Cationic copolymerization behavior of a bicyclic orthoester having hydroxy group with glycidyl phenyl ether and volume change on their copolymerization

This article describes cationic ring‐opening copolymerization of a bicyclic orthoester having hydroxy group (BOE‐OH) and glycidyl phenyl ether (GPE), and the volume shrinkage behavior during the copolymerization. THF soluble polyethers [poly(BOE‐OH‐co‐GPE)] were obtained by the copolymerizations at 80–180°C, while crosslinked poly(BOE‐OH‐co‐GPE) was obtained by the copolymerizations at 220–250°C. This crosslinking reaction may originate from the dehydration of methylol groups in the side chain of poly(BOE‐OH‐co‐GPE). The volume shrinkage during the cationic copolymerization reduced as the increase of the BOE‐OH feed ratio. By contrast, the volume shrinkage on the crosslinking polymerization was almost independent on the BOE‐OH feed ratio. Poly(BOE‐OH‐co‐GPE)s with higher BOE‐OH composition showed lower thermal weight loss temperature owing to the release of H₂O by dehydration of methylol groups. The BOE‐OH component in the THF soluble poly(BOE‐OH‐co‐GPE)s lowered the glass transition temperature (T_g), while that in the crosslinked poly(BOE‐OH‐co‐GPE) increased the T_g probably because of the higher crosslinking density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1356–1361, 2006     

Effects of the o‐aromatic ring in the molecular chain on the properties of polyester polyols

A series of liquid polyester polyols from adipic acid (AA), phthalic anhydride (PA), ethylene glycol, propanediol‐1,2, and trihydroxymethylpropane, varying in the molar ratio of PA to AA, were prepared. The effects of the o‐aromatic ring in the molecular chain, which came from PA, on the viscosity, glass‐transition temperature, and thermal degradation temperature of the polyester polyols were studied with viscometry, differential scanning calorimetry, and thermogravimetry. The intrinsic viscosity and glass‐transition temperature increased with the concentration of the o‐aromatic ring increasing. The temperature of the maximum thermal degradation rate for aliphatic polyester polyols was 434.20°C. Two steps of thermal degradation were found when there were o‐aromatic rings in the molecular chain. One thermal degradation temperature was 358.36–360.48°C, and the other was 412.85–427.18°C. Polyester polyols with o‐aromatic rings had higher stability at lower temperatures (<240.00°C). However, aliphatic polyester polyols had higher stability at higher temperatures (300.00–480.00°C). The activation energy and order of degradation were calculated from thermogravimetric curves. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1617–1624, 2002     

The ring transformations of 1,2,3,4-diepoxybutane (2,2′-bioxirane) catalysed by various aluminosilicates

The transformations of a molecule containing two adjacent epoxide rings, 2,2-bioxirane that is, were studied over various acidic aluminosilicates (HZSM-5, HY-FAU, AlMCM-41), for the first time, In the 373–473 K temperature range, in a pulse reactor, a ring-opening–ring-enlargment reaction producing furan only occured over the zeolites and it was the predominant reaction on AlMCM-41 as well. The driving force of this transformation route is water formation via elimination from 2,2-bioxirane. Suprising is the lack of the mono- or dialdehyde, the would-be products of the cleavage of the sterically more hindered C–O bonds – an acid-catalysed reaction typical for alkyl-substituted oxiranes.     

Degradation of the oxirane ring of epoxidized vegetable oils with solvated acetic acid using cation‐exchange resins

Vegetable oil epoxides (oxiranes) are customarily manufactured using acetic acid (AA) as oxygen carrier and reactant source, in aqueous/organic media. Further attack of the oxirane ring by AA proceeds in this acid‐catalyzed process, lowering yield. We report a study of the degradation of the ring by water‐solvated AA, using Amberlite IR‐120 as heterogeneous catalyst. The ring opening with solvated AA was found to be first order with respect to the concentration of epoxide groups and second order with respect to the carboxylic acid, with an activation energy of 58.7 ± 0.42 kJ mol^?1. This value is within the range found in liquid‐liquid systems (51.3–66.3 kJ mol^?1). Yet, using IR‐120, the degradation increases identically either by adding more mass of catalyst or by reducing its particle diameter while keeping the total mass constant, as both situations lead to higher external (exposed) area of the acidic catalyst (i.e., free protons associated to the sulfonic group) on the outer surface of the ion exchange resin beads. These free protons, in turn, become available to catalyze the attack on the oxirane groups of the long‐chain fatty acids, which cannot enter (diffuse) into the gel phase of the resin. Despite the unavoidable presence of surface‐exposed protons, the degradation can be reduced by several orders of magnitude – for similar process conditions – by using this type of heterogeneous catalysts instead of mineral acids.     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

