A novel series of polyphosphazene-grafl-polystyrene (PP-g-PS) copolymers were successfully prepared by atom transfer radical polymerization (ATRP) of styrene monomers and brominated poly(bis(4-methylphenoxy)pho...A novel series of polyphosphazene-grafl-polystyrene (PP-g-PS) copolymers were successfully prepared by atom transfer radical polymerization (ATRP) of styrene monomers and brominated poly(bis(4-methylphenoxy)phosphazene) macroinitiator. The graft density and the graft length could be regulated by changing the bromination degree of the macroinitiator and the ATRP reaction time, respectively. The PP-g-PS copolymers readily underwent a regioselective sulfonation reaction, which occurred preferentially at the polystyrene sites, producing the sulfonated PP-g-PS copolymers with a range of ion exchange capacities. The resulting sulfonated PP-g-PS membranes prepared by solution casting showed high water uptake, low water swelling and considerable proton conductivity. They also exhibited good oxidative stability and high resistance to methanol crossover. Morphological studies of the membranes by transmission electron microscopy showed clear nanophase-separated structures resulted from hydrophobic polyphosphazene backbone and hydrophilic polystyrene sulfonic acid segments, indicating the formation of proton transferring tunnels. Therefore, these sulfonated copolymers may be candidate materials for proton exchange membranes in direct methanol fuel cell (DMFC) applications.展开更多
Poly(organophosphazenes) have potential applications in making water-soluble and biocompatible quantum dots (QDs) due to their wide variety of properties. The CdSe QDs of green emission and the core-shell CdSe/ZnS QDs...Poly(organophosphazenes) have potential applications in making water-soluble and biocompatible quantum dots (QDs) due to their wide variety of properties. The CdSe QDs of green emission and the core-shell CdSe/ZnS QDs of red emission were prepared. Subsequently the trioctylphosphine oxide-stabilized CdSe/ZnS QDs were transferred from chloroform into water through a ligand exchange process with poly(glycino amino acid)phosphazenes, which can be obtained from the saponification of poly (glycino amino ester)phosphazenes at room temperature. The resulting QDs-polymer nanocomposite particles can form colloidally stable suspensions in water and exhibit good photostability.展开更多
Polydichlorophosphazene(PDCP)was synthesized from PCl5 and NH4Cl via a one-pot approach,and then further reacted with glycine ethyl ester and methylparaben via a two-step nucleophilic substitution approach to give pol...Polydichlorophosphazene(PDCP)was synthesized from PCl5 and NH4Cl via a one-pot approach,and then further reacted with glycine ethyl ester and methylparaben via a two-step nucleophilic substitution approach to give poly(methylparaben/glycine ethyl ester)phosphazene(PMGP),which was a kind of mix-substituted biodegradable polymer.NMR and FT-IR were used to characterize its structure.A series of experiments were conducted to study the effects of the ratio of methylparaben to glycine ethyl ester and the experimental conditions to the degradability of PMGP samples.The degradability of PMGP can be adjusted by altering the ratio of methylparaben to glycine ethyl ester easily.展开更多
以不同比例的重氮盐分别与聚双(N-羟基己氧基咔唑)磷腈(P-1)进行偶合反应,得到了一组以咔唑和对硝基偶氮咔唑为官能团的双功能型光折变聚合物P-2,P-3和P-4,用31 P NMR,1 H NMR,IR,TG,DSC和UV-Vis光谱对该组聚合物进行表征和分析,以325n...以不同比例的重氮盐分别与聚双(N-羟基己氧基咔唑)磷腈(P-1)进行偶合反应,得到了一组以咔唑和对硝基偶氮咔唑为官能团的双功能型光折变聚合物P-2,P-3和P-4,用31 P NMR,1 H NMR,IR,TG,DSC和UV-Vis光谱对该组聚合物进行表征和分析,以325nm的激发波长对P-1,P-2,P-3和P-4进行固体荧光稳态发射光谱的测试。结果表明,该组聚合物具有良好的热稳定性(Td≈300℃)和较低的玻璃化温度(Tg≈30~40℃),P-1具有良好的荧光活性,硝基的引入,导致P-2,P-3和P-4的荧光发生不同程度的猝灭,咔唑与对硝基偶氮咔唑的数量及其空间分布排列的都会对其荧光性能产生影响。展开更多
