Controllable synthesis of naphthalene-derived isotropic pitch with linear molecular structure via Blanc chloromethylation–dechlorination reaction

Abstract

Isotropic pitches with high softening points were controllably synthesized using naphthalene (NAP) via Blanc chloromethylation–dechlorination. Under mild conditions, chloromethyl was introduced into the NAP ring in the presence of chloromethylation reagent. The chloromethylation products of NAP are mainly composed of 1-chloromethylnaphthalene (1-CMNP) and a small amount of 1,4-dichloromethylnaphthalene (1,4-DCMNP). The results of the thermodynamic and kinetic calculations confirmed that the alpha-hydrogen on the NAP ring was more susceptible to being substituted by chloromethyl during chloromethylation, resulting in the formation of 1-CMNP and 1,4-DCMNP. High-quality isotropic pitches with linear methylene-bridged NAP ring structures, characterized by high purity, a high H/C ratio, 100 % solubility in quinoline, and excellent spinnability, were obtained after thermal dechlorination polymerization. Due to their homogeneous isotropic phase, appropriate viscosity, and outstanding spinnability, the as-synthesized pitches were adopted as precursors to prepare isotropic pitch-based carbon fibers via melt spinning. Additionally, the investigation of the carbonization behavior of the as-synthesized pitches showed that the naphthalene-derived isotropic pitch obtained at a polymerization temperature of 380 °C had a 57 % carbon yield at 800 °C, and its derived semi-cokes displayed an isotropic texture, even when carbonized at 550 °C.