The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

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 (k_H/k_D = 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.     

Pulse radiolysis study of the initial steps of the polymerization of cyclohexyl acrylate and cyclohexyl methacrylate

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 (2k_t) 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.     

Dicyclopentadienyl complexes of titanium,niobium, and tungsten in the controlled synthesis of poly(methyl methacrylate)

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.     

Synthesis And Properties Of Functional Ultra-High Molecular Weight Transparent Styrene-Butadiene Block Copolymer

Functional ultra-high molecular weight transparent styrene-butadiene block copolymer possesses both high transparency and impact resistance and has excellent comprehensive properties prior to other transparent resins. In this paper we not only use anionic polymerization process which includes 1 time addition of initiator and 3 time addition of monomers, but also introduce functional coupling agent for the fist time to prepare mentioned functional block copolymer. The typical preparation proces…     

Diene complexes of early transition metals: ideas and progresses at Osaka University

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.     

A study of the polymerization of styrene initiated by K-THF-GIC system

In this paper, the polymerization of styrene initiated by potassium (K)-tetrahydrofuran (THF)-graphite intercalation compound (GIC) (K-THF-GIC) was studied. The mechanism of the polymerization was determined to be anionic polymerization according to its characteristics. The effect of the concentration of the initiator and monomer was studied. It was found that the polymerization mainly occurred on the surface and edge of the intercalated graphite. It was also shown that the polarity of solvent has little effect on the polymerization yield in this system.     

(甲基)丙烯酸酯的基团转移聚合

<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     

N-取代N′-苯基哌嗪类化合物与硫杂蒽酮体系光诱导电子转移引发聚合体系的研究

本工作对N-苯基-N'-乙基呱嗪作为酮/胺光引发体系中组分之一的作用机制进行了研究。发现该特殊的胺类化合物虽包括二甲基苯胺和三乙胺两个部分,但它和酮类相组合形成的光引发体系只有较低的尤引发速率。对上述现象进行了讨论,并通过加入酸类化合物使其中一个胺发生季胺盐化,用以改进光引发效率来进一步证实文中所讨论的机制。     

Synthesis of multi-hydroxyl and sulfonyl dual-functionalized room temperature ionic liquids

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).     

聚噁唑啉的合成及其共混物

综述了唑啉单体的合成及其聚合方法，并对其聚合物的化学改性及共混物作了概述。