Microcapsulated chlorocyclophosphazenes were synthesized,and then microcapsulated chlorocyclo- phosphazene/polypropylene(PP)composites were prepared.The results showed that microcapsulated chlorocyclo- phosphazene had...Microcapsulated chlorocyclophosphazenes were synthesized,and then microcapsulated chlorocyclo- phosphazene/polypropylene(PP)composites were prepared.The results showed that microcapsulated chlorocyclo- phosphazene had good high thermal stability through thermogravimetric analysis(TGA).The flammability and mechanical properties of microcapsulated chlorocyclophosphazene/polypropylene composites were investigated by limiting oxygen index experiment,UL 94V flame retardancy test,cone calorimetry,tensile experiment,and impact test,respectively.It was shown that the microcapsulated chlorocyclophosphazene/PP composites had better tensile strength,impact strength,flame retardant properties and smoke suppress properties compared with chlorocyclo- phosphazene/PP composites.展开更多
Some known and new hexaaryloxyphosphazene: N3P3(O-C6H4-R)(1)/(R=H.CH.OCH3. C(CH3)(3). CHO.F.C6H5COOR. etc) were readily obtained with ca. 70% isolated yield in refluxing acetonitriie in the presence of anhydrous potas...Some known and new hexaaryloxyphosphazene: N3P3(O-C6H4-R)(1)/(R=H.CH.OCH3. C(CH3)(3). CHO.F.C6H5COOR. etc) were readily obtained with ca. 70% isolated yield in refluxing acetonitriie in the presence of anhydrous potassium phosphate. All compounds were characterized by means of elemental analysis. H-1-NMR.P-31-NMR sprctroscopy.展开更多
Poly[（alanino ethyl ester）0.67 （glycino ethyl ester）0.33 phosphazene] （PAGP） was synthesized, and morphology and diameter of the electrospun PAGP nanofibers were systematically evaluated by using a cool field em...Poly[（alanino ethyl ester）0.67 （glycino ethyl ester）0.33 phosphazene] （PAGP） was synthesized, and morphology and diameter of the electrospun PAGP nanofibers were systematically evaluated by using a cool field emission scanning electron microscope （SEM） with changing the important processing variables such as applied voltage, polymeric concentration, and ambient temperature. The average diameter of PAGP nanofibers was inversely proportional to the applied voltage, but increased with the increase of solution concentration. Lower environmental temperature was unfavorable due to the nanofibers conglutination.展开更多
Cyclophosphazene nanotube （PZT） incorporated poly（benzoxazine-co-g-caprolactam） （P（BZ-co-CPL）） nano- composites were developed for improving flame retardant properties. The effects of PZT on the flammability p...Cyclophosphazene nanotube （PZT） incorporated poly（benzoxazine-co-g-caprolactam） （P（BZ-co-CPL）） nano- composites were developed for improving flame retardant properties. The effects of PZT on the flammability properties of P（BZ-co-CPL） matrix were evaluated through UL-94 flammability test and limiting oxygen index （LOI）. The UL-94 results of P（BZ-co-CPL）/PZT hybrid nanocomposites showed V-1 rating, whereas neat P（BZ-co-CPL） showed burning rating. The LOI values are increased from 25.4 to 31.4 for 1.5 wt% PZT incorporated P（BZ-co-CPL） nanocomposite systems. SEM was used to study the char morphology of P（BZ-co-CPL）/PZT after being exposed to UL-94 flammability test. Data from thermal studies indicate that the PZT incorporated P（BZ-co-CPL） systems possess better Tg and thermal degradation behavior when compared to the neat P（BZ-co-CPL）. The values of dielectric constant are decreased with increasing temperature. From the values, it is ascertained that the P（BZ-co-CPL）/PZT systems exhibit stable dielectric behavior with regard to variation in temperature. The TEM images ascertain the uniform dispersion of PZT in the P（BZ-co-CPL） matrix.展开更多
A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectros...A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectroscopy, and multinuclear 31P NMR.展开更多
A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR, 13C NMR, 31...A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR, 13C NMR, 31P NMR, FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA), differential scanning calorimentry (DSC) and FTIR, while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss, and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions, it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37°C. And the sample hydrolytic degradation still remains at the stage of side groups’ break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP), hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%, 47% and 47% at 800°C, respectively, probably due to cross-linking between molecules.展开更多
Cyclotriphosphazene lubricants were synthesized and the relationship between theirstructures and tribological properties was investigated using an Optimol SRV oscillating frictionand wear tester and one-way reciprocat...Cyclotriphosphazene lubricants were synthesized and the relationship between theirstructures and tribological properties was investigated using an Optimol SRV oscillating frictionand wear tester and one-way reciprocating friction tester. It was found that aryloxyphosphazenewith polar substituent as a lubricant of steel/steel and steel/aluminum pair gave low wear, whilearyloxyphosphazene with nonpolar group on the phenyl pendant led to high wear. Phosphazeneprovides poor lubricity for steel/aluminum system under low load (0.5-3 N). The XPS analyticalresults of the antiwear films generated on the steel and aluminum surface indicate that phos-phazene reacted with steel or aluminum counterface and formed a surface protecting film consist-ing of fluoride and organic compounds containing O, C, F, N, P during friction. This contributes tcreduce the friction and wear of steel/aluminum system.展开更多
