In this paper, a novel and ideal synthetic method of the phosphorus and sulfur hybrid atom ligand is reported. The speciality of this method is that the by-products of some reactions could be used circularly as starti...In this paper, a novel and ideal synthetic method of the phosphorus and sulfur hybrid atom ligand is reported. The speciality of this method is that the by-products of some reactions could be used circularly as starting materials in the synthetic route. Further, we synthesized a series of organopalladium complexes containing these hybrid atom chelate ligands, among them the molecular structures of novelorganopalladium complexes Pd((i-Pr)_2-P(CH_2)_2SEt)Cl_2, Pd(Et_2P(CH_2)_2SEt)Cl_2 and Pd(Ph_2P(CH_2)_2SEt)Cl_2 were determined by using the X-ray single crystal diffraction method. We first used the organotransition metal complexes containing phosphorus and sulfur hybrid atom ligands to activate the σ-C—H bond, and researched the catalytic activity, i.e. the photochemical carbonylation of benzene was catalyzed by these palladium complexes.展开更多
Recent studies have shown interest in flame retardants containing phosphorus, nitrogen and sulfur a combination small molecule with a promising new approach in preparing an important class of flame retardant materials...Recent studies have shown interest in flame retardants containing phosphorus, nitrogen and sulfur a combination small molecule with a promising new approach in preparing an important class of flame retardant materials. Tetraethyl piperazine-1,4-diyldiphosphonate (TEPP) and O,O,O’,O’- tetramethyl piperazine-1,4-diyldiphosphonothioate (TMPT), based on Piperazine derivatives, were prepared successfully and their structures were proved by means of 1H, 13C and 31P NMR. Cotton twill fabric was treated with both compounds to provide different add-on levels. Thermogravimetric Analysis (TGA), microscale combustion calorimeter (MCC), vertical and 45° flame test and limiting oxygen index (LOI) were performed on the treated cotton fabrics and showed promising results. When the treated twill fabrics (5 wt% - 7 wt% add-ons) were tested using the vertical flammability test (ASTMD6413-11), we observed that the ignited fabrics self extinguished and left behind a streak of char. Limiting oxygen index (LOI, ASTM 2863-09) was utilized to determine the effectiveness of the flame retardant on the treated fabrics. LOI values increased from 18 vol% oxygen in nitrogen for untreated twill fabric to a maximum of 30 vol% for the highest add-on of twill. Furthermore, Scanning Electron Microscope (SEM), Attenuated Total Reflection-Infrared (ATR-IR), and Thermogravimetric Analysis-Fourier Transform Infrared (TGA-FTIR) spectroscopy were employed to characterize the chemical structure on the treated fabrics, as well as, the surface morphology of char areas of treated and untreated fabrics. Additionally, analysis of the release gas products by TGA-FTIR shows some distinctive detail in the degradation of the treated fabrics during the burning process.展开更多
基金Project supported by the National Natural Science Foundation of China.
文摘In this paper, a novel and ideal synthetic method of the phosphorus and sulfur hybrid atom ligand is reported. The speciality of this method is that the by-products of some reactions could be used circularly as starting materials in the synthetic route. Further, we synthesized a series of organopalladium complexes containing these hybrid atom chelate ligands, among them the molecular structures of novelorganopalladium complexes Pd((i-Pr)_2-P(CH_2)_2SEt)Cl_2, Pd(Et_2P(CH_2)_2SEt)Cl_2 and Pd(Ph_2P(CH_2)_2SEt)Cl_2 were determined by using the X-ray single crystal diffraction method. We first used the organotransition metal complexes containing phosphorus and sulfur hybrid atom ligands to activate the σ-C—H bond, and researched the catalytic activity, i.e. the photochemical carbonylation of benzene was catalyzed by these palladium complexes.
文摘Recent studies have shown interest in flame retardants containing phosphorus, nitrogen and sulfur a combination small molecule with a promising new approach in preparing an important class of flame retardant materials. Tetraethyl piperazine-1,4-diyldiphosphonate (TEPP) and O,O,O’,O’- tetramethyl piperazine-1,4-diyldiphosphonothioate (TMPT), based on Piperazine derivatives, were prepared successfully and their structures were proved by means of 1H, 13C and 31P NMR. Cotton twill fabric was treated with both compounds to provide different add-on levels. Thermogravimetric Analysis (TGA), microscale combustion calorimeter (MCC), vertical and 45° flame test and limiting oxygen index (LOI) were performed on the treated cotton fabrics and showed promising results. When the treated twill fabrics (5 wt% - 7 wt% add-ons) were tested using the vertical flammability test (ASTMD6413-11), we observed that the ignited fabrics self extinguished and left behind a streak of char. Limiting oxygen index (LOI, ASTM 2863-09) was utilized to determine the effectiveness of the flame retardant on the treated fabrics. LOI values increased from 18 vol% oxygen in nitrogen for untreated twill fabric to a maximum of 30 vol% for the highest add-on of twill. Furthermore, Scanning Electron Microscope (SEM), Attenuated Total Reflection-Infrared (ATR-IR), and Thermogravimetric Analysis-Fourier Transform Infrared (TGA-FTIR) spectroscopy were employed to characterize the chemical structure on the treated fabrics, as well as, the surface morphology of char areas of treated and untreated fabrics. Additionally, analysis of the release gas products by TGA-FTIR shows some distinctive detail in the degradation of the treated fabrics during the burning process.
