A series of CexPr1-xO2-δ mixed oxides were synthesized by sol-gel method and characterized by Raman and XRD techniques. When x value was changed from 1.0 to 0.5, only a cubic phase CeO2 was observed. The samples were very well crystallized on decreasing x from 0.50 to 0.99. For CexPr1-xO2-δ samples 465 cm-1 and 1 150 cm-1 Raman peaks are attributed to the Raman active F2g mode of CeO2. The broad peak at about 570 cm-1 in the region of 0.3 ≤x≤ 0.99 can be linked to lattice defects resulting in oxygen vacancies. The new band at about 195 cm-1 may be attributed to the asymmetric vibration caused by the formation of oxygen vacancies. Calcination temperatures had great effect on the peak intensity for CeO2 but less effect on Ce0.8Pr0.2O2-δ in Raman spectra. It might be due to the transformation of the colors for the mixed oxides, the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides. 相似文献
Summary: The evolution of the various structural units incorporated into hyperbranched polymers formed from the copolymerization of AB2 and AB monomers has been derived by the kinetic scheme. The degree of branching was calculated with a new definition given in this work. The degree of branching monotonously increased with increasing A group conversion (x) and the maximum value could reach 2r/(1 + r)2, where r is the initial fraction of AB2 monomers in the total. Like the average degree of polymerization, the mean‐square radius of gyration of the hyperbranched polymers increased moderately with A group conversion in the range x < 0.9 and displayed an abrupt rise when the copolymerization neared completion. The characteristic ratio of the mean‐square radius of gyration remained constant for the linear polymers. However, the hyperbranched polymers did not possess this character. In comparison with the linear polymerization, the weight average and z‐average degree of polymerization increased due to the addition of the branched monomer units AB2 and the mean‐square radius of gyration decreased quickly for the products of copolymerization.
The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB_2 polycondensation with substitution effect were derived by the kinetic mechanism.The reactivity difference between the B group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained.The concentration of terminal units has a maximum with the increase of the conversion of A groups(x).The higher the reactivity... 相似文献
Highly branched structure has the essential influence on macromolecular property and functionality in physics and chemistry. In this work, we proposed a diffusion-limited reaction model with the consideration of macromolecular unit relaxations and substitution effect of monomers to study the structure of hyperbranched polymers prepared by slow monomer addition to a core molecule. The exponential relationship (R(g) ~ N(λ)) between the radius of gyration R(g) and the degree of polymerization N, was systematically analyzed at various branching degrees. It is shown that the effective exponent λ(eff) decreases at lower N and but increases toward that of diffusion-limited aggregation (DLA) clusters (λ(DLA) = 0.4) with the degree of polymerization increasing. The substitution effect of monomers in reaction strongly influences the evolution pathway of λ(eff). With the static light scattering technique, the fractal property of internal chains was further calculated. A general law about the radial distribution of the units of diffusion-limited hyperbranched polymers was found that, at smaller reactivity ratio k(12), the radial density of all monomer units D(A) declines from the center region to the peripheral layer revealing the dense core structure; however, at larger k(12), the density distribution shows a loose-dense-loose structure. These structural characteristics are helpful to deeply understand the property of hyperbranched polymers. 相似文献
A series of novel hyperbranched polyselenides and polytellurides with multiple catalytic sites at the branching units has been synthesized via the polycondensation of A2 + B3 monomers. The GPx‐like activities of these polymer mimics were assessed and it was found that the polytellurides showed higher GPx‐like activities than the corresponding polyselenides. Interestingly, the polymers with higher molecular weights and degree of branching (DB) showed higher GPx‐like activities than the analogous lower molecular weight polymer. The enhancement in the catalytical activity of the hyperbranched polymers with increasing molecular weight affirmed the importance of the incorporation of multiple catalytic groups in the macromolecule which increases the local concentration of catalytic sites. 相似文献
Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB2 monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed CuI, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83. 相似文献