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Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
3.
Andrey V. Lunchev Dr. Samuel A. Morris Dr. Rakesh Ganguly Prof. Andrew C. Grimsdale 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1819-1823
A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes. 相似文献
4.
Erqiang Liu Jianguo Wu Huaying Li Haitao Liu Guanghui Zhao Lingyu Kong Jinbao Lin Gesheng Xiao You Jia 《Journal of polymer science. Part A, Polymer chemistry》2021,59(5):451-461
Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness. 相似文献
5.
Let be an abelian group. A finite multiset A over G is said to give a λ-fold factorization of G if there exists a multiset B over G such that each element of G occurs λ times in the multiset . In this article, restricting G to a cyclic group, we will provide sufficient conditions on a given multiset A under which the exact value or an upper bound of the minimum multiplicity λ of a factorization of G can be given by introducing a concept of ‘lcm-closure’. Furthermore, a couple of properties on a given factor A will be shown when A has a prime or prime power order (cardinality). A relation to multifold factorizations of the set of integers will be also glanced at a general perspective. 相似文献
6.
《大分子反应工程》2018,12(1)
A model is used to simulate batch copolymerization of caprolactam with hexamethylene diamine (HMD) and adipic acid (ADA) to produce nylon 6/6,6. Four different recipes are considered: a recipe containing caprolactam and an aqueous solution of HMD and ADA, a recipe containing caprolactam and dry HMD/ADA salt, and two recipes with a portion of the caprolactam replaced by nylon 6 cyclic dimer (CD). Consuming CD would be advantageous because CD is an undesirable side product from nylon 6 production. Simulation results lead to three important findings: (i) operation using dry salt rather than aqueous salt solution leads to higher degree of polymerization, (ii) substantial quantities of CD can be consumed to produce nylon 6/6,6 copolymer, and (iii) including water in the recipe is beneficial for achieving improved consumption of CD. The results of this study will be helpful in designing experiments aimed at improving industrial nylon 6/6,6 copolymerization processes. 相似文献
7.
The tidal energy industry is progressing rapidly, but there are still barriers to overcome to realise the commercial potential of this sector. Large magnitude and highly variable loads caused by waves acting on the turbine are of particular concern. Composite blades with in-built bend-twist elastic response may reduce these peak loads, by passively feathering with increasing thrust. This could decrease capital costs by lowering the design loads, and improve robustness through the mitigation of pitch mechanisms. In this study, the previous research is extended to examine the performance of bend-twist blades in combined wave–current flow, which will frequently be encountered in the field. A scaled 3 bladed turbine was tested in the flume at IFREMER with bend-twist composite blades and equivalent rigid blades, sequentially under current and co-directional wave–current cases. In agreement with previous research, when the turbine was operating in current alone at higher tip speed ratios the bend-twist blades reduced the mean thrust and power compared to the rigid blades. Under the specific wave–current condition tested the average loads were similar on both blade sets. Nevertheless, the bend-twist blades substantially reduced the magnitudes of the average thrust and torque fluctuations per wave cycle, by up to 10% and 14% respectively. 相似文献
8.
鉴于纤维增强复合材料(Fiber Reinforced Polymer, FRP)已在混凝土结构加固中普遍应用, 能有效提高结构的承载和变形能力. 为揭示动载作用下FRP-混凝土界面的剥离机理, 本文基于ABAQUS平台, 采用内聚力模型模拟CFRP-混凝土界面层, 实现了快速荷载下CFRP-混凝土界面剥离的高效模拟. 结果表明: CFRP表面应变在加载过程中由加载端向自由端方向传递, 随着加载速率的提高, 界面承载能力也随之提高; 界面峰值剪应力也存在显著的应变率效应; 模拟结果与试验结果基本吻合, 说明了新方法的有效性. 相似文献
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10.
Synthesis of poly(isopropenylphenoxy propylene carbonate) and its facile side‐chain functionalization into hydroxy‐polyurethanes 下载免费PDF全文
Chun Chieh Huang Ching Hsuan Lin Shenghong A. Dai 《Journal of polymer science. Part A, Polymer chemistry》2016,54(6):802-808
4‐Isopropenyl phenol ( 4‐IPP ) is a versatile dual functional intermediate that can be prepared readily from bisphenol‐A ( BPA ). Through etherification with epichlorohydrin to the phenolic group of 4‐IPP , it can be converted into 4‐isopropenyl phenyl glycidyl ether ( IPGE ). On further reaction with carbon dioxide in the presence of tetra‐n‐butyl ammonium bromide ( TBAB ) as the catalyst, IPGE was transformed into 4‐isopropenylphenoxy propylene carbonate ( IPPC ) in 90% yield. Cationic polymerization of IPPC with strong acid such as trifluoromethanesulfonic acid or boron trifluoride diethyl etherate as the catalyst at ?40 °C gave a linear poly(isopropenylphenoxy propylene carbonate), poly( IPPC ), with multicyclic carbonate groups substituted uniformly at the side‐chains of the polymer. The cyclic carbonate groups of poly( IPPC ) were further reacted with different aliphatic amines and diamines resulting in formation of polymers with hydroxy‐polyurethane on side‐chains. Syntheses, characterizations of poly( IPPC ) and its conversion into hydroxy‐polyurethane crosslinked polymers were presented. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 802–808 相似文献