精密钢球环槽等速传动机构运动精度及可靠性分析

在分析精密钢球环槽等速传动机构结构基础上,利用其等效机构和误差分析理论,研究了钢球环槽等速传动机构结构参数对其机构传动精度的影响规律,应用机构可靠性理论,建立了钢球环槽等速传动机构的运动精度可靠性模型,并研究分析了机构的运动精度可靠性,研究结果为精密钢球行星传动的设计和应用提供了理论依据。     

撞击构造的特征及对贵州息烽县环形构造的成因解释

对行星的撞击构造特征进行了总结。地球上的撞击构造,一般通过地貌以及冲击变质产生的岩石和矿物来确认。对贵州省息烽县境内的疑似撞击构造的环形构造进行了比较研究,通过对已有地质资料的详细调研、实地仔细的勘测和采样以及对样品的岩相学分析,并未观察到冲击变质特征,因此认为此处环形构造并非撞击成因,而是古老的盆状向斜经历了多期的构造作用形成的涡旋构造。     

基于多项式拟合的CT图像环状伪影校正

探测器探元的响应不一致性会使CT图像中出现环状伪影,环状伪影是影响CT图像像质的重要因素,影响图像的分析及后续处理。为此提出一种基于分段多项式拟合的环状伪影校正方法,该方法适用于单材质或图像中的材质衰减系数相差不大的情况。采用分段多项式拟合正弦图累加曲线得到修正因子,用修正因子修正不一致的探元,最后重建图像。实验结果证明此方法能有效抑制图像正中间部分环状伪影。     

钢管混凝土梁柱节点受力性能有限元分析

采用大型有限元分析软件ANSYS,对深圳福田大型地下车站主体结构标准段的钢管混凝土柱顶-横纵梁、柱脚-底纵梁以及柱-地下1层梁等节点在梁端及柱端的弯矩、剪力和轴力等荷载作用下的力学性能进行模拟和分析.从钢管混凝土梁柱节点的受力状态出发,分析在梁端及柱端的弯矩、轴力和剪力等荷载作用下节点模型各组成构件(包括柱钢管、梁、加强环梁、承台、抗拔桩等部位)的主应力及切应力分布情况、变形情况和各个截面的内力分布情况等,与各个构件所对应的设计强度值进行对比分析,根据分析结果建议了更合理的节点结构设计与加固方案.     

Study on the characteristics of erbium-doped waveguide ring laser

A theoretical model of the erbium-doped waveguide ring laser is established according to the theory of erbium-doped waveguide amplifier and the transmission matrix of waveguide directional coupler. The influence of bend radius, coupling coefficient and doped erbium ion concentration on the characteristics of waveguide ring laser is investigated. It is shown that due to the co-action of waveguide bend loss and other relevant loss there is an optimal bend radius which can provide simultaneously low threshold pumping power and high laser light output power. As one part of the resonator’s loss, the laser light coupling coefficient of directional coupler has an impact on the laser property. The analysis indicates that the laser achieves the high output power when the coupling coefficient is about 0.2. The threshold pumping power is the minimum when the doped erbium ion concentration is 0.85×10²⁶ m⁻³. Increasing the concentration of doped erbium ions will enhance the output power of laser light as long as the concentration doesn’t introduce remarkable up-conversion effect. The results give a good theoretical basis for the design and fabrication of erbium-doped waveguide ring laser devices. Supported by the National Natural Science Foundation of China (Grant No. 60807015), the Specialized Research Fund for the Doctoral Program of Higher Education (Grant No. 200801411037), the Young Teacher Cultivation Foundation of Dalian University of Technology (Grant No. 893210) and Doctor Start-up Foundation of Dalian University of Technology (Grant No. 893322)