Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their ...Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.展开更多
Phosphorus-containing compounds are the promising halon alternatives for flame inhibitions. However, some literatures suggested that the phosphorus-related inhibitors may behave as the unfavorable ones that will incre...Phosphorus-containing compounds are the promising halon alternatives for flame inhibitions. However, some literatures suggested that the phosphorus-related inhibitors may behave as the unfavorable ones that will increase the burning velocity under lean-burn conditions, and this indeed posed potential threats to the fire prevention and fighting. To seek deeper insights into the reaction process, a numerical investigation was actualized to study the phosphorus-related effects on methane-air flames. By replacing a phosphorus-related inhibitor with the corresponding decomposed molecules, the detailed promoting and inhibiting effects of combustion were separated from the general chemical effect. A comparative study was carried out to identify the interaction between the two effects under different combustion conditions. It is observed that the promoting effect becomes the dominant factor during the reaction process when the equivalence ratio is smaller than 0.60. In this lean-burn condition, the exothermic reactions were faster than the others within the reaction chains due to the reduction of radical recombination in hydrocarbon oxidation. The results are believed to be useful for the further application and improvement of flame inhibitors.展开更多
31P NMR has become a widely applied spectroscopic probe of the structure of phosphorus-containing compounds. Meanwhile, the application of 31P NMR has been rapidly expanded to biochemistry and medicinal chemistry of p...31P NMR has become a widely applied spectroscopic probe of the structure of phosphorus-containing compounds. Meanwhile, the application of 31P NMR has been rapidly expanded to biochemistry and medicinal chemistry of phosphorus-containing compounds because the growing importance of the phosphorus compounds is now widely realized. We report here the results of 31P NMR study on some phosphorus-containing compounds, namely, O-alkyl O-4-nitrophenyl methyl phosphonates with different alkyl chain-length (MePO-n), 4-nitrophenyl alkylphenylphosphinates with different alkyl chain-length (PhP-n), diethyl phosphono- acetonitrile anion and diethyl phosphite anion . Our results indicate that 31P NMR can not only be applied to not only the study of the hydrolytic reactions of MePO-8 and PhP-8 but also be applied to the study of the presence of the anions of diethylphosphonoacetonitrile and diethyl phosphite in nucleophilic reactions.展开更多
A phosphorus-containing monomer (lO-oxo-10-hydro-9-oxa-10λ^5-phosphaphenanthrene-10-yl)-methyl acrylate (MD was copolymerized with styrene to give a potential flame retardant copolymer of high thermal stability. T...A phosphorus-containing monomer (lO-oxo-10-hydro-9-oxa-10λ^5-phosphaphenanthrene-10-yl)-methyl acrylate (MD was copolymerized with styrene to give a potential flame retardant copolymer of high thermal stability. The structures of monomer and copolymer were characterized by FT-IR and ^1H NMR measurements. The reactivity ratios for free-radical of the monomer (M1) and styrene (Mz) were studied. The calculated results are as follows: r1 = 0.225, r2 = 0.503; Q1 = 0.413, e1 = 0.476; azeotropic point = 0.37. TGA and DTG curves indicated that Ml is a potential flame retarding monomer for styrenic polymers. C 2009 Yu Bin Zheng. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
The novel spirophosphoroheterocycle (C14H19N2OPS2, Mr = 326.40) was synthesized by the treatment of Lawesson磗 reagent with amino cyclohexanenitrile, and its crystal structure was analyzed by X-ray diffraction method....The novel spirophosphoroheterocycle (C14H19N2OPS2, Mr = 326.40) was synthesized by the treatment of Lawesson磗 reagent with amino cyclohexanenitrile, and its crystal structure was analyzed by X-ray diffraction method. The title compound is of monoclinic, space group P21/n with a = 14.296(4), b = 11.028(3), c = 21.715(6) ? ?= 101.823(6), V = 3351.1(2) 3, Z = 8, Dc = 1.294 g/cm3, ?= 0.71073 ? (MoK? = 0.410 mm―1 and F(000) = 1376. The structure was refined to R = 0.0521 and wR = 0.0744 for 5909 observed reflections with I > 2(I). X-ray diffraction analysis reveals that there are three rings in the molecule. The saturated 6-membered ring presents in chair conformation and the 5-membered phosphoroheterocycle is planar. The molecules are found to exist in couples. The existence of d-p?bonds between P and two N atoms and the intermolecular hydrogen bonds are found as well.展开更多
The novel benzoxazine monomer containing phosphorus has been synthesized based on multifianctional amine route from bis(4-aminophenyl)phenylphosphate, p-cresol and formaldehyde. Subsequently, the benzoxazine monomer...The novel benzoxazine monomer containing phosphorus has been synthesized based on multifianctional amine route from bis(4-aminophenyl)phenylphosphate, p-cresol and formaldehyde. Subsequently, the benzoxazine monomer was thermo-cured into polybenzoxazine containing phosphorus. The chemical structures were identified by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR). The curing reaction was monitored by differential scanning calorimetry (DSC) and FT-IR. The thermal and flame-retardant properties of obtained polybenzoxazine were evaluated by dynamic mechanical thermal analysis (DMA), thermal gravimetric analysis (TGA) and oxygen index meter, respectively. The results show that the novel polybenzoxazine has high limiting oxygen index (38.1) and glass transition temperature (232℃).展开更多
文摘Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.
