In this study, polyimide fibers at different stages of imidization were characterized by TGA, DSC, and FTIR. The imidization degree (ID) calculated by TGA was based on the weight loss of each sample, which was cause...In this study, polyimide fibers at different stages of imidization were characterized by TGA, DSC, and FTIR. The imidization degree (ID) calculated by TGA was based on the weight loss of each sample, which was caused by the imidization of residual amic acid groups. The results of TGA showed good regularity with the thermal treatment temperature of the PI fibers. For DSC, the ID was calculated based on the area of endothermal peak of each sample. Compared with TGA, DSC showed a relatively higher value because the endothermal peak was reduced by the exothermic re-formation of polyamic acid which may be partially degraded during thermal treatment. The IDs obtained by the FTIR spectra generally showed poorer regularities than those obtained by both TGA and DSC, especially for the results calculated using the 730 cm^-1 band. Based on the 1350 cm^-1 band, the obtained IDs showed better agreement with the TGA or DSC results. The results obtained by these three methods were compared and analyzed. The ID obtained by TGA showed much more reliability among these three methods.展开更多
Eight 6FDA-TFDB polyimide(PI)samples with absolute molecular weights ranging from 1.25 × 10^5 g mol^-1 to 3.11 × 10^5 g mol^-1 are obtained by precipitation fractionation.Rheological experiments are conducte...Eight 6FDA-TFDB polyimide(PI)samples with absolute molecular weights ranging from 1.25 × 10^5 g mol^-1 to 3.11 × 10^5 g mol^-1 are obtained by precipitation fractionation.Rheological experiments are conducted to determine the influence of molecular weight on the associating behavior of PI in A/X-dimethylformamide(DMF)solutions in a broad volume fraction,including abnormal steady shear flow,solution heterogeneity,and scaling behavior.Abnormal flow behaviors,i.e.,multi-region shear thinning and weak shear thickening,are studied,and these behaviors have not been reported in literature.The heterogeneity of PI/DMF solutions is examined by dynamic rheological test.By plotting qsp versus four concentration regions of l-IV can be distinguished for all PI samples with various molecular weights.The scaling results in different concentration regions are in good agreement with the associative polymer theory proposed by Rubinstein and Semenov.The scaling exponents do not show molecular weight dependence in concentration regions I and II.In concentration regions Ⅲ and Ⅳ,the scaling exponents change little when the molecular weight is below 242 k but increase when the molecular weight increases from 242 k to 311 k.This work can help us to understand polyimide solution properties from dilute to semidilute entangled solutions,and will guide the polyimide solution preparation for different processing.展开更多
This report details the properties of fluorine-containing anion exchange membranes(AEMs) synthesized by chloromethylation and quaternization of fluorinated poly(arylene ether)s(FPAEs) based on decafluorobiphenyl...This report details the properties of fluorine-containing anion exchange membranes(AEMs) synthesized by chloromethylation and quaternization of fluorinated poly(arylene ether)s(FPAEs) based on decafluorobiphenyl and bisphenol A. Meanwhile, we compared their properties with those of their non-fluorinated counterparts, Udel-based AEMs. The reactivity of the chloromethylation of fluorinated poly(arylene ether)s was lowered by the strong elec- tron-withdrawing group, per-fluorinated biphenyl residue. Therefore higher temperature, more chloromethylation reagent, and longer reaction time were needed in the chloromethylation of FPAEs. Because of the hydrophobicity of fluorine, the swelling of FPAEs was depressed. In the FPAE-based AEMs, the water uptake of FPAE-1 membrane(F-1) was just 30%. There is a strong correlation between water uptake and conductivity for both Udel- and FPAE-based AEMs. Among all the membranes, the water uptake and the conductivity of FPAE-3 membrane(F-3) could reach up to 100% and 13.47 mS/cm respectively at 30 ℃. The mechanical properties of FPAE-based AEMs at room tempera- ture were worse than those of Udel-based ones because of the weak intermolecular interaction caused by the low po- larizability of fluorine. However, their high temperature mechanical properties are better, which can be explained in terms of low swelling.展开更多
