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
A reduced mechanism for propane/air combustion and its flame inhibition by phosphorus-containing compounds (PCCs) is constructed with the level of importance (LOI) method. The analysis is performed on solutions of fre...A reduced mechanism for propane/air combustion and its flame inhibition by phosphorus-containing compounds (PCCs) is constructed with the level of importance (LOI) method. The analysis is performed on solutions of freely propagating premixed flames with detailed chemical kinetics involving 121 species and 682 reactions proposed by Jayaweera et al. For the non-homogeneous reaction-diffusion system, the chemical lifetime of each species is weighted by its diffusion timescale, and the characteristic flame timescale is used to normalize the chemical lifetime. The definition of sensitivity in LOI is extended so that multi-parameters can be used as sensitivity targets. Propane, oxygen, dimethyl methylphosphonate (DMMP), and flame speed are selected to be perturbed for sensitivity analysis, the species with low LOI index are removed, and reactions involving the redundant species are excluded from the mechanism. A skeletal mechanism is obtained, which consists of 57 species and 268 elementary reactions. Calculations for laminar flame speeds, key flame radicals and catalytic cycles using the skeletal mechanism are in good agreement with those by using the detailed mechanism over a wide range of equivalence ratio undoped and doped with DMMP.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
Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)...Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)polymerization of phosphorus-containing monomers. In addition, different properties of the polymers involved in the phosphonate group in various chemical environments are demonstrated, and their potential applications are briefly discussed.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
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 Diels-Alder reaction of bis(diphenylphosphine oxide)butadiyne (BDPPOB) with spiro[2.4]hepta-4,6-diene affords the title compound, 2-(diphenylphosphine oxide)-3-(diphen- ylphosphine oxide ethynyl)spiro[bicyclo[2.2....The Diels-Alder reaction of bis(diphenylphosphine oxide)butadiyne (BDPPOB) with spiro[2.4]hepta-4,6-diene affords the title compound, 2-(diphenylphosphine oxide)-3-(diphen- ylphosphine oxide ethynyl)spiro[bicyclo[2.2.1] hepta-2,5-diene-7,1-cyclopropane] (DDSHC, C35H28O2P2, Mr = 542). Its crystal structure belongs to monoclinic system, space group P21/n with a =12.708(3), b = 14.666(4), c = 15.048(4) ? = 93.903(5) ? V = 2798.1(13) ?, Z = 4, Dc = 1.288g/cm3, F(000)=1136, (MoK? = 0.187mm-1, final R = 0.0626 and wR= 0.1422 for 4685 independent reflections with I > 2(I). Structural analyses reveal that the title compound is nonplanar and the dihedral angles between two phenyl rings around each phosphorus atom are 71.7(2) and 70.7(3)? respectively.展开更多
The immunomodulation of several charged synthetic polymers containing phosphorus in the backbone was studied in vitro through examining their inhibition or promotion effect on the proliferation of both T and B lymphoc...The immunomodulation of several charged synthetic polymers containing phosphorus in the backbone was studied in vitro through examining their inhibition or promotion effect on the proliferation of both T and B lymphocytes. It is found that polymers based on long chain alkyl ester of tyrosine exhibit immunomodulative activity. Negatively charged polymers show stimulative activiactivity on LPS-induced B lymphocytes proliferation. Positively charged polymers exhibit inhibitory activity on both Con A-induced T lymphocytes and LPS-induced B lymphocytes proliferation.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Supported by the National Natural Science Foundation of China （50876097） the Program for New Century Excellent Talents in University of China （NCET-06-0546）
文摘A reduced mechanism for propane/air combustion and its flame inhibition by phosphorus-containing compounds (PCCs) is constructed with the level of importance (LOI) method. The analysis is performed on solutions of freely propagating premixed flames with detailed chemical kinetics involving 121 species and 682 reactions proposed by Jayaweera et al. For the non-homogeneous reaction-diffusion system, the chemical lifetime of each species is weighted by its diffusion timescale, and the characteristic flame timescale is used to normalize the chemical lifetime. The definition of sensitivity in LOI is extended so that multi-parameters can be used as sensitivity targets. Propane, oxygen, dimethyl methylphosphonate (DMMP), and flame speed are selected to be perturbed for sensitivity analysis, the species with low LOI index are removed, and reactions involving the redundant species are excluded from the mechanism. A skeletal mechanism is obtained, which consists of 57 species and 268 elementary reactions. Calculations for laminar flame speeds, key flame radicals and catalytic cycles using the skeletal mechanism are in good agreement with those by using the detailed mechanism over a wide range of equivalence ratio undoped and doped with DMMP.
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.
基金supported by the National Natural Science Foundation of China(21174096,21274100,21234005)the Specialized Research Fund for the Doctoral Program of Higher Education(20123201130001)+2 种基金the Project of Science and Technology Development Planning of Suzhou(ZXG201413,SYG201430)the Project of Science and Technology Development Planning of Jiangsu Province(BK20141192)the Project Fund of the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘Special research attention has been paid to phosphorus-containing materials and their corresponding applications. This mini review considers recent publications devoted to the "living"/controlled radical(co)polymerization of phosphorus-containing monomers. In addition, different properties of the polymers involved in the phosphonate group in various chemical environments are demonstrated, and their potential applications are briefly discussed.
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℃）.
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This work was supported by the NNSFC (No. 29832030 and 20072018)
文摘The Diels-Alder reaction of bis(diphenylphosphine oxide)butadiyne (BDPPOB) with spiro[2.4]hepta-4,6-diene affords the title compound, 2-(diphenylphosphine oxide)-3-(diphen- ylphosphine oxide ethynyl)spiro[bicyclo[2.2.1] hepta-2,5-diene-7,1-cyclopropane] (DDSHC, C35H28O2P2, Mr = 542). Its crystal structure belongs to monoclinic system, space group P21/n with a =12.708(3), b = 14.666(4), c = 15.048(4) ? = 93.903(5) ? V = 2798.1(13) ?, Z = 4, Dc = 1.288g/cm3, F(000)=1136, (MoK? = 0.187mm-1, final R = 0.0626 and wR= 0.1422 for 4685 independent reflections with I > 2(I). Structural analyses reveal that the title compound is nonplanar and the dihedral angles between two phenyl rings around each phosphorus atom are 71.7(2) and 70.7(3)? respectively.
文摘The immunomodulation of several charged synthetic polymers containing phosphorus in the backbone was studied in vitro through examining their inhibition or promotion effect on the proliferation of both T and B lymphocytes. It is found that polymers based on long chain alkyl ester of tyrosine exhibit immunomodulative activity. Negatively charged polymers show stimulative activiactivity on LPS-induced B lymphocytes proliferation. Positively charged polymers exhibit inhibitory activity on both Con A-induced T lymphocytes and LPS-induced B lymphocytes proliferation.