基金Project supported by the National Natural Science Foundation of China(Grant No.51576183)the Fundamental Research Funds for the Central Universities,China(Grant Nos.WK2320000035 and WK2320000041)
文摘Phosphorus-containing compounds are the promising halon alternatives for flame inhibitions. However, some literatures suggested that the phosphorus-related inhibitors may behave as the unfavorable ones that will increase the burning velocity under lean-burn conditions, and this indeed posed potential threats to the fire prevention and fighting. To seek deeper insights into the reaction process, a numerical investigation was actualized to study the phosphorus-related effects on methane-air flames. By replacing a phosphorus-related inhibitor with the corresponding decomposed molecules, the detailed promoting and inhibiting effects of combustion were separated from the general chemical effect. A comparative study was carried out to identify the interaction between the two effects under different combustion conditions. It is observed that the promoting effect becomes the dominant factor during the reaction process when the equivalence ratio is smaller than 0.60. In this lean-burn condition, the exothermic reactions were faster than the others within the reaction chains due to the reduction of radical recombination in hydrocarbon oxidation. The results are believed to be useful for the further application and improvement of flame inhibitors.
文摘31P NMR has become a widely applied spectroscopic probe of the structure of phosphorus-containing compounds. Meanwhile, the application of 31P NMR has been rapidly expanded to biochemistry and medicinal chemistry of phosphorus-containing compounds because the growing importance of the phosphorus compounds is now widely realized. We report here the results of 31P NMR study on some phosphorus-containing compounds, namely, O-alkyl O-4-nitrophenyl methyl phosphonates with different alkyl chain-length (MePO-n), 4-nitrophenyl alkylphenylphosphinates with different alkyl chain-length (PhP-n), diethyl phosphono- acetonitrile anion and diethyl phosphite anion . Our results indicate that 31P NMR can not only be applied to not only the study of the hydrolytic reactions of MePO-8 and PhP-8 but also be applied to the study of the presence of the anions of diethylphosphonoacetonitrile and diethyl phosphite in nucleophilic reactions.
文摘A phosphorus-containing monomer (lO-oxo-10-hydro-9-oxa-10λ^5-phosphaphenanthrene-10-yl)-methyl acrylate (MD was copolymerized with styrene to give a potential flame retardant copolymer of high thermal stability. The structures of monomer and copolymer were characterized by FT-IR and ^1H NMR measurements. The reactivity ratios for free-radical of the monomer (M1) and styrene (Mz) were studied. The calculated results are as follows: r1 = 0.225, r2 = 0.503; Q1 = 0.413, e1 = 0.476; azeotropic point = 0.37. TGA and DTG curves indicated that Ml is a potential flame retarding monomer for styrenic polymers. C 2009 Yu Bin Zheng. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘The novel spirophosphoroheterocycle (C14H19N2OPS2, Mr = 326.40) was synthesized by the treatment of Lawesson磗 reagent with amino cyclohexanenitrile, and its crystal structure was analyzed by X-ray diffraction method. The title compound is of monoclinic, space group P21/n with a = 14.296(4), b = 11.028(3), c = 21.715(6) ? ?= 101.823(6), V = 3351.1(2) 3, Z = 8, Dc = 1.294 g/cm3, ?= 0.71073 ? (MoK? = 0.410 mm―1 and F(000) = 1376. The structure was refined to R = 0.0521 and wR = 0.0744 for 5909 observed reflections with I > 2(I). X-ray diffraction analysis reveals that there are three rings in the molecule. The saturated 6-membered ring presents in chair conformation and the 5-membered phosphoroheterocycle is planar. The molecules are found to exist in couples. The existence of d-p?bonds between P and two N atoms and the intermolecular hydrogen bonds are found as well.
基金financially SUpponed by the National Natural Science Foundation of ChiNa(No.21074067)the Natural Science FOUNdation of Shandong Province(No.Y2008804)
文摘The novel benzoxazine monomer containing phosphorus has been synthesized based on multifianctional amine route from bis(4-aminophenyl)phenylphosphate, p-cresol and formaldehyde. Subsequently, the benzoxazine monomer was thermo-cured into polybenzoxazine containing phosphorus. The chemical structures were identified by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR). The curing reaction was monitored by differential scanning calorimetry (DSC) and FT-IR. The thermal and flame-retardant properties of obtained polybenzoxazine were evaluated by dynamic mechanical thermal analysis (DMA), thermal gravimetric analysis (TGA) and oxygen index meter, respectively. The results show that the novel polybenzoxazine has high limiting oxygen index (38.1) and glass transition temperature (232℃).