present invention further compositions and products formed from methylene beta-diketone monomers of the invention, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom

The process for the production of malonic acid dinitrile which includes quickly preheating acetonitrile to a temperature between 110° and 700°C. Cyanogen chloride and the preheated acetonitrile, both in the gaseous state, are reacted at a temperature between 700° and 1200°C. Malonic acid dinitrile, in the gaseous state, results. The reaction product mixture of gaseous malonic acid dinitrile, gaseous cyanogen chloride, gaseous acetonitrile and HCl, a reaction byproduct, is chilled with liquid reaction product mixture to a temperature between 40°C. and the boiling point of the reaction product mixture. A liquid reaction product results. Simultaneously with the chilling step, the exhaust gas resulting from the chilling of the reaction product mixture is distilled or refined to separate the cyanogen chloride and acetonitrile from the HCl component in the exhaust gas. The malonic acid dinitrile is isolated from the liquid reaction product mixture and purified.

Adriano Dr Faucci

Papers

Process for the production of malonic acid dinitrile