异丁烯两段催化氧化制甲基丙烯酸催化剂研究 Ⅰ．异丁烯气相氧化制甲基丙烯醛多元复合氧化物催化剂的研究

本文报导用于异丁烯（叔丁醇）选择氧化制ＭＡＬ（甲基丙烯醛）的多元复合氧化物催化剂的研究结果。同共沉淀法制备的催化剂的活性主要决定于其化学组成，同时受到制备条件的影响。最佳催化剂的主要物相组成为ＰｂＯ３，Ｂｉ２ＭｏＯ３．３、ＮｉＭｏＯ４、Ｓｂ２Ｏ３及ａ－Ｆｅ２Ｏ３小颗粒。在３５５℃，１０００～２５００ｈ－１空速范围，叔丁醇：水：空气＝１：３．３：７（摩尔比）的条件下可获得异丁烯转化率达９６％，ＭＡＬ选择性达８９％的结果。     

Water-soluble and amphiphilic polymers

Summary Three PEO-PSt-PEO triblock polymers and their parent ho-nopolystyrene have been studied by means of light scattering technique in chloroform, toluene and ethyl acetate. It has been found that the weight average molecular weights calculated by using the equation Mapp- were unbelievable negative values; and the largest deviation appeared for the sample with PEO mole content of about 50%. Data of PSt-PEO-PSt triblock polymers in literature have been quoted and discussed.     

The determination of the pore structural parameters of isoporous resins by inverse GPC

The swollen pore structure of a series of microporous isoporous resins (7.4–140 Å) are investigated with inverse GPC, n-alkylbenzenes and linear polystyrenes being used as probe molecules. The results indicated that, with the lowering of crosslinking degree of isoporous resins, the average pore diameter increased and the pore distribution curve broadened. All pore volume distribution obeyed a log-normal distribution. Based on the linear regression method, the experimental data were fitted to a monotonously declining exponential function and a normal distribution function by a computer, and some important structural parameters such as average pore diameter, pore volume distribution, specific surface area, etc. were obtained. The specific surface area of swollen gels were found much greater than those in the dry state measured by N₂ adsorption.     

Synthesis and characterization of copolythiophene

Copolythiophenes (Co‐PTs), poly(3‐hexylthiophene‐co‐3‐thiophene carboxylic acid) (P3HT‐TCa), poly(3‐hexyloxylthiophene‐co‐3‐thiophene carboxylic acid) (P3HOT‐TCa), and poly(3‐phenylthiophene‐co‐3‐thiophene carboxylic acid) (P3PhT‐TCa), were synthesized by chemical oxidized polymerization to investigate the effect of copolymerization on the properties of polythiophenes (PTs). Gel permeation chromatography showed that the molecular weight (MW) of Co‐PT was lower than that of homopolythiophene. Fourier transform infrared (FTIR) spectra indicated that the copolymerization was successful between the monomers. The λ_max of Co‐PTs gave a “blue shift” in ultraviolet‐visible (UV‐VIS) spectra. Photoluminescence (PL) spectra showed that the PL intensity of Co‐PT became weaker than that of homopolythiophene and the disappearance of PL had been observed in P3HOT‐TCa. The thermal stability of Co‐PT was influenced by the carboxyl for its low decomposition temperature. Furthermore, the copolymerization between multi‐wall carbon nanotube containing thiophene ring (MWNT‐Th) and 3‐hexyloxylthiphene could also take place successfully. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

混合物MH-81状态方程的研究——从无限稀释活度系数预测混合物汽液平衡

本文由无限稀释活度系数求取混合物MH-81状态方程的二元相互作用参数,预测了二元混合物的汽液平衡,获得了较满意的结果。     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

Synthesis and Morphology of TiO2 Nanotube Arrays by Anodic Oxidation Using Modified Glycerol-Based Electrolytes

Titanium dioxide (TiO₂) nanotube arrays were prepared by electrochemical anodization of titanium sheets in the glycerol 176 mL/H₂O 44 mL/NH₄F 0.5 wt% electrolytes modified with H₂SO₄ and NaAc addition. The surface morphologies, average inner diameter, and the length of the nanotube arrays changed with the solution pH in the range from 5.6 to 4.0 by adding H₂SO₄. A uniform surface morphology of the nanotubes with average inner diameter of ∼80 nm and a length of ∼1000 nm was obtained when the solution pH was 5.0. The growth rates of the nanotubes were remarkably enhanced by NaAc addition in the range of 0.04–0.14 M . With NaAc addition of 0.10 M , the length of the nanotube arrays reached 4.16 μm after an 8-h anodization, increasing 3.23 μm compared with no NaAc addition. The relationship between solution pH and growth of TiO₂ nanotubes was analyzed by current–time curves, solution electrical conductivities, and scanning electron microscopy (SEM), and the role of NaAc was also discussed based on SEM and solution electrical conductivities.     

微晶纤维素增粘剂的研制

以棉浆为原料，废盐酸为水解催化剂，所得合成革用微晶纤锥素增粘剂的质量指标达到了德国和日本同类产品的标准。     

Study of different effect on foaming process of biodegradable bionolle in supercritical carbon dioxide

Microcellular foaming of biodegradable Bionolle in supercritical CO₂ has been produced. The effects of a series of variable factors, such as saturation temperature, saturation pressure, and depressurization time and step on the foam structures and density, were studied through measurement of density and SEM observation. The experimental results show that higher saturation temperatures lead to an increase in bulk densities; and different depressurization time and step result in different product cell morphology. In addition, at some saturation temperature, the orientation of the cells can be found in the product morphology. XRD experimental results show that the foaming treatment with SC CO₂ increased the crystallinity of Bionolle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2901–2906, 2006     

Effect of fretting amplitudes on fretting wear behavior of steel wires in coal mines

Given that fretting wear causes failure in steel wires, we carried out tangential fretting wear tests of steel wires on a self-made fretting wear test rig under contact loads of 9 and 29 N and fretting amplitudes ranging from 5 to 180 μm. We observed morphologies of fretted steel wire surfaces on an S-3000N scanning electron microscope in order to analyze fretting wear mecha-nisms. The results show that the fretting regime of steel wires transforms from partial slip regime into mixed fretting regime and gross slip regime with an increase in fretting amplitudes under a given contact load. In partial slip regime, the friction coefficient has a relatively low value. Four stages can be defined in mixed fretting and gross slip regimes. The fretting wear of steel wires in-creases obviously with increases in fretting amplitudes. Fretting scars present a typical morphology of annularity, showing slight damage in partial slip regime. However, wear clearly increases in mixed fretting regime where wear mechanism is a combination of plastic deformation, abrasive wear and oxidative wear. In gross slip regime, more severe degradation is present than in the other regimes. The main fretting wear mechanisms of steel wires are abrasive wear, surface fatigue and friction oxidation.