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21.
Piotr Dobrzynski Janusz Kasperczyk 《Journal of polymer science. Part A, Polymer chemistry》2006,44(10):3184-3201
Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the 13C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006 相似文献
22.
Piotr Dobrzynski Janusz Kasperczyk 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):98-114
The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in 1H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006 相似文献
23.
Peng Xu Haitao Wang Rui Lv Qiangguo Du Wei Zhong Yuliang Yang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(12):3911-3920
A novel microphase‐inversion method was proposed for the preparation of TiO2–SiO2/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006 相似文献
24.
Jon Samseth Richard J. Spontak Kell Mortensen 《Journal of Polymer Science.Polymer Physics》1993,31(4):467-474
Poly(siloxaneimide) (PSI) segmented copolymers exhibit organized microdomains if the blocks are sufficiently incompatible. As with neat diblock and triblock copolymers, the processing route employed to prepare films of PSI materials is expected to influence the dimensions and/or morphology of the resultant microstructure. In this work, small-angle neutron scattering (SANS) is utilized to characterize the disordered microstructure found in films of a series of PSI copolymers which are subjected to solvent casting and various thermal treatments. Microstructural dimensions such as the periodicity and correlation length are deduced from the Teubner-Strey (TS) model for disordered microemulsions. The scattering intensity of each copolymer up to q = 5.0 nm?1, where q is the scattering vector, is found to scale as q?2.8+?0.1. Results indicate that processing the materials as cast films or as melt-pressed films allowed to cool slowly has a small, but discernible, effect on microstructural characteristics. SANS profiles of films quenched from elevated temperatures reveal a clear transition in microdomain periodicity, which correlates well with the glass transition temperature of the imide microphase in these and other materials of similar chemical structure. © 1993 John Wiley & Sons, Inc. 相似文献
25.
Polyethylene terephthalate(PET)/polycaprolactone(PCL) segmented copolymers with different hard segment contents and a blend of two of them were studied by using DSC, WAXS, TEM and IR techniques and dynamic mechanical, stress-strain and isothermal crystallization measurements. Emphasis was laid on the studies of influence of compositional heterogeneity on the morphology and properties of these segmented copolymers. It was found that the solution cast specimens of the more heterogeneous sample exhibit better segregation of segments, high crystallinity and melting temperature. They have higher thermal stability of mechanical properties at small deformations. However, they are less stable against large deformations and may become softer than the more homogeneous ones. 相似文献
26.
Ni-SDC固体氧化物燃料电池阳极的合成和性质 总被引:4,自引:0,他引:4
采用柠檬酸-硝酸盐溶胶-凝胶低温自蔓延燃烧法制备氧化镍(NiO)粉末和Ce0.8Sm0.2O1.9(SDC)粉末,并将NiO与SDC按不同质量比和不同制备工艺制备了固体氧化物燃料电池(SOFC)的阳极前身。再用自组装的还原装置将其在820℃经2.5h还原后,采用四端子法测量其电导率值。分析了阳极片电导率与阳极片微结构、Ni的质量百分数、混合研磨时间及烧结温度之间的关系。结果显示,阳极片的电导率强烈依赖于镍含量和制备工艺。 相似文献
27.
A. I. Kovalev Yu. I. Lyakhovetskli M. M. Teplyakov A. L. Rusanov P. V. Petrovskii S. O. Yakushin 《Russian Chemical Bulletin》1993,42(9):1529-1535
The chemical heterogeneity of polyphenylenes obtained by trimerization poiycycio-condensation of acetylaromatic compounds has been investigated by GLC-MS analysis of the products of trimerization cyclocondensation of acetophenone. The mechanism for the formation of side products of the reaction is discussed. The presence of dypnone fragments in the polyphenylene structure results in a decrease in the thermal stability of these polymers.Deceased March, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1595–1601, September, 1993. 相似文献
28.
Ti-47Al-1.2Ce合金显微组织及稀土相 总被引:8,自引:2,他引:8
TiA1金属间化合物以其低密度 ,高比强度和比弹性模量 ,良好的抗蠕变及抗氧化能力等特点 ,已成为航天、航空、能源及汽车工业极具竞争力的高温结构材料。虽然TiAl基合金有众多优点 ,但仍存在室温塑性较低、成形性差、性能不平衡等问题 ,还需要深入研究TiAl基合金的合金化及制备工艺等方面技术 ,以此来控制并改善合金的显微组织 ,提高TiAl基合金的综合性能[1~ 4 ] 。合金化是改善TiAl基合金显微组织和性能的重要途径之一 ,通常添加的合金元素有V ,Cr ,Nb ,W ,Mo ,Si ,B等[5~ 7] 。稀土元素一般被用来细化材料… 相似文献
29.
K. Masenelli‐Varlot E. Reynaud G. Vigier J. Varlet 《Journal of Polymer Science.Polymer Physics》2002,40(3):272-283
Intercalated and exfoliated nanocomposites were prepared by extrusion and injection of polyamide‐6 and highly swollen or slightly swollen montmorillonite, respectively. The microstructure of the nanocomposites has been studied previously. In this article, we investigated the influence of the preferential orientation of the montmorillonite sheets on the mechanical properties of the nanocomposites. Dynamic mechanical analysis and tensile tests showed that the elastic modulus depends mainly on the filler loading. A parallel coupling could well account for the behavior of the nanocomposites. The calculated elastic and storage moduli of montmorillonite were set to 140 and 40 GPa, respectively. Compression tests were performed to study the anisotropy of the mechanical properties. The elastic modulus and flow strain were sensitive to the filler orientation. A Tandon–Weng approach was applied to consider the geometry of the filler. In all low‐deformation tests, no significant difference between intercalated and exfoliated systems was observed. Finally, the influence of the dispersion and exfoliation state of the filler on the ultimate properties of the nanocomposites (tensile tests) is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 272–283, 2002 相似文献
30.
In this article we study the effect of energetic heterogeneity of a crystalline surface on the adsorption of hydrogen ions (protons) from the liquid phase. In particular, we examine the influence of the shape of the adsorption energy distribution on the equilibrium isotherms of hydrogen ions. To that purpose, a few popular distribution functions, including rectangular, exponential, and asymmetric Gaussian are considered. Additionally, multimodal distribution functions, which may correspond to the adsorption on different crystal planes of the oxide, are also used. Lateral interactions between adsorbed charges are modeled using the potential function proposed by Borkovec et al., which accounts also for polarization of the liquid medium. The results presented here are obtained using both Monte Carlo (MC) simulations and theoretical calculations involving Mean Field Approximation (MFA). They indicate that increased energetic heterogeneity of the adsorbing surface may, in general, considerably change the behavior of the adsorption isotherms, regardless of the assumed distribution function. It is also shown that the predictions of the proposed theory are consistent with the data obtained from the MC simulations. 相似文献