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81.
Kinetics and mechanism of metallocene‐catalyzed olefin polymerization: Comparison of ethylene,propylene homopolymerizations,and their copolymerization
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Yintian Guo Zhen Zhang Wenqi Guo Akbar Khan Zhisheng Fu Junting Xu Zhiqiang Fan 《Journal of polymer science. Part A, Polymer chemistry》2017,55(5):867-875
A series of ethylene, propylene homopolymerizations, and ethylene/propylene copolymerization catalyzed with rac‐Et(Ind)2ZrCl2/modified methylaluminoxane (MMAO) were conducted under the same conditions for different duration ranging from 2.5 to 30 min, and quenched with 2‐thiophenecarbonyl chloride to label a 2‐thiophenecarbonyl on each propagation chain end. The change of active center ratio ([C*]/[Zr]) with polymerization time in each polymerization system was determined. Changes of polymerization rate, molecular weight, isotacticity (for propylene homopolymerization) and copolymer composition with time were also studied. [C*]/[Zr] strongly depended on type of monomer, with the propylene homopolymerization system presented much lower [C*]/[Zr] (ca. 25%) than the ethylene homopolymerization and ethylene–propylene copolymerization systems. In the copolymerization system, [C*]/[Zr] increased continuously in the reaction process until a maximum value of 98.7% was reached, which was much higher than the maximum [C*]/[Zr] of ethylene homopolymerization (ca. 70%). The chain propagation rate constant (kp) of propylene polymerization is very close to that of ethylene polymerization, but the propylene insertion rate constant is much smaller than the ethylene insertion rate constant in the copolymerization system, meaning that the active centers in the homopolymerization system are different from those in the copolymerization system. Ethylene insertion rate constant in the copolymerization system was much higher than that in the ethylene homopolymerization in the first 10 min of reaction. A mechanistic model was proposed to explain the observed activation of ethylene polymerization by propylene addition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 867–875 相似文献
82.
A subgroup H of a finite group G is called Hall normally embedded in G if H is a Hall subgroup of the normal closure H G . Groups which contain a Hall normally embedded subgroup of order d for every factor d of | G | are characterized. Such groups are supersolvable with a cyclic nilpotent residual of square-free order. 相似文献
83.
Bing Xu Zhisheng Wu Zhaozhou Lin Chenglin Sui Xinyuan Shi Yanjiang Qiao 《Analytica chimica acta》2012
Ethanol precipitation plays a major role in the pretreatment of Flos Lonicerae Japonicae of Qingkailing injection, and is also one of the most popular purification techniques in Chinese herbal medicines. In order to monitor and have a better understanding of the ethanol precipitation process, a PLS model was built based on NIR spectroscopy and HPLC analysis of chlorogenic acid content within the framework of FDA's PAT initiative. Nevertheless, due to the complex mechanism of and the raw materials’ natural variability introduced into the ethanol precipitation process, it was unable to foresee the variations in new batches which may jeopardize the robustness of the established model. Therefore, based on the simple interval calculation (SIC) theory, a new model expansion updating strategy which could continuously expand the variation coverage of the calibration model along with the batch proceeding of ethanol precipitation process was proposed. Effects of model updating were validated by an individual batch with 60 samples. After two times of updating, the root mean squared error of prediction (RMSEP) decreased from 0.268 mg mL−1 to 0.199 mg mL−1, while the insiders in the object status plot (OSP) increased from 44 to 58, demonstrating the good performance of the proposed approach. 相似文献
84.
85.
Hong Nhan Nong Hyung‐Suk Oh Tobias Reier Elena Willinger Marc‐Georg Willinger Valeri Petkov Detre Teschner Peter Strasser 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(10):3018-3022
Active and highly stable oxide‐supported IrNiOx core–shell catalysts for electrochemical water splitting are presented. IrNix@IrOx nanoparticles supported on high‐surface‐area mesoporous antimony‐doped tin oxide (IrNiOx /Meso‐ATO) were synthesized from bimetallic IrNix precursor alloys (PA‐IrNix /Meso‐ATO) using electrochemical Ni leaching and concomitant Ir oxidation. Special emphasis was placed on Ni/NiO surface segregation under thermal treatment of the PA‐IrNix /Meso‐ATO as well as on the surface chemical state of the particle/oxide support interface. Combining a wide array of characterization methods, we uncovered the detrimental effect of segregated NiO phases on the water splitting activity of core–shell particles. The core–shell IrNiOx /Meso‐ATO catalyst displayed high water‐splitting activity and unprecedented stability in acidic electrolyte providing substantial progress in the development of PEM electrolyzer anode catalysts with drastically reduced Ir loading and significantly enhanced durability. 相似文献
86.
87.
采用第一原理方法计算了O2分子在 Mo(001) 表面的吸附,得到了吸附构型的各种参数,并且计算了O2分子在 Mo(001) 表面4个位置(顶位,桥位,穴位垂直,穴位平行)吸附后的能量,结果表明在顶位吸附能最高。通过对O2分子在 Mo(001) 表面吸附的原子轨道电荷分布与态密度图的分析可以看出在吸附过程中主要是O原子的2p轨道电子与钼的4s和4d轨道电子的相互作用。 相似文献
88.
The influence of the negative substrate bias on the interfacial and microstructural characteristics of nanocrystalline silicon (nc-Si) thin films was deposited by hot wire chemical vapor deposition (HWCVD). Structural characterization of nc-Si films was performed by small angle X-ray diffraction (SAXRD), Raman spectroscopy, X-ray reflectivity (XRR) and field emission scanning electron microscopy (FESEM). Crystalline fraction and crystallite size increases from 61.31 to 74.13% and 13.3 to 21.6 nm, respectively, with an increasing negative bias from 0 to ?200 V. Furthermore, the deposition rate of nc-Si films increases from 25 to 68 nm/min by increase of negative substrate bias from 0 to ?200 V. 相似文献
89.
Cheng Hai Gao Xu Hua Nong Shu Hua Qi Xiong Ming Luo Si Zhang Hai Rong Xiong 《中国化学快报》2010,21(11):1355-1357
A new nine-membered lactone, cladospolide E (1), was isolated from a culture broth of a marine fungus Cladosporium sp. F14. The structure of compound 1 was determined on the basis of extensive spectroscopic analysis, including 1D and 2D NMR data. 相似文献
90.
电化学式生物传感器是生物传感器的很重要组成部分。新材料用于生物传感器是其新发展的重要研究方向,它包括PVC膜的替代材料,离子交换聚合物膜,有机导电聚合物和氧化还原聚合物等。各学科的相互渗透,使生物传感器出现新颖的设想和概念,包括氧化还原酶的电子导通,超薄组成膜和化学敏感微电化学装置及离子通道传感器与膦酯膜电极。电子鼻和组电极以及生物传感器的微型化都是生物传感器的新发展动向。 相似文献