OH‐Initiated Photooxidations of 1‐Pentene and 2‐Methyl‐2‐propen‐1‐ol: Mechanism and Yields of the Primary Carbonyl Products

The products of the gas‐phase reactions of OH radicals with 1‐pentene and 2‐methyl‐2‐propen‐1‐ol (221MPO) at T=298±2 K and atmospheric pressure were investigated by using a 4500 L atmospheric simulation chamber that was built especially for this work. The molar yield of butyraldehyde was 0.74±0.12 mol for the reaction of 1‐pentene. This work provides the first product molar yield determination of formaldehyde (0.82±0.12 mol), 1‐hydroxypropan‐2‐one (0.84±0.13 mol), and methacrolein (0.078±0.012 mol) from the reaction of 221MPO with OH radicals. The mechanism of this reaction is discussed in relation to the experimental results. Additionally, taking into consideration the complex mechanism, the rate coefficients of the reactions of OH with formaldehyde, 1‐hydroxypropan‐2‐one, and methacrolein were derived at atmospheric pressure and T=298±2 K.; the obtained values were (8.9±1.6)×10^?12, (2.4±1.4)×10^?12, and (22.9±2.3)×10^?12 cm³ molecule^?1 s^?1, respectively.     

Solution properties of polymethyl acrylate I. Properties of PMA chain by viscometric method

Fundamental properties of polymethyl acrylate solutions were examined: the reasonable Houwink-Mark-Sakurada relations and the theta temperature (θ) were determined to be 5 °C in toluene. Further, the measurements of intrinsic viscosity for polymethyl acrylate solutions as a function of temperature yielded a thermal transition due to a conformation change at 56 ± 1 °C, irrespective of molecular weight and solvent. An application of the two-parameter theory to such a transition gave a stepwise change of the short-range interaction: K×10²=9.5 below 50 °C and 10.3 above 60 °C. This conformation transition is explained on the basis of the steric hindrance of the planar substituent to the main chain above 60 °C.     

Analyzing physical characteristics and shielding efficiency for non-lead medical radiation shielding sheets improved using PMMA

ABSTRACT

Recently, the research for replacing heavy lead goods, such as medical radiation shielding sheets with environmentally friendly shielding materials has been widely carried out. The use of tungsten injected into the base material of polyethylene resin may be a good alternative for manufacturing lightweight shielding sheets. However, the increase of the mass ratio of tungsten in the shielding sheets is accompanied by the degradation of their physical properties such as tensile strength and flexibility. In this report, we have tried to fix this problem by adding Polymethyl Methacrylate (PMMA) to the mixing process of materials. If the portion of the added PMMA is 20%, it leads to a 25% increase of the particle packing ratio while there is a simultaneous 28% enhancement of tensile strength compared to before adding it. In the final test for shielding efficiency, it also turned out that the increase of the particle packing ratio for tungsten exhibits the same shielding efficiency as that of 0.2?mmPb. This consequence may imply that mass production of sheets that can prevent scattering rays in the medical radiation frequency range is possible through the calender process using a 0.3?mm tungsten sheet.     

微模塑法制备PMMA球面微透镜阵列

借助微透镜及其阵列的光学器件,采用软刻蚀技术中的微模型方法成功制备了聚甲基丙烯酸甲酯(PMMA)的柱体及球面微透镜阵列,并对该微透镜阵列进行了光学显微和SEM分析．通过考察制备过程中的影响因素,探讨了减少阵列缺陷和提高光学性能的适宜参数．并对该透镜阵列的光学成像性能进行了初步研究．     

Comparison of caustics and the strain gage method for measuring mode I stress intensity factor of PMMA material

Both caustics and strain gage methods are shown to be effective in the determination of mode I stress intensity factor (SIF) at the crack tip. However, there is a lack of investigation with regard to the quantitative comparison of the two methods. In this paper, dynamic three-point bending tests were performed on polymethyl methacrylate (PMMA) specimens using the caustic and the strain gage methods simultaneously. The SIFs calculated by these two methods were analyzed and compared. The results show that the deviations of the SIF values between caustics and the strain gage method are slightly more significant when the orientation of the gage is obtuse rather than acute. Furthermore, this deviation increases with the gage mounted closer to the edge of the specimen when the orientation is acute. In addition, the whole cracking process could be clearly recorded by the caustic method, while the time-evolution of SIF can be roughly obtained with a limited number of strain gages during the crack propagation.     