A series of novel metal halide-stabilized linear phosphazene derivatives were synthesized. The friction-reducing and antiwear abilities of the resulting products as the lubricants for a steel-on-steel contact were com...A series of novel metal halide-stabilized linear phosphazene derivatives were synthesized. The friction-reducing and antiwear abilities of the resulting products as the lubricants for a steel-on-steel contact were comparatively investigated on an Optimol SRV oscillating friction and wear tester. The morphology of the worn steel surface was observed on a scanning electron microscope, while the chemical states of some typical elements on the worn steel surface were examined by means of X-ray photoelectron spectroscopy. It was found that both the side branch structures and central metals influenced the friction-reducing and antiwear behaviors of the synthetic derivatives as the lubricants, which was related to the different adsorption activities of the organic compounds composed of different organic ingredients and metallic ions on a nascent metal surface. All the synthetic lubricants except for the iron (III) derivative showed increased antiwear abilities with increasing metallic ionic radius. A protective layer originated from the tribochemical reaction together with the adsorbed boundary lubricating layer containing organic fluorine compounds, nitrogen oxide, and Fe 3 (PO 4 ) 2 plays an important role in improving the friction and wear behavior of the steel-on-steel system.展开更多
Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for prepa...Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for preparing degradable polyester elastomers.By using cyclic trimeric phosphazene base(CTPB)as an organocatalyst,we succesfully synthesized PMs with different molecular weights(8.2 kDa to 100.7 kDa)in high yields via ring-opening polymerization(ROP)of menthide.When a CTPB/urea binary catalytic system was adopted,the polymerizations proceeded in a more controlled manner.Using glycerol as initiator,star shaped PMs with well.defined structure were synthesized and subsequently end-capped by acrylate.UV iradiation of the terminal acrylate groups in the star-shaped PMs resulted in formation of chemically cos-linked polyester elastomers without heat or other stimuli.The obtained polyester elastomers exhibit matched modulus(3.8-5.5 MPa),tensile strength(0.56-0.68 MPa),and strain at break(280%-320%)with soft body tssues,displaying great potential in biomedical applications.展开更多
The anionic polymerization of methyl methacrylate(MMA) was carried out using phosphazene base t-BuP_4 and ethyl acetate(EA) as the catalyst and the initiator, respectively. Gas chromatography(GC), size exclusion chrom...The anionic polymerization of methyl methacrylate(MMA) was carried out using phosphazene base t-BuP_4 and ethyl acetate(EA) as the catalyst and the initiator, respectively. Gas chromatography(GC), size exclusion chromatography(SEC) measurements, and nuclear magnetic resonance(NMR) analyses were used to reveal the polymerization mechanism and to confirm the polymer structure. The results confirmed the proposed polymerization mechanism and the polymer structure, while the initiator efficiency was low. Meanwhile,the initiation by methoxy anion coming from hydrolysis of the ester bond in MMA was also observed. As a result, there is a marked deviation between the theoretical molecular weight and the measured molecular weight, and it is essential to carry out the polymerization at excessive dosage of t-BuP_4 for preparing polymers with narrow molecular weight distribution.展开更多
Lithium metal batteries(LMBs)show great promise for achieving energy densities over 400 Wh·kg^(-1).However,highly flammable organic electrolytes are a long-lasting problem that triggers safety hazards and hinders...Lithium metal batteries(LMBs)show great promise for achieving energy densities over 400 Wh·kg^(-1).However,highly flammable organic electrolytes are a long-lasting problem that triggers safety hazards and hinders the commercial application of LMBs.Here,a nonflammable diluted highly concentrated electrolyte(DHCE)with ethoxy(pentafluoro)cyclotriphosphazene(PFPN)as a diluent is developed to simultaneously achieve high safety and cycling stability of high-voltage LMBs.The optimal DHCE not only ensures reversible Li deposition/dissolution behavior with a superior average Coulombic efficiency(CE)over 99.1%on lithium metal anode(LMA),but also suppresses side reactions and stress crack on the LiCoO_(2)(LCO)under high cut-off voltage.The newly developed DHCE exhibits high thermal stability,showing complete nonflammability and reduced heat generation between the electrolyte and delithiated LCO/cycled LMA.This work offers an opportunity for rational designing nonflammable electrolytes toward high-voltage and safe LMBs.展开更多
基金Supported by the National Natural Science Foundation of China （No.50303005）, the Natural Science Foundation of Shanxi Province （No.20041029） and the Project of Science and Technology of Shanxi Province （No.012078）.
