Diluent effects on carbonate mobility in bisphenol-A polycarbonate in the solid state

The effect of miscible low molecular weight additives on the mobility of the carbonate group in bisphenol-A polycarbonate (BPAPC) has been studied using n.m.r. and dielectric relaxation experiments in the solid state. Proton-enhanced dipolar-decoupled carbon-13 n.m.r. spectra of BPAPC, isotopically enriched at the carbonate position, are obtained without magic-angle sample spinning. The resolved chemical shift anisotropy allows study of nuclear spin relaxation for the carbonate groups in the polymer that have different orientations relative to the static magnetic field in the laboratory frame. The spin-lattice relaxation time in the rotating frame (m>Tm>_1m>?m>) is measured at a motional-probe frequency of 50 kHz for the undiluted polymer and for BPAPC-diluent blends containing either dibutylphthalate or dinitrobiphenyl. The m>Tm>_1m>?m> exhibits some dependence on orientation in all systems studied. In the blend containing dibutylphthalate (DBP), m>Tm>_1m>?m> is decreased by a factor of two for all orientations of the carbonate group. This implies that DBP substantially increases the spectral density of 50 kHz motions in the carbonate region of the polymer at ambient temperature. In contrast, dinitrobiphenyl does not significantly alter the Fourier component of thermal fluctuations at 50 kHz. Dielectric relaxation measurements at 10 kHz reveal that the primary (m>Tm>_g) and secondary (β) motional processes in BPAPC are affected by low molecular weight additives. An intermediate relaxation process appears in the temperature interval between the glass transition temperature (m>Tm>_g) and the sub-m>Tm>_g β-relaxation (m>Tm>_m>βm>) in the polymer-diluent blends. The n.m.r. spin-lattice relaxation rate in the rotating frame, m>Tm>^?1_1m>?m>, correlates well with the relative magnitude of the dielectric dissipation factor (tan m>δm>_m>εm>) between m>Tm>_g and m>Tm>_m>βm>.     

常压气固催化间甲苯胺N-乙基化研究

合成了复合金属氧化物催化剂 ,进行了以乙醇和间甲苯胺为原料 ,常压固定床反应工艺研究。考察了反应温度、进料空速、原料配比对反应结果的影响。优化条件下 ,间甲苯胺的转化率为 96 %以上 ,N 乙基间甲苯胺的选择性为 93%以上     

Multidimensional ARKN methods for general oscillatory second-order initial value problems

Based on B-series theory, the order conditions of the multidimensional ARKN methods are presented for the general multi-frequency and multidimensional oscillatory second-order initial value problems by Wu et&amp;nbsp;al. (2009). These multidimensional ARKN methods exactly integrate the multi-frequency and multidimensional unperturbed oscillators. In this paper, we pay attention to the analysis of the concrete multidimensional ARKN methods for the general multi-frequency oscillatory second-order initial value problems whose right-hand side functions m>depend on both &amp;#xA0;m>y<math altimg="si3.gif" overflow="scroll"><mi>ymi>math>m>and &amp;#xA0;m>y^&amp;prime;<math altimg="si4.gif" overflow="scroll"><msup><mrow><mi>ymi>mrow><mrow><mo>&amp;prime;mo>mrow>msup>math> (the class of physical problems which fall within its scope is broader). Numerical experiments are carried out to show that the new multidimensional ARKN methods are more efficient compared with some well-known methods for dealing with the oscillatory problems in the scientific literature.     

High resolution solid state 13C n.m.r. of butadiene grafted polypropylene

¹H dipolar decoupled ¹³C n.m.r. experiments with the aid of the magic angle spinning technique have been used to determine the graft content and the isomer content of the polybutadiene grafts in a graft copolymer with isotactic polypropylene.     

用岩石导电效率理论来说明低孔渗储层孔隙结构对m指数的影响

通过对库车地区储层孔隙结构的研究,发现在低孔渗储层条件下,储层孔隙结构比中高孔渗储层复杂很多,阿尔奇公式中的m指数不能简单的当作常数,随着孔隙结构的变化反应十分灵敏。本文从岩石导电效率理论来分析了m指数随孔隙结构的变化特征。     

108m3PVC聚合釜的研制

介绍了新开发的大型聚氯乙烯生产设备——108m3PVC聚合釜,通过对其技术特性、结构特点及生产能力等的介绍,阐明了该釜又是一个适应我国PVC行业发展需求的新釜型。     

Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/mg src="/content/m51x787331t24l32/xxlarge947.gif" alt="gamma" align="MIDDLE" BORDER="0">-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.     

锂离子电池炭负极材料研究现状与发展

综述了近年来各种炭材料作为锂离子电池负极材料的新进展，着重分析了石墨、焦炭和难石墨化炭在放电容量、不可逆容量损失、充放电电位和充放电速率等主要性能上的差异以及与其结构之间的联系；指出以PAS为代表的热解炭(低于800℃)和纳米炭材料将是锂离子电池负极材料的发展方向。     

硝化法制备对氨基间硝基苯磺酸的研究

以对氨基苯磺酸为起始原料 ,经过乙酰化、硝化、水解三步来制备标题物。通过正交试验找出了酰化的最佳反应条件为 :对氨基苯磺酸与乙酐的摩尔比为 1∶1.0 5 ,反应总时间为 1.5h ,反应温度为 2 5℃ ,酰化介质为酰化反应前用碳酸钠及水将对氨基苯磺酸完全溶解 ,使混合液 pH值为 5～ 6 ,反应过程中不再补加碳酸钠 ,其酰化转化率可达 99.6 % ,酰化产物的固体收率可达 96 .0 % ;硝化反应的最佳条件为 :硝化剂用 90 .2 %的硝酸 ,对乙酰氨基苯磺酸与硝化剂的摩尔比为 1∶1.0 5 ,反应温度为 10℃ ,浓硫酸与对乙酰氨基苯磺酸的摩尔比为 8.3∶1,其硝化转化率可达 96 .0 % ,硝化反应的选择性好 ,对氨基邻硝基苯磺酸的量不到 1.0 %。     

Structure–Function Relations in Supported Ni–W Sulfide Hydrogenation Catalysts

Ni&amp;#x2013;W catalysts were prepared by impregnation of commercial mg src="/content/g0805166532221m8/xxlarge947.gif" alt="gamma" align="MIDDLE" BORDER="0">-alumina and silica supports. The sulfidation, performed directly after drying at 100&amp;deg;C, yielded fully sulfided Ni&amp;#x2013;W species on both supports (SEM-EDAX, XPS, XRD). At optimal metals loading (mg src="/content/g0805166532221m8/xxlarge8764.gif" alt="sim" align="MIDDLE" BORDER="0">50 wt% NiO + WO₃, Ni/W = 2), the sulfided catalysts had similar texture (N₂ adsorption) and displayed similar activity in dibenzothiophene hydrodesulfurization (DBT HDS), while the activity of the Ni&amp;#x2013;W/SiO₂ catalyst in toluene hydrogenation (HYD) was six times higher than that of Ni&amp;#x2013;W/Al₂O₃. This is due to the more than two times higher WS₂ slabs stacking number in Ni&amp;#x2013;W/SiO₂ compared with Ni&amp;#x2013;W/Al₂O₃ (XRD, HR-TEM), yielding stronger adsorption of toluene (TPD).