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1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2kt) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers. 相似文献
3.
Grishin D. F. Semyonycheva L. L. Telegina E. V. Smirnov A. S. Nevodchikov V. I. 《Russian Chemical Bulletin》2003,52(2):505-507
Organometallic compounds Cp2TiCl2, (EtC5H4)2NbCl2, and (PriC5H4)2WCl2 were assessed as additives that control polymer chain growth in the polymerization of methyl methacrylate. In the presence of compounds mentioned in amounts comparable with that of the initiator, a uniform process with no gel-effect occured and respective linear increase in the molecular weight of the polymer up to high degrees of the monomer conversion was observed. 相似文献
4.
We observe that a term of the WZW-type can be added to the Lagrangian of the Poisson σ-model in such a way that the algebra of the first class constraints remains closed. This leads to a natural generalization of the concept of Poisson geometry. The resulting “WZW–Poisson” manifold M is characterized by a bivector Π and by a closed three-form H such that 1/2[Π,Π]Schouten=H,ΠΠΠ. 相似文献
5.
Historical perspectives for the chemistry of diene complexes of early transition metals developed at Osaka University in the period after 1970s were reviewed briefly and personally. Preparative chemistry of this field commenced from the magnesium-diene 1:1 compounds and quickly extended to almost all the early transition metals. By the studies operated together with other researchers, unique features of these diene complexes, especially their bonding and structure, selective reactions, and catalysis performances are described. 相似文献
6.
聚(酪氨酸酯对苯二甲酰胺)碳酸酯药物控制释放材料的研究 总被引:2,自引:0,他引:2
报道了一类生物可降解聚(酪氨酸酯对苯二甲酰胺)碳酸酯的合成和结构表征,研究了聚合物的性质和体外降解性能,并以5 氟脲嘧啶和牛血清白蛋为模型,对它们作为药物控制释放材料的性能进行了初步评价. 相似文献
7.
本实验开展了醋酸乙烯酯的可逆加成-断裂链转移自由基聚合(RAFT),分别运用偶氮二异丁腈(AIBN)引发和可见光引发两种方式进行了聚合反应,运用核磁共振和凝胶色谱等多种手段对所得聚合物结构进行了表征与分析。通过比较AIBN引发与光引发所获得聚合物端基结构的异同,加深了学生对RAFT聚合方法原理的理解。同时,运用该方法实现了聚合物两端端基结构的高度功能化,深入体会聚合物合成设计概念。本综合实验教学不仅通过对比法加深了学生对实验原理和专业知识的理解,提升了学生创新研究能力,而且训练了学生的实验操作技能、大型仪器使用能力和结果分析能力,提升了综合素质。 相似文献
8.
(甲基)丙烯酸酯的基团转移聚合 总被引:2,自引:5,他引:2
<正> 基团转移聚合方法自问世以来,由于其突出的优点,受到日益广泛的重视。本文来用丙二酸二乙酯的硅烯醇醚类引发剂3-乙氧基-3-三甲基硅氧基丙烯酸乙酯 (CH_3CH_2O_2CCH=C(OCH_2CH_3)OSiMe_3)和亲核型催化剂四乙基二氯化氢氨((CH_3CH_2)_4NHF_2)进行甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸乙酯(EA)和丙烯酸甲酯(MA)的基因转移聚合。得到了近 相似文献
9.
10.
Guo Yang Zhu Rong Wang Guo Hua Liu Li Qun Xu Bei Zhang Xia Qin Wu College of Life Environment Science Shanghai Normal University Shanghai China State Key Laboratory of Chema/Biosensing Chemometrics Hunan University Changsha China 《中国化学快报》2007,18(6):633-635
Starting from the hydroxylamine (dimethyl amino ethanol, triethanolamine) and 1,3-propane sultone, a series of hydroxyl and sulfonyl dual-functionalized zwitterionic salts and corresponding acidic room temperature ionic liquids have been synthesized. The hydroxyl groups of the synthesized substances were confirmed by the 1H NMR measurement. These zwitterionic salts and ionic liquids may be used for synthesizing other functionalized ionic liquids or ionic liquid-polymer (polyelectrolyte). 相似文献