929 resultados para Nucleophilic additions


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The electrochemical corrosion behavior of Mg-6Al-0.4Mn and Mg-6Al-4RE-0.4Mn (RE = Mischmetal) alloys is investigated in 3.5% NaCl solution. The results of corrosion process, polarization behavior, and electrochemical impedance spectroscopy of the alloys reveal that Mg-6Al-4RE-0.4Mn exhibits enhanced corrosion resistance. The addition of RE stabilizes the solid solution and modifies the passive film through a finer microstructure.

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The effect of Nd addition on the microstructure and mechanical properties of a die-cast AZ91 alloy was investigated in the present work. The results show that the die-cast AZ91 alloy is composed of alpha-Mg matrix and gamma-Mg17Al12 phase. Nd addition into the AZ91 alloy leads to the formation of rare earth containing intermetallic phase. Al4Nd phase forms when Nd content is less than or equal to 1.0 wt.%. Al2Nd phase appears simultaneously when Nd content reaches to 3.0 wt.%.

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Microstructure and mechanical properties of peak-aged Mg-4.5Zn-xGd (x=0, 0.5, 1.0 and 1.5 wt.%) alloys have been investigated. The results showed that the grain size of the alloys was refined gradually with increasing Gd. Mg5Gd and Mg3Gd2Zn3 phases were found in the Gd-containing alloys. The strengths were greatly improved with Gd additions, and the highest strength level was obtained in the Mg-4.5Zn-1.5Gd alloy, in which the ultimate tensile strength and yield strength were 231 MPa and 113 MPa, respectively.

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Microstructures and mechanical properties of the peak-aged Mg-4.5Zn-xGd (x = 0, 2, 3 and 5 wt.%) alloys have been investigated. The results showed that grain size increased with increasing Gd. Phase analysis showed that MgZn2 phase was observed in the Mg-4.5Zn alloy. While with Gd additions, Mg3Gd and Mg3Gd2Zn3 phases formed, and the volume fraction of the Mg3Gd2Zn3 phase increased with increasing Gd. Tensile test results indicated that the optimal mechanical properties were obtained in the Mg-4.5Zn-2Gd alloy, and the ultimate tensile strength and yield strength were 215 MPa and 121 MPa, respectively.

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A facile and efficient one-pot synthesis of halogenated pyridin-2(1H)-ones from a series of readily available enaminones under Vilsmeier conditions is described, and a mechanism involving sequential halogenation, formylation, and intramolecular nucleophilic cyclization is proposed.

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The reaction mechanism of Pt(0)-catalyzed diboration reaction of allenes is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. The electronic mechanisms of the allene insertion into the Pt-B bond are discussed in terms of the electron donation, back-donation, and d-pi interaction. During allene insertion into the Pt-B bond, the internal carbon atom of allene is preferred over the terminal one due to the stronger electron back-donation and stronger charge transfer in the former case than that in the latter one.

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In order to study the properties of Mg-Al-RE (AE) series alloys, the Mg-4Al-4RE-0.4Mn (RE= La, Ce/La mischmetal or Ce) alloys were developed. Their microstructures, tensile properties and corrosion behavior have been investigated. The results show that the phase compositions of Mg-4Al-4La-0.4Mn alloy consist of alpha-Mg and Al11La3 phases. While two binary Al-RE (RE = Ce/La) phases, Al11RE3 and Al2RE, are formed in Mg-4Al-4Ce/La-0.4Mn alloy, and Al11Ce3 and Al2Ce are formed in Mg-4Al-4Ce-0.4Mn alloy.

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Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H-T linkages over 83%, and number-average molecular weight (M-n) up to 100 kg/mol was synthesized at room temperature using Y(CCl3OO)(3)-ZnEt2-glycerine catalyst and 1,10-phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio-specific in attacking carbon in PO, leading to PPC with improved H-T linkages.

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The electrochemical corrosion behavior of Mg-5Al-0.4Mn-xNd (x = 0, 1, 2 and 4 wt.%) alloys in 3.5% NaCl solution was investigated. The corrosion behavior of the alloys was assessed by open circuit potential measure, potentiodynamic polarization, and electrochemical impedance spectroscopy. The electrochemical results show the intermetallic precipitates with Nd behave as less noble cathodes in micro-galvanic corrosion and suppress the cathodic process. During corrosion, Al2O3 and Nd2O3, in proper ratio, is incorporated into the corrosion film, and enhances the corrosion resistance.

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Mg-3Al-0.5Mn-0.5Zn-1MM alloy was prepared by metal mould casting method. The as-cast ingot was homogenized and then hot-rolled at 673 K with total thickness reduction of 65%. Microstructure and mechanical properties of the as-cast and hot-rolled samples were investigated. The results showed that the as-cast sample mainly consisted of alpha-Mg, beta-Mg17Al12, Al10Ce2Mn7, and Al11RE3 (RE = La and Ce) phases. The average grain size of the sample homogenized at 673 K was about 240 gm, and it was greatly refined to about 7 mu m by dynamic recrystallization for the hot-rolled sample.

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Four aromatic tetraamine monomers possessing flexible ether linkages were successfully synthesized by nucleophilic aromatic substitution of hydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-bis(4-hydroxyphenyl)propane, and 2,7-dihydroxynaphthalene with 5-chloro-2-nitroaniline, followed by reduction, respectively. With these monomers, a new class of soluble poly[ bis(benzimidazobenzisoquinolinones)] was prepared by a one-step, high-temperature solution polycondensation. The resulting polymers were completely soluble in phenolic solvents and had high inherent viscosities ranging from 1.2 to 1.5 g dL(-1). These polymers had glass transition temperatures in the range of 427-449 degrees C. Thermogravimetric analysis showed that all polymers were thermally stable, with 5% weight loss recorded above 510 degrees C in nitrogen.

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A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.

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Bisphenol monomer 4-carboxylphenyl hydroquinone (4C-PH) containing carboxyl groups was synthesized by diazotization reaction of p-aminobenzoic acid and 1,4-benzoquinone and subsequent reductive reaction. Copolymerization of bisphenol A, 4C-PH, sodium 5,5'-carbonylbis(2-fluorobenzene-sulfonate) and 4,4'-difluorobenzophenone at various molar ratios through aromatic nucleophilic substitution reaction resulted in a new sulfonated poly(ether ether ketone) containing pendant carboxyl groups (C-SPEEK). The structures of the monomer 4C-PH and copolymers were confirmed by FT-IR and H-1 NMR. Flexible and transparent membranes with sulfonic and carboxylic acid groups as the proton conducting sites were prepared. The dependence of ion-exchange capacity (IEC), water uptake, proton conductivity and methanol permeability on the degree of sulfonation has been studied.

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A novel strategy in which the benzimidazole group and sulfonic group are simultaneously attached to an aromatic polymer has been reported in this paper. For this purpose, sulfonated poly(arylene ether ketone) copolymers containing carboxylic acid groups (SPAEK-x-COOH, x refers to the molar percentage Of sulfonated repeating units) are prepared by the aromatic nucleophilic polycondensation of sodium 5,5'-carbonyl-bis(2-fluobenzene-sulfonate) (SDFBP), 4,4'-difluorobenzophenone (DFBP) and phenolphthalin (PPL). Then the carboxylic acid groups attached to the SPAEK-x-COOH are transformed to benzimidazole units through condensation reactions (referred to as SPAEK-x-BI). Fourier transform infrared spectroscopy and H-1 NMR measurements are used to characterize and confirm the structures of these copolymers.

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The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.