文摘Microcapsulated chlorocyclophosphazenes were synthesized,and then microcapsulated chlorocyclo- phosphazene/polypropylene(PP)composites were prepared.The results showed that microcapsulated chlorocyclo- phosphazene had good high thermal stability through thermogravimetric analysis(TGA).The flammability and mechanical properties of microcapsulated chlorocyclophosphazene/polypropylene composites were investigated by limiting oxygen index experiment,UL 94V flame retardancy test,cone calorimetry,tensile experiment,and impact test,respectively.It was shown that the microcapsulated chlorocyclophosphazene/PP composites had better tensile strength,impact strength,flame retardant properties and smoke suppress properties compared with chlorocyclo- phosphazene/PP composites.
基金We are grateful to the National Natural Science Foundation of China (grant NO. 59825116) and Chinese Academy of Sciences for the
文摘Some known and new hexaaryloxyphosphazene: N3P3(O-C6H4-R)(1)/(R=H.CH.OCH3. C(CH3)(3). CHO.F.C6H5COOR. etc) were readily obtained with ca. 70% isolated yield in refluxing acetonitriie in the presence of anhydrous potassium phosphate. All compounds were characterized by means of elemental analysis. H-1-NMR.P-31-NMR sprctroscopy.
基金Funded by the National Natural Science Foundation of China (No.50873012)
文摘Poly[（alanino ethyl ester）0.67 （glycino ethyl ester）0.33 phosphazene] （PAGP） was synthesized, and morphology and diameter of the electrospun PAGP nanofibers were systematically evaluated by using a cool field emission scanning electron microscope （SEM） with changing the important processing variables such as applied voltage, polymeric concentration, and ambient temperature. The average diameter of PAGP nanofibers was inversely proportional to the applied voltage, but increased with the increase of solution concentration. Lower environmental temperature was unfavorable due to the nanofibers conglutination.
基金financially supported by the BRNS,G.No.2012/37C/9/BRNS,Mumbai,Govt.of India
文摘Cyclophosphazene nanotube （PZT） incorporated poly（benzoxazine-co-g-caprolactam） （P（BZ-co-CPL）） nano- composites were developed for improving flame retardant properties. The effects of PZT on the flammability properties of P（BZ-co-CPL） matrix were evaluated through UL-94 flammability test and limiting oxygen index （LOI）. The UL-94 results of P（BZ-co-CPL）/PZT hybrid nanocomposites showed V-1 rating, whereas neat P（BZ-co-CPL） showed burning rating. The LOI values are increased from 25.4 to 31.4 for 1.5 wt% PZT incorporated P（BZ-co-CPL） nanocomposite systems. SEM was used to study the char morphology of P（BZ-co-CPL）/PZT after being exposed to UL-94 flammability test. Data from thermal studies indicate that the PZT incorporated P（BZ-co-CPL） systems possess better Tg and thermal degradation behavior when compared to the neat P（BZ-co-CPL）. The values of dielectric constant are decreased with increasing temperature. From the values, it is ascertained that the P（BZ-co-CPL）/PZT systems exhibit stable dielectric behavior with regard to variation in temperature. The TEM images ascertain the uniform dispersion of PZT in the P（BZ-co-CPL） matrix.
文摘A new organophosphazene polyoxotungstate, [(N3P3)(SiW11O39H2)3]12-, has been prepared by reaction of hexachlorocyclotriphosphazene with undecatungstosilicate, and characterized by elemental analysis, infrared spectroscopy, and multinuclear 31P NMR.
基金Supported by the National Natural Science Foundation of China (Grant No. 20774016)Heilongjiang Science Fund for Distinguished Young Scholars (Grant No. JC 04-06)
文摘A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR, 13C NMR, 31P NMR, FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA), differential scanning calorimentry (DSC) and FTIR, while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss, and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions, it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37°C. And the sample hydrolytic degradation still remains at the stage of side groups’ break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP), hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%, 47% and 47% at 800°C, respectively, probably due to cross-linking between molecules.
