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1.
甲醇两步制芳烃反应中低碳烯烃芳构化反应稳定性优异,为分析其内在机制,制备了不同硅铝比(nSiO2/nAl2O3)及Zn负载量的ZSM-5催化剂,以丙烯芳构化为模型反应,分析ZSM-5表面酸性对低碳烯烃芳构化反应性能的影响规律,并探究反应微观特性。发现当硅铝比由150降至75时,增加的酸密度促进了烯烃氢转移芳构化过程,使芳烃选择性由31.0%增至34.4%,但丙烯直接参与的氢转移过程也被强化,使丙烷产物选择性由28.2%增至36.0%。引入Zn助剂可将部分Brønsted酸转变为Zn-Lewis酸,强化烯烃脱氢芳构化过程,使芳烃选择性进一步显著增加到62.4%。丙烯芳构化过程中芳烃烷基化深度比甲醇芳构化过程低,提升总芳烃选择性的同时,也明显抑制了难溶性积碳的形成,使反应稳定性明显提升。由此得出,甲醇两步制芳烃过程中甲醇制低碳烯烃过程对甲醇的预先消耗,抑制了低碳烯烃芳构化反应芳烃产物的深度烷基化,是该反应表现出优异稳定性的重要原因。 相似文献
2.
Jorge Ferreira Raquel Zilz Igor S. Boeira Sabrina M. da Silva Adriana C.A. Casagrande Osvaldo L. Casagrande 《应用有机金属化学》2019,33(3)
A new set of Cr(III) complexes, {L}CrCl3(THF), based on thiophene–imine ( 2a , L = PhOC6H4(N═CH)‐2‐SC4H3; 2b , L = PhOC2H4(N═CH)‐2‐SC4H3; 2c , L = Ph(NH)C2H4(N═CH)‐2‐SC4H3; 2d , L = PhOC6H4(N═CH)‐2‐SC4H2‐5‐Ph; 2e , L = Ph(NH)C2H4(N═CH)‐2‐SC4H2‐5‐Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α‐olefins with turnover frequencies in the range 9500–93 500 (mol ethylene) (mol Cr)?1 h?1, and producing mostly oligomers (95.0–99.3 wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2 wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined. 相似文献
3.
The incorporation of comonomers during ethylene polymerization can efficiently modulate important material properties of the polyolefins. Utilizing bioresourced comonomers for the generation of high‐performance polyolefin materials is attractive from a sustainability point of view. In this contribution, bioresourced eugenol and related comonomers were incorporated into polyolefins through palladium‐catalyzed copolymerization and terpolymerization reactions. Importantly, high‐molecular‐weight catechol‐functionalized polyolefins can be generated. The introduction of different metal ions induces efficient interactions with the incorporated catechol groups, leading to enhanced mechanical properties and self‐healing properties. Moreover, the catechol functionality can greatly improve other properties such as surface properties, adhesion properties, and compatibilizing properties. The catechol‐functionalized polyolefin was demonstrated as a versatile platform polymer for accessing various materials with dramatically different properties. 相似文献
4.
碱金属/液氨溶液具有很强还原性,在有机合成中有着广泛的运用。在高等教育出版社出版的由邢其毅、裴伟伟、徐瑞秋以及裴坚等人编著的《基础有机化学》(第3版)中描述了在碱金属/液氨作用条件下的两类还原反应:炔烃被还原为烯烃的反应和Birch还原反应。一般认为这两种反应均生成了自由基负离子中间体。本文结合近几年的文献报道,对它们的机理进行进一步的探讨。 相似文献
5.
Guizhou Yue Kaining Lei Hajime Hirao Jianrong Zhou 《Angewandte Chemie (International ed. in English)》2015,54(22):6531-6535
Asymmetric reductive Heck reaction of aryl halides is realized in high stereoselectivity. Hydrogen‐bond donors, trialkylammonium salts in a glycol solvent, were used to promote halide dissociation from neutral arylpalladium complexes to access cationic, stereoselective pathways. 相似文献
6.
采用共沉淀法分别制备了Y_2O_3,La_2O_3和Ce O_2改性的Cu O-Zn O-Zr O_2,表征结果表明,稀土改性的Cu O-Zn O-Zr O_2分散性良好,比表面积增大.将稀土改性的Cu O-Zn O-Zr O_2与SAPO-34分子筛机械混合用于催化CO_2加氢一步法合成了低碳烯烃,在反应温度400℃,压力3 MPa,空速为1800 m L·g~(-1)_(cat)·h~(-1),氢碳体积比为3∶1,Ce O_2改性Cu O-Zn O-Zr O_2与SAPO-34质量比为1∶1,催化剂用量为1.0 g时,CO_2的单程转化率为54.6%,低碳烯烃的选择性和产率分别为51.1%和27.9%. 相似文献
7.
Dr. Xun Zhang Dr. Jing Li Hua Tian Prof. Dr. Yian Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11658-11663
The dimeric cinchona alkaloid (DHQD)2PHAL is used to catalyze an effective asymmetric bromohydroxylation of unfunctionalized olefins with H2O as nucleophile an N‐bromobenzamide as a bromine source. A variety of optically active bromohydrins are formed with up to 88 % ee. 相似文献
8.
Haobing Wang Xia Wu Yang Yang Masayoshi Nishiura Zhaomin Hou 《Angewandte Chemie (International ed. in English)》2020,59(18):7173-7177
The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of functional polymers, but studies toward this goal have met with only limited success to date. Now, the co‐syndiospecific alternating copolymerization of methoxyphenyl‐ and N,N‐dimethylaminophenyl‐functionalized propylenes with styrene by half‐sandwich rare‐earth catalysts is reported. This reaction efficiently afforded the corresponding functionalized propylene‐alt‐styrene copolymers with a perfect alternating sequence and excellent co‐syndiotacticity (rrrr >99 %), thus constituting the first example of co‐stereospecific alternating copolymerization of polar and non‐polar olefins. 相似文献
9.
Raphael Bigler Kyle A. Mack Jeff Shen Paolo Tosatti Chong Han Stephan Bachmann Haiming Zhang Michelangelo Scalone Andreas Pfaltz Scott E. Denmark Stefan Hildbrand Francis Gosselin 《Angewandte Chemie (International ed. in English)》2020,59(7):2844-2849
Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio‐ and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio‐ and diastereoselectivity. 相似文献
10.