Ring‐opening polymerization of lactones initiated by diphenylzinc–coinitiator systems

Diphenylzinc, alone or in combination with water and butanone as coinitiators, was used as a polymerization initiator system for a variety of lactones at varying temperatures. The resulting data indicate that the course of the polymerization is greatly influenced by the lactone structure, as well as by the molar ratio of coinitiator to diphenylzinc. When used alone, diphenylzinc exhibited high activity as an initiator in δ‐valerolactone polymerizations, although it was less efficient when used in the β‐butyrolactone and the β‐propiolactone polymerizations. Activity in the polymerization of β‐lactones was increased by adding small amounts of butanone or water. It was also observed that the diphenylzinc–butanone combination was more effective than the diphenylzinc–water mixture in the polymerizations of β‐butyrolactone and β‐propiolactone. Copyright © 2003 Society of Chemical Industry     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

Hull-less Barley Varieties: Storage Proteins and Amino Acid Distribution in Relation to Nutritional Quality

Barley (Hordeum vulgare L.) has had an important impact on human nutrition. Hull-less barley is a genetically improved type that has been widely used in recent years. Six Brazilian hull-less barley varieties (IAC-IBON 214-82; IAC 8612-421; IAC 8501-31; IAC 8501-12; IAPAR 39-ACUMAI; IAC 8501-22) were analyzed for storage protein constituents, amino acid contents, and similarity among the hull-less barley varieties. Albumins, globulins, prolamins I and II, and glutelins were extracted and separated by SDS-PAGE. The total protein amino acid contents of the flour were also determined for each variety by TLC and HPLC. Variations in intensity and appearance and disappearance of protein bands were observed among the varieties suggesting genetic variability. However, the amino acid profile did not indicate any major variations in the amino acid concentrations. The high lysine and threonine total concentrations detected in the seeds of the hull-less barley varieties encouraged an investigation into the regulation of amino acid metabolism and storage protein synthesis.     

Photo-reversible Reaction in Polymer Langmuir-Blodgett Films

Preparation of photoreactive Langmuir-Blodgett (LB) films was carried out using polymers/oligomers prepared from long-chain dialkyl esters of di-and tetra-olefins and having cyclobutane rings in the main chain. These polymers/oligomers formed stable monolayers on a water surface when mixed with arachidic acid. These monolayers could be deposited onto a substrate successfully forming Y-type films. The oligomer LB films were polymerized on irradiation. The polymer LB films showed a photo-reversible process between polymers and oligomers, depending on wavelength of the irradiating light. On the basis of spectral data and molecular weight change, this behaviour was found to be caused by cleavage and formation of cyclobutane rings.     

A storage heat pump using an ‘ozone-friendly’ refrigerant

The paper describes the integration of a chemical and a vapour-compression heat pump for energy storage applications. The vapour-compression system is designed to operate using the UK cheap rate ‘Economy 7’ electricity tariff. The system is characterized thermodynamically using various refrigerant/absorbent pairs in the chemical storage circuit and an ozone-friendly refrigerant, R134a, in the vapour-compression circuit. Results indicate that the H₂O/Na₂S pair provides a high energy storage density and is the most suitable for use in this system. The paper also describes the design features of a domestic-sized version of this heat pump system. Air in the sunspace (conservatory) of a house was used as a heat source for the heat pump.     

Simulation of Temperature Distribution in Stored Wheat without Aeration

A neural-deterministic simulation model applied for calculating distributions of temperatures and moisture content in a bed of wheat stored in a steel silo without aeration is presented in the article. The model consists of differential equations of heat and moisture transfer, initial and boundary conditions, and three artificial neural networks used during simulated ambient air conditions. Experiments and computer simulations were carried out in order to determine temperature fields in wheat grain stored in a steel silo for two months. The computer simulations were carried using MATLAB and FEMLAB software. The difference between measured and simulated temperature in grain near the silo wall at a height of 2.5 m from the bottom was less than 3.0°C. On the basis of the analysis performed it was concluded that the temperature distributions obtained with the model were consistent with the measured results obtained for grain stored in a steel silo without aeration.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

一种可用于可调谐环行Ti：Al_2O_3激光器的宽带单向器

本文介绍一种宽带单向器的原理及设计。选用ＴＧＧ作磁旋光介质，旋光石英晶片作补偿片，所设计的色散补偿型宽带单向器预计可在７００～１０００ｎｍ波长范围内实现环行激光腔中的单向行波运行；将其应用在可调谐环行Ｔｉ：Ａｌ２Ｏ３激光器中，获得了良好的实验结果。     

Numerical Simulation of Deforming Manufacture Process for Automobile Bevel Gear Blank

1 Introduction Rear axle bevel gearis a vital kind of annular accessory with high precision and hugeload availablefeatures ,andit is widely used as the differential drive in automobiles and tractor .In China ,the traditional manufactureapproach of producing the rear axle bevel gear blankis die forging,which not only requires a highinvestment ofproduct equipments , but also involves a low material utilization and great noise .In order to overcome thesedrawbacks , manyresearchers have done a gre…