Dynamic Properties of Di(cyclopentadienecarboxylic Acid) Dimethyl Esters

Abstract

Di(cyclopentadienecarboxylic acid) dimethyl ester (DCPDME) is a potential dynamic covalent system. When such molecules are used as dynamic crosslinkers in polymers, understanding the reversibility of cyclopentadiene dimerization is crucial to determine optimal melt processing conditions. To this end, we synthesized DCPDME, which consists of three regioisomers with different physicochemical properties, which were investigated by isolating them and further characterizing them using 1H NMR, FTIR and DSC. There have been many attempts to improve the synthesis process to increase the reaction yield and purity of isomer 3, and this goal remains a challenge today. In this work, we show that pure isomers 1 and 2 irreversibly convert to the more stable DCPDME isomer 3 at temperatures between 120 and 140 °C in N2. This shows that isolation of the pure isomer 3 from the DCPDME isomer mixture is not necessary. The DCPDME isomer 3 is reversibly cleaved to the monomeric cyclopentadienecarboxylic acid methyl ester (CPME), as confirmed with GC–MS and the resulting mass spectrum. The conversion of DCPDME isomers 1 and 2 to isomer 3 was confirmed by heating the synthesized mixture of DCPDME isomers at 135 °C for 5 min in N2, producing an almost pure isomer 3 which increased its synthesis yield by 35%.

Keywords

• cyclopentadiene
• Thiele’s acid ester
• regioisomers
• NMR spectroscopy
• differential scanning calorimetry (DSC)
• FTIR spectroscopy