G-Quadruplexes(GQs),which are formed by G-rich DNA sequences in human telomeres,have become an attractive target for cancer treatment.The ligands to stabilize the conformation of human telomeric GQs in vivo are partic...G-Quadruplexes(GQs),which are formed by G-rich DNA sequences in human telomeres,have become an attractive target for cancer treatment.The ligands to stabilize the conformation of human telomeric GQs in vivo are particularly important for structure-based ligand design and drug development targeting the noncanonical DNA structure.Here we report the conformational conversion of Tel26 induced by a naphthalene diimide(NDI)ligand in K^(+)buffer,even at cellular physiological temperature(37℃)and under mimetic cellular crowding conditions created by Ficoll 70.We provide an insight into the dynamic conversion from initial hybrid-2 GQ topology to final parallel GQ topology.These results are helpful for the design of ligands with GQ conformation regulation.展开更多
The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step ...The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step method using 2,2′,3,3′-biphenyltetracarboxylic dianhydride(3,3′-BPDA) and aromatic diamines as the monomers, and 4-phenylethynyl phtlialic anhydride(PEPA) as the end-capping agent. The imide oligomers based on 3,3′-BPDA showed excellent solubility in low boiling point solvents and low melt viscosity, which were attributed to their unique bent architectures. High-performance thermosetting polyimides were produced from these oligomers via thermal crosslinking of the phenylethynyl groups. The mechanical and thermal properties of the thermosets were studied using tensile testing, dynamic mechanical thermal analysis(DMTA), and thermogravimetric analysis(TGA). The 3,3′EPDA-based thermosets exhibited excellent thermal properties, with glass transition temperatures of up to 455℃, and 5% mass loss temperatures of up to 569℃ in air. The thermosets based on 3,3-BPDA showed superior thermal properties compared to those derived from TriA-X series oligomers.展开更多
基金financially supported by the National Basic Research Program of China(No.2014CB643603)the National Natural Science Foundation of China(No.51173178)
文摘In this study, polyimide fibers at different stages of imidization were characterized by TGA, DSC, and FTIR. The imidization degree (ID) calculated by TGA was based on the weight loss of each sample, which was caused by the imidization of residual amic acid groups. The results of TGA showed good regularity with the thermal treatment temperature of the PI fibers. For DSC, the ID was calculated based on the area of endothermal peak of each sample. Compared with TGA, DSC showed a relatively higher value because the endothermal peak was reduced by the exothermic re-formation of polyamic acid which may be partially degraded during thermal treatment. The IDs obtained by the FTIR spectra generally showed poorer regularities than those obtained by both TGA and DSC, especially for the results calculated using the 730 cm^-1 band. Based on the 1350 cm^-1 band, the obtained IDs showed better agreement with the TGA or DSC results. The results obtained by these three methods were compared and analyzed. The ID obtained by TGA showed much more reliability among these three methods.
基金the National Basic Research Program of China(No.2014CB643604)the National Natural Science Foundation of China(No.51173178).
文摘Eight 6FDA-TFDB polyimide(PI)samples with absolute molecular weights ranging from 1.25 × 10^5 g mol^-1 to 3.11 × 10^5 g mol^-1 are obtained by precipitation fractionation.Rheological experiments are conducted to determine the influence of molecular weight on the associating behavior of PI in A/X-dimethylformamide(DMF)solutions in a broad volume fraction,including abnormal steady shear flow,solution heterogeneity,and scaling behavior.Abnormal flow behaviors,i.e.,multi-region shear thinning and weak shear thickening,are studied,and these behaviors have not been reported in literature.The heterogeneity of PI/DMF solutions is examined by dynamic rheological test.By plotting qsp versus four concentration regions of l-IV can be distinguished for all PI samples with various molecular weights.The scaling results in different concentration regions are in good agreement with the associative polymer theory proposed by Rubinstein and Semenov.The scaling exponents do not show molecular weight dependence in concentration regions I and II.In concentration regions Ⅲ and Ⅳ,the scaling exponents change little when the molecular weight is below 242 k but increase when the molecular weight increases from 242 k to 311 k.This work can help us to understand polyimide solution properties from dilute to semidilute entangled solutions,and will guide the polyimide solution preparation for different processing.