文摘Cyclotriphosphazene lubricants were synthesized and the relationship between theirstructures and tribological properties was investigated using an Optimol SRV oscillating frictionand wear tester and one-way reciprocating friction tester. It was found that aryloxyphosphazenewith polar substituent as a lubricant of steel/steel and steel/aluminum pair gave low wear, whilearyloxyphosphazene with nonpolar group on the phenyl pendant led to high wear. Phosphazeneprovides poor lubricity for steel/aluminum system under low load (0.5-3 N). The XPS analyticalresults of the antiwear films generated on the steel and aluminum surface indicate that phos-phazene reacted with steel or aluminum counterface and formed a surface protecting film consist-ing of fluoride and organic compounds containing O, C, F, N, P during friction. This contributes tcreduce the friction and wear of steel/aluminum system.
基金This work was supported by the National Natural Science Foundation of China(Grant No.50275142)the“863”project(Grant No.2002AA302609).
文摘A series of novel metal halide-stabilized linear phosphazene derivatives were synthesized. The friction-reducing and antiwear abilities of the resulting products as the lubricants for a steel-on-steel contact were comparatively investigated on an Optimol SRV oscillating friction and wear tester. The morphology of the worn steel surface was observed on a scanning electron microscope, while the chemical states of some typical elements on the worn steel surface were examined by means of X-ray photoelectron spectroscopy. It was found that both the side branch structures and central metals influenced the friction-reducing and antiwear behaviors of the synthetic derivatives as the lubricants, which was related to the different adsorption activities of the organic compounds composed of different organic ingredients and metallic ions on a nascent metal surface. All the synthetic lubricants except for the iron (III) derivative showed increased antiwear abilities with increasing metallic ionic radius. A protective layer originated from the tribochemical reaction together with the adsorbed boundary lubricating layer containing organic fluorine compounds, nitrogen oxide, and Fe 3 (PO 4 ) 2 plays an important role in improving the friction and wear behavior of the steel-on-steel system.
基金This work was financially supported by the National Natural Science Foundation of China(No.21704048)the 111 Project(No.D17004)the Taishan Scholars Constructive Engineering Foundation(No.tsqn20161031).
文摘Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for preparing degradable polyester elastomers.By using cyclic trimeric phosphazene base(CTPB)as an organocatalyst,we succesfully synthesized PMs with different molecular weights(8.2 kDa to 100.7 kDa)in high yields via ring-opening polymerization(ROP)of menthide.When a CTPB/urea binary catalytic system was adopted,the polymerizations proceeded in a more controlled manner.Using glycerol as initiator,star shaped PMs with well.defined structure were synthesized and subsequently end-capped by acrylate.UV iradiation of the terminal acrylate groups in the star-shaped PMs resulted in formation of chemically cos-linked polyester elastomers without heat or other stimuli.The obtained polyester elastomers exhibit matched modulus(3.8-5.5 MPa),tensile strength(0.56-0.68 MPa),and strain at break(280%-320%)with soft body tssues,displaying great potential in biomedical applications.
基金finanically supported by the National Natural Science Foundation of China (No. 21474010)the Priority Academic Program Development of Jiangsu Province
文摘The anionic polymerization of methyl methacrylate(MMA) was carried out using phosphazene base t-BuP_4 and ethyl acetate(EA) as the catalyst and the initiator, respectively. Gas chromatography(GC), size exclusion chromatography(SEC) measurements, and nuclear magnetic resonance(NMR) analyses were used to reveal the polymerization mechanism and to confirm the polymer structure. The results confirmed the proposed polymerization mechanism and the polymer structure, while the initiator efficiency was low. Meanwhile,the initiation by methoxy anion coming from hydrolysis of the ester bond in MMA was also observed. As a result, there is a marked deviation between the theoretical molecular weight and the measured molecular weight, and it is essential to carry out the polymerization at excessive dosage of t-BuP_4 for preparing polymers with narrow molecular weight distribution.
基金supported by the Science and Technology Project of State Grid Corporation of China(No.4000-202320087A-1-1-ZN).
文摘Lithium metal batteries(LMBs)show great promise for achieving energy densities over 400 Wh·kg^(-1).However,highly flammable organic electrolytes are a long-lasting problem that triggers safety hazards and hinders the commercial application of LMBs.Here,a nonflammable diluted highly concentrated electrolyte(DHCE)with ethoxy(pentafluoro)cyclotriphosphazene(PFPN)as a diluent is developed to simultaneously achieve high safety and cycling stability of high-voltage LMBs.The optimal DHCE not only ensures reversible Li deposition/dissolution behavior with a superior average Coulombic efficiency(CE)over 99.1%on lithium metal anode(LMA),but also suppresses side reactions and stress crack on the LiCoO_(2)(LCO)under high cut-off voltage.The newly developed DHCE exhibits high thermal stability,showing complete nonflammability and reduced heat generation between the electrolyte and delithiated LCO/cycled LMA.This work offers an opportunity for rational designing nonflammable electrolytes toward high-voltage and safe LMBs.
