Properties,Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

The mechanical properties of fibers were notably improved by incorporating 2,2＇-bis（trifluoromethyl）benzidine（TFMB） into 3,3＇,4,4＇-biphenyltetracarboxylic dianhydride（s-BPDA） and p-phenylenediamine（PPD） backbone.The best strength and modulus of BPDA/PPD/TFMB polyimide（PI） fiber（diamine molar ratio of PPD/TFMB= 90/10） were 1.60 and 90 GPa,respectively,which was over two times that of BPDA/PPD PI fiber.SEM image showed that the cross-section of fibers at each stage was round and voids free.Besides,the ＂skin-core＂ and microfibrillar structure were not observed.The thermal properties of PI fibers were also investigated.The results showed that the fibers owned excellent thermal stability,moreover,the structural homogeneity of fibers were significantly improved by heat-drawn stage.The T g values were found to be around 300 °C by dynamic mechanical analysis（DMA）.Wide angle X-ray diffraction（WAXD） and small angle X-ray scattering（SAXS） experiments indicated that the order degree of longitudinal and lateral stacks,the molecular orientation and the structural homogeneity of fibers were improved in the preparation process of fibers.

Crystal Structure and Solution Behavior of a Novel Enantiopure Helical Coordination Polymer Based on Binaphthyl-bisbipyridine Ligand

An enantiopure helical coordination polymer AgPF6·（R）-3 as crystalline solid was synthesized by the self-assembly of chiral binaphthyl-based ligand（R）-6,6＇-di[6-（2,2＇-bipyridyl）]-2,2＇-diethoxyl-1,1＇-binaphthalene [（R）-3] and Ag＋ ion.The single crystal structural analysis indicates that this polymer exhibits an infinite cylindric single-stranded M-helical structure with local Λ configuration at each tetrahedral metal center.However,the extended structure is dissociated into some oligomeric fragments in solution.The 1H NMR spectra of complex AgPF6·（R）-3 show that the ligand possesses a good C2 symmetry,and the chemical shifts of the protons depend on the concentration and temperature.In addition,there are rapid dynamic exchanges among some oligonuclear fragments in the solution of AgPF6·（R）-3.

Enantioselective Iodolactonizations of (E)-and (Z)-5-Substituted-4-pentenoic Acid Derivatives Mediated by Chiral Salen-Co(II) Complex

A number of salen-metal complexes were prepared and their enantioselective catalytic properties toward the asymmetric iodolactonization of （E）- and （Z）-5-substituted-4-pentenoic acid derivatives were investigated. The catalyst system based on salen-Co（II） complex exhibited moderate to good enantioselectivity with the e.e. value ranging from 53% to 74%, as well as high regioselectivity of δ- vs. γ-iodolactones. The salen-Co（II） complex showed the highest enantioselectivity on the asymmetric iodolactonizations of （Z）-5-substituted-4-pentenoic acid derivatives among these reagent-controlled iodolactonization protocols known so far.

Flexible Synthesis of Enantiomeric and Racemic 3-Hydroxymethyl-1,2,3,4-tetrahydroisoquinolines via Bischler-Napieralski Reaction

With methyl ester of N-acylated L-3-（3,4-dihydroxyphenyl）alanine（L-DOPA） as starting material, racemic derivatives of 3-hydroxymethyl-1,2,3,4-tetrahydroisoquinoline were obtained with cyclization by Bischler-Napie- ralski（BN） reaction followed by reduction of methyl ester group to hydroxymethyl, while the optical pure enantiomers were prepared by the reduction of the methyl ester group to hydroxymethyl prior to cyclization with BN reaction. Racemerization took place in the BN stage in the presence of methyl ester, an electron-withdrawing group adjacent to chiral center. Therefore, the sequence of synthetic stages of cyclization and reduction, and subsequently whether there is electron-withdrawing group or not determines the chiral optical activity of the products.

Synthesis and Characterization of Novel Sulfonated Polyimides from 4,6-Bis（4-aminophenoxy）-naphthalene-2-sulfonic Acid

A novel sulfonated diamine monomer, 4,6-bis（4-arninophenoxy）-naphthalene-2-sulfonic acid（BAPNS）, was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetracarboxylic dianhydride（NTDA） and nonsulfonated diamine 4,4＇-diaminodiphenyl ether（ODA）. Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide（SPI） membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃（SPI-X： Xrefers to molar fraction of BAPNS）. The membranes exhibit the permeability of methanol from 2.18×10^-7 cm2/s to 2.57×10^-7 cm2/s, which is much lower than that of Nafion（2.00×10 6 cm^2/s）. The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%（molar fraction） BAPNS is 1.35 GPa under high moisture condi- tions. The optimum concentration of BAPNS was found to be 100%（molar fraction） from the view point of proton conductivity, methanol permeability, and membrane stability.