基金Supported by the National Natural Science Foundation of China(Nos.51173178, 514"73157, 21304093).
文摘This report details the properties of fluorine-containing anion exchange membranes(AEMs) synthesized by chloromethylation and quaternization of fluorinated poly(arylene ether)s(FPAEs) based on decafluorobiphenyl and bisphenol A. Meanwhile, we compared their properties with those of their non-fluorinated counterparts, Udel-based AEMs. The reactivity of the chloromethylation of fluorinated poly(arylene ether)s was lowered by the strong elec- tron-withdrawing group, per-fluorinated biphenyl residue. Therefore higher temperature, more chloromethylation reagent, and longer reaction time were needed in the chloromethylation of FPAEs. Because of the hydrophobicity of fluorine, the swelling of FPAEs was depressed. In the FPAE-based AEMs, the water uptake of FPAE-1 membrane(F-1) was just 30%. There is a strong correlation between water uptake and conductivity for both Udel- and FPAE-based AEMs. Among all the membranes, the water uptake and the conductivity of FPAE-3 membrane(F-3) could reach up to 100% and 13.47 mS/cm respectively at 30 ℃. The mechanical properties of FPAE-based AEMs at room tempera- ture were worse than those of Udel-based ones because of the weak intermolecular interaction caused by the low po- larizability of fluorine. However, their high temperature mechanical properties are better, which can be explained in terms of low swelling.
文摘G-Quadruplexes(GQs),which are formed by G-rich DNA sequences in human telomeres,have become an attractive target for cancer treatment.The ligands to stabilize the conformation of human telomeric GQs in vivo are particularly important for structure-based ligand design and drug development targeting the noncanonical DNA structure.Here we report the conformational conversion of Tel26 induced by a naphthalene diimide(NDI)ligand in K^(+)buffer,even at cellular physiological temperature(37℃)and under mimetic cellular crowding conditions created by Ficoll 70.We provide an insight into the dynamic conversion from initial hybrid-2 GQ topology to final parallel GQ topology.These results are helpful for the design of ligands with GQ conformation regulation.
基金the Technology Innovation Fund of Chinese Academy of Sciences(NO.CXJJ-17-M159)the National Natural Science Foundation of China(No.51473157).
文摘The properties of a series of imide oligomers were characterized according to their molecular weights, solubility, and thermal and rheological properties. This series of imide oligomers was synthesized via a two-step method using 2,2′,3,3′-biphenyltetracarboxylic dianhydride(3,3′-BPDA) and aromatic diamines as the monomers, and 4-phenylethynyl phtlialic anhydride(PEPA) as the end-capping agent. The imide oligomers based on 3,3′-BPDA showed excellent solubility in low boiling point solvents and low melt viscosity, which were attributed to their unique bent architectures. High-performance thermosetting polyimides were produced from these oligomers via thermal crosslinking of the phenylethynyl groups. The mechanical and thermal properties of the thermosets were studied using tensile testing, dynamic mechanical thermal analysis(DMTA), and thermogravimetric analysis(TGA). The 3,3′EPDA-based thermosets exhibited excellent thermal properties, with glass transition temperatures of up to 455℃, and 5% mass loss temperatures of up to 569℃ in air. The thermosets based on 3,3-BPDA showed superior thermal properties compared to those derived from TriA-X series oligomers.