Five samples of perfluoroheptyl end capped polyacrylic acid ( F P A A) having ahigh surface activity were prepared by free radicalpolymerization ofacrylicacid . Theinitiatorwas perfluorooctanoyl peroxide which produce...Five samples of perfluoroheptyl end capped polyacrylic acid ( F P A A) having ahigh surface activity were prepared by free radicalpolymerization ofacrylicacid . Theinitiatorwas perfluorooctanoyl peroxide which produced the free radicalof heptyl at 45 ℃. The yieldsof F P A A were in the range of 10 % to 25 % . The weight average molecular weights were2 62 ×104 to 7 99 ×104 and the polydispersity indexes were 1 97 to 5 64 ,depending on theconcentration of the initiator in the monomer. The surface tension was about 15m N/m at30 ℃forthe aqueous solution of F P A Awith the weight average molecular weight2 62 ×104in the concentration of about 0 01g/ m L. The molecular areas of F P A A at the air waterinterface under the condition ofcritical micelle concentration were 3 2 to 4 6n m2 ,which areobviously larger than the area per molecule of perfluorooctanoic acid (2 14nm 2) and muchsmaller than that of ordinary polyacrylic acid (83 4nm 2) . It means that the polymermoleculesin the surface adsorbed layer form the brush structure because of the special effectof the perfluoroalkyl groups at the chain ends .展开更多
Two kinds of novel fluorescent hyperbranched polymers were synthesized by the end-capping approach. The fluorescent hyperbranched polyether (FPEOTM) was obtained by end capping the hyperbranched poly(hydroxyl ether) (...Two kinds of novel fluorescent hyperbranched polymers were synthesized by the end-capping approach. The fluorescent hyperbranched polyether (FPEOTM) was obtained by end capping the hyperbranched poly(hydroxyl ether) (PEOTM) with guest molecules N,N-dimethylaminobenzaldehyde (DMABA). In addition, in the presence of triethylamine, the hyperbranched polysulfone-amine with terminal double bonds (HPSA) was synthesized by polyaddition of a new AB2 type monomer (SAP, sulfone amine piperazine) at 40℃ for 60 h in chloroform solution. Then the fluorescent hyperbranched polysulfone-amine (FHPSA) was prepared by addition of guest molecules N,N-dimethylaminoanilines (DMAA) with the terminal double bonds of HPSA. The two resulting polymers fluoresce yellow-green color in both solid and solution states. The maximum emission wavelength is (460 ±10) nm and (470±10) nm, respectively. A novel 'complex quenching effect' for hyperbranched polymer was observed. The fluorescence can be quenched by transition metal展开更多
Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However,the influence of the non-fluorinated block on ...Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However,the influence of the non-fluorinated block on the surface structure of the copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl methacrylate (FMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS),sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid interface,which favors the -(CF2)7CF3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers,in addition to the fluorinated monomer content,plays an important role in structure formation on the solid surface.展开更多
以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外...以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外分光光度计研究了其热分解现象和热分解动力学,采用表面张力仪对其表面活性进行了测定.结果表明,所合成的引发剂AIBL具有预想的结构和较高的纯度,其热分解反应属于一级反应,热分解活化能为134.80 k J/mol,70℃下水中的半衰期约为4 h;AIBL在水溶液中具有表面活性,其临界胶束浓度为0.13 g/L,对应的表面张力为33.57 m N/m.以丙烯酰胺为单体、AIBL为引发剂制备了水溶性端基疏水聚合物SPAM.采用溴化法研究其转化率,应用乌氏黏度法、零切黏度法以及荧光探针对其缔合作用进行了研究.结果表明,AIBL具有良好的引发丙烯酰胺聚合的能力;相对于不带疏水长链的引发剂所合成的聚合物PAM,SPAM具有明显的疏水缔合效应,这说明AIBL成功地将疏水长链引入到聚合物的端基中,从而形成端基疏水聚合物.展开更多
文摘Five samples of perfluoroheptyl end capped polyacrylic acid ( F P A A) having ahigh surface activity were prepared by free radicalpolymerization ofacrylicacid . Theinitiatorwas perfluorooctanoyl peroxide which produced the free radicalof heptyl at 45 ℃. The yieldsof F P A A were in the range of 10 % to 25 % . The weight average molecular weights were2 62 ×104 to 7 99 ×104 and the polydispersity indexes were 1 97 to 5 64 ,depending on theconcentration of the initiator in the monomer. The surface tension was about 15m N/m at30 ℃forthe aqueous solution of F P A Awith the weight average molecular weight2 62 ×104in the concentration of about 0 01g/ m L. The molecular areas of F P A A at the air waterinterface under the condition ofcritical micelle concentration were 3 2 to 4 6n m2 ,which areobviously larger than the area per molecule of perfluorooctanoic acid (2 14nm 2) and muchsmaller than that of ordinary polyacrylic acid (83 4nm 2) . It means that the polymermoleculesin the surface adsorbed layer form the brush structure because of the special effectof the perfluoroalkyl groups at the chain ends .
