Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model. II. Number-average molecular weight and apparent initiator efficiency

The equations for predicting the number-average molecular weight are derived on the basis of the three stage polymerization model (TSPM) in this paper. By applying the equations, a plotting approach is proposed to determine the apparent initiator efficiency defined as f[(α_td+1)/2] and the constant of chain transfer to monomer, where f is the initiator efficiency and α_td denotes the fraction of the termination rate constants by disproportionation. Using the approach to plot the experimental data in the literature, it is found that the chain transfer to monomer can be neglected for both methylmethacrylate (MMA) and styrene (St) polymerizations, but it can exert a significant effect on ethylmethacrylate (EMA) polymerization. In addition, the apparent initiator efficiency is found to be independent of reaction temperature and initiator concentration at each stage. The values of f[(α_td+1)/2] at gel effect stage are slightly reduced as compared with that at low conversion stage for MMA and EMA polymerizations. However, it decreases significantly at gel effect stage for St polymerization. Using the equations derived and the apparent initiator efficiencies obtained from TSPM plots, the number-average molecular weights at different conversions can be predicted. Comparisons show that the agreement between predictions and experimental data is satisfactory.     

Thermally induced microstructural changes in cotton fibers: A free‐volume study

I measured positron lifetime in natural polymer–cotton fibers as a function of isochronal annealing temperature in the range 27–290°C. The variations in the positron results indicated structural changes occurring in the cotton fibers and determined the glass‐transition temperature as 80°C. Activation energies were measured separately for the crystalline and amorphous regions, indicating the versatility of the technique. These values were close to the O? H bond dissociation energy, suggesting O? H bond dissociation, the most probable process occurring under thermal treatment. As an extension of the positron results, the molecular weight of the cotton fibers was determined to be 1,200,000 based on free volume, which was within the range suggested for cotton. There seemed to be an indication that crosslinking changed the spiral structure of cotton fibers to the network type. However, this needs to be validated by other measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3336–3345, 2002     

Defects in molecular beam epitaxial GaAs grown at low temperatures

We have utilized a variable energy positron beam and infrared transmission spectroscopy to study defects in GaAs epilayers grown at low temperatures (LT-GaAs) by molecular beam epitaxy. We have measured the Doppler broadening of the positron-electron annihilation gamma ray spectra as a function of positron implantation energy. From these measurements, we have obtained results for the depth profiles of Ga monovacancies in unannealed LT-GaAs and Ga monovacancies and arsenic cluster related defects in annealed LT-GaAs. We have also studied the effects of the Si impurities in annealed LT-GaAs. The infrared transmission measurements on unannealed LT-GaAs furnish a broad defect band, related to As antisites, centered at 0.370 eV below the conduction band.     

固载于SBA-15分子筛中的同双核金属配合物催化剂

合成了3种同双核金属配合物[M2LCl3]Cl(L代表配体三亚乙基四胺,M代表Co,Cu,Cr),采用微波加热法合成了SBA-15分子筛,采用浸渍法将3种同双核金属配合物分别固载在表面官能化的SBA-15分子筛(SBA-15-NH2分子筛)中制得负载型催化剂。傅里叶变换红外光谱、X射线衍射、紫外可见光谱和热分析表征结果表明,同双核金属配合物被固载后,其结构仍保持完整。以环己烷氧化反应为探针反应,考察了[Co2LCl3]Cl/SBA-15-NH2,[Cu2LCl3]Cl/SBA-15-NH2,[Cr2LCl3]Cl/SBA-15-NH2催化剂的活性,环己烷转化率分别为11.0%,49.5%,57.9%;对于[Cr2LCl3]Cl/SBA-15-NH2催化剂,当分别以乙睛、丙酮和冰醋酸为溶剂时,环己烷转化率分别为57.9%,52.1%,34.2%,3次重复实验的环己烷转化率分别为57.9%,47.8%,46.5%,表明该催化剂具有较好的活性和重复使用性。     

Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations

Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H⁺, using acid treatment or exchanging with NH₄⁺ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H⁺ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O⁻) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction.     

