Poly(styrene)-supported N-heterocyclic carbene coordinated iron chloride as a catalyst for delayed polyurethane polymerization

초록

An advanced organometallic catalyst based on N-heterocyclic carbene (NHC) coordinated FeCl3 has been synthesized and used to control the reaction rate in polyurethane (PUR) polymerization. The imidazolium (Im)-based NHC was functionalized on the surface of the supporting material of bead-type chloromethyl polystyrene (PS) resin. The PS-Im-FeCl3 catalyst was synthesized through the coordination reaction between Im and FeCl3. The successful formation, functional groups, structure, and geometry of the PS-Im- FeCl3 catalysts were confirmed by Fourier transform infrared and X-ray photoelectron spectroscopy techniques. A thin layer of Im was observed to be coated uniformly on the PS bead surface and FeCl3 nanoparticles were observed to cover the coating layer homogeneously, as determined by fieldemission scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectroscopy measurements. The PUR polymerization reaction was investigated through viscosity measurements and non-isothermal activation energy calculations by differential scanning calorimetry analysis. Based on the viscosity measurements, delayed PUR polymerization was achieved using the PS-Im- FeCl3 catalyst system. The highest viscosity (6000 cP) was achieved without any catalyst, with triphenylene bismuth, and with the PS-Im-FeCl3 catalyst after 23, 5, and 25 h of reaction time, respectively. Furthermore, the calculated activation energies (Ea) were 27.92 and 36.35 kJ mol(-1) for the no-catalyst and the PS-Im-FeCl3 systems, respectively. Thus, the viscosity measurements and DSC analyses confirm that the PS-Im-FeCl3 catalyst considerably increases the PUR reaction time. The Im-FeCl3 catalyst supported by CMPS can control the reaction rate in PUR synthesis because of its high activity. Thus, the PS-Im-FeCl3 catalyst can be used as a curing retardant in the PUR industry.

키워드