基金financially supported by the National Natural Science Foundation of China(No.51103012)
文摘A novel series of polyphosphazene-grafl-polystyrene (PP-g-PS) copolymers were successfully prepared by atom transfer radical polymerization (ATRP) of styrene monomers and brominated poly(bis(4-methylphenoxy)phosphazene) macroinitiator. The graft density and the graft length could be regulated by changing the bromination degree of the macroinitiator and the ATRP reaction time, respectively. The PP-g-PS copolymers readily underwent a regioselective sulfonation reaction, which occurred preferentially at the polystyrene sites, producing the sulfonated PP-g-PS copolymers with a range of ion exchange capacities. The resulting sulfonated PP-g-PS membranes prepared by solution casting showed high water uptake, low water swelling and considerable proton conductivity. They also exhibited good oxidative stability and high resistance to methanol crossover. Morphological studies of the membranes by transmission electron microscopy showed clear nanophase-separated structures resulted from hydrophobic polyphosphazene backbone and hydrophilic polystyrene sulfonic acid segments, indicating the formation of proton transferring tunnels. Therefore, these sulfonated copolymers may be candidate materials for proton exchange membranes in direct methanol fuel cell (DMFC) applications.
基金Project(2006CB601005) supported by the National Basic Research Program of Chinaproject(200331) supported by the National Excellent Doctoral Dissertations of Chinaproject(Q5009001200801) supported by the Post-Doctoral Science and Technology Foundation from Beijing University of Technology
文摘Poly(organophosphazenes) have potential applications in making water-soluble and biocompatible quantum dots (QDs) due to their wide variety of properties. The CdSe QDs of green emission and the core-shell CdSe/ZnS QDs of red emission were prepared. Subsequently the trioctylphosphine oxide-stabilized CdSe/ZnS QDs were transferred from chloroform into water through a ligand exchange process with poly(glycino amino acid)phosphazenes, which can be obtained from the saponification of poly (glycino amino ester)phosphazenes at room temperature. The resulting QDs-polymer nanocomposite particles can form colloidally stable suspensions in water and exhibit good photostability.
文摘Polydichlorophosphazene(PDCP)was synthesized from PCl5 and NH4Cl via a one-pot approach,and then further reacted with glycine ethyl ester and methylparaben via a two-step nucleophilic substitution approach to give poly(methylparaben/glycine ethyl ester)phosphazene(PMGP),which was a kind of mix-substituted biodegradable polymer.NMR and FT-IR were used to characterize its structure.A series of experiments were conducted to study the effects of the ratio of methylparaben to glycine ethyl ester and the experimental conditions to the degradability of PMGP samples.The degradability of PMGP can be adjusted by altering the ratio of methylparaben to glycine ethyl ester easily.
文摘以不同比例的重氮盐分别与聚双(N-羟基己氧基咔唑)磷腈(P-1)进行偶合反应,得到了一组以咔唑和对硝基偶氮咔唑为官能团的双功能型光折变聚合物P-2,P-3和P-4,用31 P NMR,1 H NMR,IR,TG,DSC和UV-Vis光谱对该组聚合物进行表征和分析,以325nm的激发波长对P-1,P-2,P-3和P-4进行固体荧光稳态发射光谱的测试。结果表明,该组聚合物具有良好的热稳定性(Td≈300℃)和较低的玻璃化温度(Tg≈30~40℃),P-1具有良好的荧光活性,硝基的引入,导致P-2,P-3和P-4的荧光发生不同程度的猝灭,咔唑与对硝基偶氮咔唑的数量及其空间分布排列的都会对其荧光性能产生影响。