On the synthesis of ethyl‐2‐cyanoacrylate from waste residue

Abstract

SYNOPSISThe aim of the present study is to clarify some problems concerning the synthesis of additional quantities of ethyl-2-cyanoacrylate monomer ( ECA) utilizing the waste residue (WR) from the large-scale depolymerization of ECA oligomers. The composition of WR was established by GPC and IR spectroscopy. WR was found to consist mostly of diethyl dicyanoglutarate (DEDCG) and low molecular weight products of its condensation with paraformaldehyde (pFA) . The DEDCG-pFA interaction was studied as a model, and the influence of DEDCG conversion on the average degree of polymerization (X, and Fw) of the oligomers formed was also followed. On this basis, it was found that oligomer formation in condensation of WR with pFA is consistent with a stepgrowth mechanism, the polymer chain length being determined by steric hindrance and destructive reactions. wherein R = alkyl and B-= organic or inorganic base.

Anionic Polymerization of n-Butyl Cyanoacrylate in Emulsion and Miniemulsion

“…Oligomer peaks in the SEC trace are de facto assigned according to their retention time, which decreases with increasing chain length . In a previous study on the ring-opening polymerization of phenyl glycidyl ether in miniemulsion, the open monomer (A 1 ) peak was coming out at longer elution volume that the monomer one.…”

Synthesis and characterization of four alkyl 2‐cyanoacrylate monomers and their precursors for use in latent fingerprint detection

“…The majority of the remaining alternative approaches for the synthesis of cyanoacrylates are either poorly documented,51 involve the use of extremely reactive intermediates (such as 2‐cyanoacryloyl chloride),50 involve a complex multistep synthesis53, 54 and/or still involve a depolymerisation step 52, 56. The exception is the Diels‐Alder protection and deprotection route that was first described in a patent by Ray and Doran in 1969 40.…”

“…These include fluorinated, higher alkyl and difunctional or bis‐cyanoacrylates. These alternative routes include: the use of acid catalysts for the condensation reaction between alkyl cyanoacetates and formaldehyde35–38 Diels‐Alder protection and deprotection39–49 esterification of 2‐cyanoacryloyl chloride with an alcohol or diol (for bis cyanoacrylates)50 direct transesterification of methyl cyanoacrylate with a diol to form the corresponding bis‐cyanoacrylate51 condensation of either methyl or ethyl cyanoacetate with paraformaldehyde followed by transesterification of the intermediate oligomer with a higher alkyl alcohol and subsequent thermal depolymerisation52 oxidation of a phenylselenide precursor53, 54 condensation of diethyl 2,4‐dicyanoglutarate (from the waste residue of large scale cyanoacrylate synthesis) with paraformaldehyde and subsequent depolymerization55, 56 …”

“…condensation of diethyl 2,4‐dicyanoglutarate (from the waste residue of large scale cyanoacrylate synthesis) with paraformaldehyde and subsequent depolymerization55, 56…”