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James C. W. Chien Borg-Ping Wang 《Journal of polymer science. Part A, Polymer chemistry》1989,27(5):1539-1557
The initial active site concentrations, [C*]0, have been determined with CH3OT radiolabeling for the Cp2ZrCl2/MAO and CpZrCl3/MAO catalysts (Cp = η5 : cyclopentadienyl, MAO = methyl aluminoxane). Almost all the Zr are found to be catalytically active in 70°C ethylene polymerizations; [C*]0 = [Zr] and [C*]0 = 0.8[Zr] at Al/Zr ratios of 104 and 103, respectively. Lowering the temperature to 50°C and Al/Zr to 5.5 × 102 reduces [C*]0 to 0.2[Zr]. The rate constant of propagation at 70°C was calculated to be 1.6 × 103(M s)?1 for both catalysts at Al/Zr = 1.1 × 104; the values are decreased fivefold and tenfold, respectively, for the CpZrCl3 and Cp2ZrCl2 systems. The usage of 14CO to determine the propagating Zr–P species was investigated. With regard to the time of reaction of 14CO with the polymerization mixture, the initial phase is attributed to reversible CO complexation and reversible migratory insertion. The second slower phase may be due to the formation of enediolate. During the course of a batch polymerization the 14C radioactivity incorporated is small compared to the number of active sites found by CH3OT determination; it is only ca. 10% of [C*]0 at maximum rate of polymerization. Therefore, 14CO radiolabeling cannot be used to count C*. 相似文献
44.
Sadik Elshani Randal Noriyuki Chien M. Wai N. R. Natale Richard A. Bartsch 《Journal of heterocyclic chemistry》1998,35(4):875-885
Twenty-six new lariat ether carboxylic and hydroxamic acids based upon dibenzo-13-crown-4, dibenzo-14-crown-4, dibenzo-16-crown-5 and dibenzo-19-crown-6 ring systems are synthesized and the solid-state structure for a dibenzo-19-crown-6 lariat ether hydroxamic acid is determined. The efficiency and selectivity for lanthanide ion extraction into chloroform by these proton-ionizable lariat ethers is strongly influenced by the crown ether ring size, lipophilic group attachment site and identity of the acidic function. In general, the lariat ether hydroxamic acids were more efficient and selective lanthanide ion extractants than the corresponding lariat ether carboxylic acids. The 1H nmr and ir binding studies indicate that both the macrocyclic polyether unit and the proton-ionizable group are involved in lanthanide ion complexation. 相似文献
45.
Ai-Huei Chiou Tse-Chang Chien Ching-Kuei Su Jheng-Fong Lin Chun-Yao Hsu 《Current Applied Physics》2013,13(4):717-724
A simple and low cost method to generate single-crystalline, well-aligned silicon nanowires (SiNWs) of large area, using Ag-assisted electroless etching, is presented and the effect of differently sized Ag catalysts on the fabrication of SiNWs arrays is investigated. The experimental results show that the size of the Ag catalysts can be controlled by adjusting the pre-deposition time in the AgNO3/HF solution. The optimum pre-deposition time for the fabrication of a SiNWs array is 3 min (about 162.04 ± 38.53 nm Ag catalyst size). Ag catalysts with smaller sizes were formed in a shorter pre-deposition time (0.5 min), which induced the formation of silicon holes. In contrast, a large amount of Ag dendrites were formed on the silicon substrate, after a longer pre-deposition time (4 min). The existence of these Ag dendrites is disadvantageous to the fabrication of SiNWs. Therefore, a proper pre-deposition time for the Ag catalyst is beneficial to the formation of SiNWs.SiNWs were synthesized in the H2O2/HF solution system for different periods of time, using Ag-assisted electroless etching (pre-deposition of the Ag catalyst for 3 min). The length of the SiNWs increases linearly with immersion time. From TEM, SAED and HRTEM analysis, the axial orientation of the SiNWs is identified to be along the [001] direction, which is the same as that of the initial Si wafer. The use of HF may induce Si–Hx bonds onto the SiNW array surface. Overall, the Ag-assisted electroless etching technique has advantages, such as low temperature, operation without the need for high energy and the lack of a need for catalysts or dopants. 相似文献
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Hsiu‐Fu Hsu Corresponding author Shih‐Jay Chien Hsiu‐Hui Chen Chien‐Hsing Chen Li‐Ya Huang Chung‐Hao Kuo 《Liquid crystals》2013,40(6):683-689
Liquid crystalline α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes (bi‐ and ter‐thiophene) have been synthesized and their mesogenic behaviour and optical properties investigated. They all exhibited a nematic mesophase, and compounds with long alkoxy chains also showed lamellar phases. Increasing the number of thiophene units increased both the transition temperatures and the mesophase ranges. As for their optical properties, incorporating more thiophene units results in red‐shifted absorption and emission spectra, slightly enhanced quantum efficiency, and a larger Stoke's shift. Most importantly, in terms of the absorption and emission maxima, the incorporation of one 4‐alkoxyphenylethynyl moiety was found to be equivalent to adding one thiophene ring. 相似文献
48.
Abstract North Vietnamese NR latexes were successfully epoxidized using peracetic acid at moderate temperature and pH range. The epoxide contents of pure epoxidized natural rubber (ENR) are from 5 to 70 mol%. The ENR products were characterized and determined by spectral and thermal analysis besides the chemical titration. Conditions of longlasting or excessive temperature, or high acidic pH led to side ring opened products, proved easily by IR, 1H-NMR, and DSC analysis. The ENR were vulcanized using a semiefficient system. The epoxidation increased the adhesion between rubber and tire cord and metal. This effect becomes stronger beyond 25 mol% and tends to be limited at over 60 mol%. The ENRs were used to formulate special-purpose adhesives. The shear strength of the adhesive ranges from 32 to 45 kg/cm2 for bonding rubber to nylon and rubber to metal, respectively. 相似文献
49.
Hou Chien Chang Ching Hsuan Lin Hung Tse Lin Shenghong A. Dai 《Journal of polymer science. Part A, Polymer chemistry》2012,50(5):1008-1017
Generally, protection and deprotection procedures of amino groups are required in preparing propargyl ether‐containing benzoxazines. In this study, we report a facile, deprotection‐free preparation of a propargyl ether‐containing phosphinated benzoxazine (2) from the nucleophilic substitution of a phenolic OH‐containing phosphinated benzoxazine (1) and propargyl bromide in the catalysis of potassium carbonate. The structure of (2) was characterized and confirmed by a high‐resolution mass spectrum, 1H, 13C, 1H‐1H, 1H‐13C nuclear magnetic resonance (NMR) spectra, and X‐ray single crystal diffractogram. infrared (IR) and differential scanning calorimetry were used to monitor the ring‐opening of benzoxazine and crosslinking of propargyl ether. The microstructure and the structure–property relationship of the resulting homopolymers and copolymers are discussed. The Tg of homopolymer of (2) is 208 °C by dynamic mechanical analysis, the coefficient of thermal expansion is 43 ppm/°C, and Td 5% (N2) is 393 °C, respectively, which are higher than those of the homopolymer of (1) . Similar trends were observed in the copolymerization system. The results demonstrate the beneficial effect of crosslinking afforded by the propargyl ether group is higher than that by the phenolic OH group. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
50.