基于2,5-二(4′-甲酰基苯基)苯乙烯的螺旋链光学活性聚合物的合成与表征

通过2,5-二溴苯乙烯与对甲酰基苯硼酸的Suzuki偶联反应得到2,5-二(4′-甲酰基苯基)苯乙烯.在催化剂量的冰乙酸存在下,与光学纯的(S)-(-)-α-甲基苄胺或(R)-(+)-α-甲基苄胺发生缩和反应,得到了一对手性非外消旋单体,(+)-2,5-二{4-′[(N-(S)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯和(-)-2,5-二{4′-[(N-(R)-α-甲基苄亚胺基)次甲基]苯基}苯乙烯.以偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO)为引发剂,经自由基溶液聚合得到光学活性聚合物.比旋光度、紫外-可见吸收光谱以及圆二色光谱研究表明,聚合物主链可能形成了某一方向占优的稳定螺旋构象,且该螺旋构象的旋光方向与单体的旋光方向相反.聚合条件对聚合物的光学活性有很大影响,在极性较大的芳香族溶剂和较高温度下得到的聚合物具有和单体相差更大的比旋光度.侧基的手性基团脱除后,聚合物仍具有一定的旋光性,说明聚合过程中形成的螺旋手性具有一定的记忆效应.     

BF3-doped polyaniline: A novel conducting polymer

We review the unusual structural, transport and magnetic properties of highly conducting polyaniline, doped with boron trifluoride. Our studies establish the unique conducting state of this system, which is in distinct contrast with the conventional proton-doped polyaniline samples.     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

12-Ring Network Coordination Polymer——{[Cu(C_4N_2H_(10))_4]_2·H_4V_4O_(14)}_n Formed by Linking cyclo-[H_4V_4O_(14)]~(4-) with Cu(C_4N_2H_(10))~(2+)_4 Cation Clusters

IntroductionThe interest in polyoxometalates that are widelyused in medical chemistry, catalyst reactions, and ma-terial sciences stems from their complicated aggregatesformed by means of corner-, edge- and face-sha-ring[1—4]. The exploitation of new str…     

Elastic and Thermophysical Properties of Poly(Vinyl Chloride) and Chlorinated Polyethylene Blends

The results of experimental and theoretical investigations of elastic and thermophysical properties of poly(vinyl chloride) (PVC) and chlorinated polyethylene (CPE) blends are presented. Eight types of specimens with different ratios of weight contents of PVC and CPE (PVC/CPE = 100/0, 90/10, 80/20, 60/40, 40/60, 20/80, 10/90, and 0/100) were tested. The effect of blend composition on the elastic constants (tensile and shear modulus) is discussed. The data on the thermal conductivity, thermal diffusivity, and heat capacity of the blends investigated are also presented.     

STUDY ON THE CONFORMATIONAL PROPERTIES OF RIGID POLYELECTROLYTE SPU IN SOLUTION

The conformation and dimension of SPU polyanion have been studied by viscosity and quasi-elastic light scattering methods. The rigidity of SPU is somewhat similar to CMC and its hydrodynamic radius decreases only slowly with increasing concentration of NaCl.     

Achievements in the field of proton-conductive portion electrolyte membranes

The 2000–2006 achievements in the field of synthesis, property examination, and application of proton-exchange membranes are reviewed on the basis of more than 120 papers.     

Synthesis and crystal structure of 1,3,5-tris [4-(phenylethynyl)phenyl]benzene

The crystal structure of 1,3,5-tris[4-(phenylethynyl)phenyl]benzene (1) has been investigated. Compound1 represents a model of the repeating unit of the most typical polyphenylene, which contains 1,3,5-trisubstituted benzene rings (chain centers) and acetylenic groups (complex-forming and cross-linking centers) in the main chain. The acetylene groups of neighboring molecules have a tendency to close mutual arrangement, which is favorable for their topochemical interaction. However, the relative conformational rigidity of molecules1 restricts not only the possibility of the optimal adjustment of the reactive sites of neighboring molecules to one another, but also hampers the close packing of molecules in the crystal, which contains channels filled by the solvent molecules (chloroform).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1986–1992, November, 1994.The work was carried out with the financial support of the International Science Foundation and the American Crystallographic Association.     

Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.