文摘Two kinds of novel fluorescent hyperbranched polymers were synthesized by the end-capping approach. The fluorescent hyperbranched polyether (FPEOTM) was obtained by end capping the hyperbranched poly(hydroxyl ether) (PEOTM) with guest molecules N,N-dimethylaminobenzaldehyde (DMABA). In addition, in the presence of triethylamine, the hyperbranched polysulfone-amine with terminal double bonds (HPSA) was synthesized by polyaddition of a new AB2 type monomer (SAP, sulfone amine piperazine) at 40℃ for 60 h in chloroform solution. Then the fluorescent hyperbranched polysulfone-amine (FHPSA) was prepared by addition of guest molecules N,N-dimethylaminoanilines (DMAA) with the terminal double bonds of HPSA. The two resulting polymers fluoresce yellow-green color in both solid and solution states. The maximum emission wavelength is (460 ±10) nm and (470±10) nm, respectively. A novel 'complex quenching effect' for hyperbranched polymer was observed. The fluorescence can be quenched by transition metal
基金Supported by the National Natural Science Foundation of China (Grant Nos. 50573069 & 20704038) Program for Changjiang Scholars and Innovative Re-search Team in University (Grant No. IRT 0654)
文摘Most research on copolymers with fluorinated monomers has focused on the relationship between fluorinated monomer content and the corresponding surface structure. However,the influence of the non-fluorinated block on the surface structure of the copolymer film is unknown. Various molecular weight poly(butyl methacrylates) (PBMA) end-capped with 2-perfluorooctylethyl methacrylate (FMA) units (PBMA-ec-FMA) have been synthesized by atom transfer radical polymerization (ATRP). The effect of the PBMA block length on the surface structure and properties of the polymers both in the solid state and in solution was investigated using various techniques. X-ray photoelectron spectroscopy (XPS),sum frequency generation (SFG) vibrational spectroscopy and X-ray diffraction (XRD) analyses indicated that longer PBMA blocks enhanced both the enrichment of the fluorinated moieties and the order of the packing orientation of the perfluoroalkyl side chains on the surface. This enhancement was attributed mainly to the molecular aggregate structure of the end-capped polymers with long PBMA blocks in the solution and to the interfacial structure at the air/liquid interface,which favors the -(CF2)7CF3 moieties self-assembling on the polymer surface during film formation. This observation suggests that the polyacrylate block structure in fluorinated diblock copolymers,in addition to the fluorinated monomer content,plays an important role in structure formation on the solid surface.
文摘以偶氮二异丁腈、十二胺为主要原料,通过Pinner反应制备了一种两端各带有12个碳烷基链的水溶性偶氮引发剂——2,2'-偶氮二异丁基十二脒盐酸盐AIBL.采用核磁氢谱、元素分析及液相色谱对AIBL进行了结构及纯度表征,采用TGA、DSC和紫外分光光度计研究了其热分解现象和热分解动力学,采用表面张力仪对其表面活性进行了测定.结果表明,所合成的引发剂AIBL具有预想的结构和较高的纯度,其热分解反应属于一级反应,热分解活化能为134.80 k J/mol,70℃下水中的半衰期约为4 h;AIBL在水溶液中具有表面活性,其临界胶束浓度为0.13 g/L,对应的表面张力为33.57 m N/m.以丙烯酰胺为单体、AIBL为引发剂制备了水溶性端基疏水聚合物SPAM.采用溴化法研究其转化率,应用乌氏黏度法、零切黏度法以及荧光探针对其缔合作用进行了研究.结果表明,AIBL具有良好的引发丙烯酰胺聚合的能力;相对于不带疏水长链的引发剂所合成的聚合物PAM,SPAM具有明显的疏水缔合效应,这说明AIBL成功地将疏水长链引入到聚合物的端基中,从而形成端基疏水聚合物.