Higher α‐olefin polymerizations catalyzed by rac‐Me2Si(1‐C5H2‐2‐CH3‐4‐tBu)2Zr(NMe2)2/Al(iBu)3/[Ph3C][B(C6F5)4]

Polymerizations of higher α‐olefins, 1‐pentene, 1‐hexene, 1‐octene, and 1‐decene were carried out at 30 °C in toluene by using highly isospecific rac‐Me₂Si(1‐C₅H₂‐2‐CH₃‐4‐^t Bu)₂Zr(NMe₂)₂ (rac‐1) compound in the presence of Al(iBu)₃/[CPh₃][B(C₆F₅)₄] as a cocatalyst formulation. Both the bulkiness of monomer and the lateral size of polymer influenced the activity of polymerization. The larger lateral of polymer chain opens the π‐ligand of active site wide and favors the insertion of monomer, while the large size of monomer inserts itself into polymer chain more difficultly due to the steric hindrance. Highly isotactic poly(α‐olefin)s of high molecular weight (MW) were produced. The MW decreased from polypropylene to poly(1‐hexene), and then increased from poly(1‐hexene) to poly(1‐decene). The isotacticity (as [mm] triad) of the polymer decreased with the increased lateral size in the order: poly(1‐pentene) > poly(1‐hexene) > poly(1‐octene) > poly(1‐decene). The similar dependence of the lateral size on the melting point of polymer was recorded by differential scanning calorimetry (DSC). ¹H NMR analysis showed that vinylidene group resulting from β‐H elimination and saturated methyl groups resulting from chain transfer to cocatalyst are the main end groups of polymer chain. The vinylidene and internal double bonds are also identified by Raman spectroscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1687–1697, 2000     

Facile Route Using Highly Arrayed PMMA Spheres as Hard Template for the Fabrication of 3D Ordered Nanoporous MgO

"Using magnesium nitrate as Mg source and regularly packed polymethyl methacrylate (PMMA) spheres were synthesized via a combined strategy of emulsifier-free emulsion polymerization and water floating technique as hard template, we fabricated ordered nanoporous magnesium oxide. The synthesized PMMA and MgO samples were characterized by N2 adsorption-desorption, X-ray diffraction, high-resolution scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction. It was observed that the synthesized PMMA spheres possessed a uniform diameter of approximately 284 nm and were in a highly ordered array, and the MgO generated by using the PMMA-templating method exhibited polycrystallinity with three-dimensionally ordered pores. BET surface area of the synthesized MgO sample is 100.7 m2/g, pore volume is 0.46 cm3/g, wall thickness is 4-24 nm, and pore sizes are in the range of 10-120 nm. Such a 3D high-surface-area nanoporous strongly basic MgO is useful in the applications of catalyst supports and acidic gas adsorbents."     

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS*

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and apolymethyl methacrylate network were synthesized and characterized. The IPN showed only one T_g, andhence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d_(33))of the IPN was measured to be 1.72×10~(-7) esu. The study of NLO temporal stability at room temperature andelevated temperature (100℃) indicated that the IPN exhibits a high stability in the dipole orientation due tothe permanent entanglements of two component networks in the IPN system. Long-term stability of secondharmonic coefficients was observed at room temperature for more than 1000 h.     

基于高斯核主成分分析的多通道拉曼光谱重建

针对多通道拉曼成像系统常会受荧光背景、噪声等非线性因素的影响而导致拉曼光谱重建结果一般的问题,提出了一种基于高斯核主成分分析的拉曼光谱重建算法.首先利用相似度因子对标定样本数据集进行预处理,其次通过高斯核函数将标定样本以非线性形式映射至高维特征空间,接着在特征空间中对映射后的数据集提取基函数并通过伪逆法求得与之对应的基函数系数.使用聚甲基丙烯酸甲酯作为测试样本,并引入均方根误差来评估拉曼光谱重建结果的准确性.实验结果表明,相比传统的伪逆法与维纳估计法,该算法具有更高的重建精度及抗噪能力,且能有效降低标定样本中不良数据和成像系统中非线性因素对拉曼光谱重建的影响.因此,该算法可以为多通道拉曼快速成像提供一种有效的拉曼光谱重建算法.     

分子筛催化的戊烯骨架异构反应机理

在密度泛函理论中的B3LYP/6-31G(d,p)水平上研究了分子筛催化戊烯骨架异构的微观作用机制,分别对各个基元反应进行了内禀反应坐标(IRC)解析。结果表明:戊烯的骨架异构存在2种反应机理:烷氧基中间体机理和类甲基环丙烷中间体机理。而烷氧基中间体机理又包括2个反应途径,1个是甲基迁移,另1个是乙基迁移。因此,整个异构反应存在3个反应途径。甲基迁移机理和乙基迁移机理都含有3个基元步骤,其中速控步骤分别是甲基迁移和乙基迁移,对应的活化能分别为206.17和207.31 kJ·mol-1,二者几乎相等,表明2个反应途径从能量的角度来说是互相竞争的。类甲基环丙烷中间体机理分2步,碳链扭转和甲基的迁移,反应中间体具有高离子性和高能量的物种。反应速控步骤是碳链扭转反应,其活化能是147.93 kJ·mol-1,明显低于甲基迁移和乙基迁移2个反应途径的能垒,意味着类甲基环丙烷中间体的反应途径更容易发生。