The standard industrial reaction for producing methyl acrylate is esterification with methanol under acid catalysis. The transesterification is facilitated because methanol and methyl acrylate form a low boiling azeotrope. The patent literature describes a one-pot route involving vapor-phase oxidation of propene or 2-propenal with oxygen in the presence of methanol.
Methyl acrylate can be prepared by debromination of methyl 2,3-dibromopropanoate with zinc. Methyl acrylate is formed in good yield on pyrolysis of methyl lactate in the presence of ethenone. Methyl lactate is a renewable "green chemical". Another patent describes the dehydration of methyl lactate over zeolites. The nickel tetracarbonyl-catalyzed hydrocarboxylation of acetylene with carbon monoxide in the presence of methanol also yields methyl acrylate. The reaction of methyl formate with acetylene in the presence of transition metal catalysts also leads to methyl acrylate. Both, the alcoholysis of propiolactone with methanol as well as the methanolysis of acrylonitrile via intermediately formed acrylamide sulfate are also proven but obsolete processes.
Use
Methyl acrylate is after butyl acrylate and ethyl acrylate the third most important acrylic ester with a worldwide annual production of about 200,000 tons per year. Methyl acrylate reacts catalysed by Lewis bases in a Michael addition with amines in high yields to β-alanine derivatives which provide amphoteric surfactants when long-chain amines are used and the ester function is hydrolysed subsequently. Methyl acrylate is used for the preparation of 2-dimethylaminoethyl acrylate by transesterification with dimethylaminoethanol in significant quantities of over 50,000 tons / year. Methyl acrylate is used as a comonomer in the polymerization with a variety of acrylic and vinyl monomers. In doing so it has a similar range of uses as ethyl acrylate. When using methyl acrylate as comonomer resulting acrylic paints are harder and more brittle than those with the homologous acrylates. Copolymerizing methyl acrylate with acrylonitrile improves their melt processability to fibers, which could be used as precursors for carbon fibers. Acrylates are also used in the preparation of poly dendrimers typically by Michael addition with a primary amine. Methyl acrylate is the precursor to fibers that are woven to make carpets. Owing to its tendency to polymerize, samples typically contain an inhibitor such as hydroquinone.