Effects of mastication on the distribution of molecular weights and on the mechanical properties of native and commercial dental gutta percha (trans-polyisoprene)

Mastication of gutta percha (trans-polyisoprene) resulted in the selective scission of molecules, producing a narrower distribution of lower molecular weights. The mechanical properties of the samples also underwent a significant change due to mastication. The greater the content of incompatible substances (salts and oxides) in commercial gutta percha. the more substantial were these effects. The atmosphere (air, N₂, O₂) in which the experiments were conducted yielded significantly different results. The decrease in molecular weight was far greater in an O₂ atmosphere than under a current of nitrogen or air, owing to the combination of double bonds with O₂.     

Studies on the synthesis of SAPO-5

Silicoaluminophosphate (SAPO-5) molecular sieves have been synthesised from reaction mixtures having a molar composition of: 0.7–1.0 Al₂O₃:0.7–1.0 P₂O₅:0.01–2.0 SiO₂:xR:40 H₂O (where R = (C₂H₃)₃N or (C₂H₃)₄NOH and x = 1.5–2.5 for (C₂H₅)⁵N and 0.5 for (C₂H₅)₄NOH, at 473 K using various sources of alumina and silica. The effects of (i) varying the crystallinity of the alumina source (boehmite) and (ii) the use of different silica sources such as freshly prepared silica either from sodium silicate or paddy husk extract, silica gel from commercial water-glass, and tetraethyl orthosilicate have been studied. The crystallinity of boehmite has been found to have a strong effect on its reactivity towards the formation of SAPO-5. The activity of boehmite for SAPO-5 formation increased with a decrease in its crystallinity (or with increase in its moisture content). Any silica source devoid of sodium ions could be employed for the synthesis of SAPO-5. The process of crystallisation started as early as within 1.5 h of reaction and incorporation of silicon into the AlPO₄ framework has been noted at this stage. Formation of some tridymite phase as impurity has been observed under conditions such as (i) SiO₂ concentration > 1.7 mole and (ii) x > 2.0 when R = (C²H₅)₃N.     

Flow of solutions of hydroxypropyl guar-poly(ethylene oxide) mixtures through a porous medium

Summary In flow through porous media, solutions of poly(ethylene oxide) (PEO) exhibit extension thickening, whereas hydroxypropyl guar (HPG) solutions are shear-thinning at high concentrations. The results show that the extension-thickening exhibited by PEO solutions becomes less critical with increasing flow rate as the concentration of HPG in the solution is increased. At high concentrations of HPG, the presence of PEO inhibits the shear-thinning behaviour, without increasing the apparent viscosity of the solution. The presence of HPG reduces the rate and extent of degradation of PEO in the flowing solution.     

Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

La-OMS-2催化剂催化甲苯氧化制苯甲醛

合成了氧化锰八面体(OMS-2)分子筛,采用离子交换法和浸渍法制备了稀土金属La改性的OMS-2分子筛(La-OMS-2)催化剂,并用于甲苯液相选择性氧化制苯甲醛,考察了催化剂用量、反应温度、反应时间、氧气流量及溶剂种类对甲苯转化率和苯甲醛选择性的影响,对La-OMS-2催化剂进行了X射线衍射表征和BET比表面积测定。实验结果表明,离子交换法制备的La-OMS-2-A催化剂的活性高于浸渍法制备的La-OMS-2-B催化剂,在甲苯0.1mol、溶剂冰乙酸10mL、氧气流量60mL/min、La-OMS-2-A催化剂用量0.10g、反应温度353K、反应时间1.0h的条件下,甲苯转化率达61%,苯甲醛收率为56%。加入La对OMS-2分子筛中的MnO晶格结构产生了影响,提高了苯甲醛的收率。