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81.
Gholam‐Reza Nejabat Mehdi Nekoomanesh Hassan Arabi Hamid Salehi‐Mobarakeh Gholam‐Hossein Zohuri Mojtaba Omidvar Stephen A. Miller 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):724-731
Various elastomeric polypropylenes (PPs) are synthesized through homogeneous propylene polymerization with metallocene catalyst (2‐PhInd)2ZrCl2 in the presence of different cocatalyst mixtures: triethylaluminum (TEA)/methylaluminoxane (MAO) or triisobutylaluminum (TIBA)/MAO in the range of AlAlR3/AlMAO = 0.0–0.9. The cocatalyst formulation impacts the resultant polymer microstructure and the thermal and dynamic mechanical properties of the produced PPs. 13C NMR analysis of the polymers reveals essentially atactic PP, with mmmm = 7.9%, when AlAlR3/AlMAO = 0.0. The mmmm pentad content is maximized when AlAlR3/AlMAO = 0.8; for TIBA, mmmm = 23.5%; and for TEA, mmmm = 17.6%. Differential scanning calorimetry analysis and dynamic mechanical thermal analysis corroborate these findings. Specifically, Tm, ΔHm, and Tg are essentially maximized under these conditions, and the minimum damping is observed for AlAlR3/AlMAO = 0.6–0.8. 1H NMR analysis of the mixtures of catalyst and cocatalysts (without monomer) shows very minor differences for [Zr]:AlAlR3 in the range of 1:1–1:5. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
82.
Sudip K. De Manish Bhattacharjee 《Journal of polymer science. Part A, Polymer chemistry》2011,49(18):3920-3927
An early transition metal metallocene compound, Cp2ZrCl2, with an anionic surfactant, sodium n‐dodecyl sulfate (SDS) as emulsifier and NaBPh4 as cocatalyst has been found to be an effective catalytic system for polymerization and copolymerization of monomers like styrene and methyl methacrylate in aqueous medium. The diameters of the latex particles were found to be in between 20 and 40 nm. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
83.
Erkki Aitola Kimmo Hakala Hedvig Byman‐Fagerholm Markku Leskelä Timo Repo 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):373-382
The influence of ligand structure on copolymerization properties of metallocene catalysts was elucidated with three C1‐symmetric methylalumoxane (MAO) activated zirconocene dichlorides, ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐cyclopentadienyl)ZrCl2 ( 1 ), ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐fluorenyl)ZrCl2 ( 2 ), and ethylene(1‐(9)‐fluorenyl‐(R)1‐phenyl‐2‐(1‐indenyl)ZrCl2 ( 3 ). Polyethenes produced with 1 /MAO had considerable, ca. 10% amount of trans‐vinylene end groups, resulting from the chain end isomerization prior to the chain termination. When ethene was copolymerized with 1‐hexene or 1‐hexadecene using 1 /MAO, molar mass of the copolymers varied from high to moderate (531–116 kg/mol) depending on the comonomer feed. At 50% comonomer feed, ethene/1‐olefin copolymers with high hexene or hexadecene content (around 10%) were achievable. In the series of catalysts, polyethenes with highest molar mass, up to 985 kg/mol, were obtained with sterically most crowded 2 /MAO, but the catalyst was only moderately active to copolymerize higher olefins. Catalyst 3 /MAO produced polyethenes with extremely small amounts of trans‐vinylene end groups and relatively low molar mass 1‐hexene copolymers (from 157 to 38 kg/mol) with similar comonomer content as 1 . These results indicate that the catalyst structure, which favors chain end isomerization, is also capable to produce high molar mass 1‐olefin copolymers with high comonomer content. In addition, an exceptionally strong synergetic effect of the comonomer on the polymerization activity was observed with catalyst 3 /MAO. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 373–382, 2008 相似文献
84.
85.
Carlos Alonso‐Moreno Pedro Carrion Fernando Carrillo‐Hermosilla Antonio Antiñolo Antonio Otero 《应用有机金属化学》2009,23(6):241-244
Activation of ansa‐zirconocenes of the type Rac [Zr{1‐Me2Si(3‐R‐(η5‐C9H5))(3‐R′‐(η5‐C9H5))}Cl2] [R = Et, R′ = H ( 1 ); R = Pr, R′ = H ( 2 ); and R = Et, R′ = Pr ( 3 ), R, R′ = Me ( 4 ) and R, R′ = Bu ( 5 )] by MAO has been studied by UV–visible spectroscopy. Compounds 1–3 have been tested in the polymerization of ethylene at different Al:Zr ratios. UV–vis spectroscopy was used to determine a correlation between the electronic structures of ( 1–5 ) and their polymerization activity. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
86.
Vasilios Kotzabasakis Konstantinos Kostakis Marinos Pitsikalis Nikos Hadjichristidis David J. Lohse Thomas Mavromoustakos Constantinos Potamitis 《Journal of polymer science. Part A, Polymer chemistry》2009,47(17):4314-4325
The Cs‐symmetry hafnium metallocene [(p‐Et3Si)C6H4]2C(2,7‐di‐tert‐BuFlu)(C5H4)Hf(CH3)2 and tetrakis(pentafluorophenyl) borate dimethylanilinium salt ([B(C6F5)4]?[Me2NHPh]+) were used as the catalytic system for the polymerization of higher α‐olefins (from hexene‐1 to hexadecene‐1) in toluene at 0 °C. The evolution of the polymerization was studied regarding the variation of the molecular weight, molecular weight distribution and yield with time. The effect of the monomer structure on the polymerization kinetics was established. The role of trioctylaluminum in accelerating the polymerization was investigated. 13C NMR spectroscopy was used to study the microstructure of the poly(α‐olefins) by the determination of the pentad monomer sequences. The thermal properties of the polymers were obtained by differential scanning calorimetry, DSC. The results were discussed in connection with the polymer microstructure. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4314–4325, 2009 相似文献
87.
Wei Cheng Ming Ji Xiaodan Li Jinwei Ren Fuling Yin Leen van Ofwegen Siwang Yu Xiaoguang Chen Wenhan Lin 《Tetrahedron》2017,73(17):2518-2528
Chemical investigation of the gorgonian coral Junceella fragilis resulted in the isolation of a new norditerpenoid fragilolide A (1), sixteen new briarane diterpenoids fragilolides B-Q (2–17), together with frajunolides H and N, and three known norcembranoids scabrolide D, sinuleptolide and 5-epi-sinuleptolide. The structures of new compounds were determined on the basis of extensive spectroscopic analysis, including the experimental and calculated ECD data and single-crystal X-ray diffraction for the configurational assignments. The structure of fragilolide A featured an unprecedented 4,13- and 7,11-fused tetracyclic norcembranoid, while the biogenetic relationships of the briarane analogues were postulated. Frajunolide H exerted significant inhibition against a panel of tumor cell lines, and six briarane diterpenoids (3, 6, 8, 12, 16, and frajunolide N) exhibited the inhibitory effects against the HBeAg express of hepatitis B virus in HepAD38 cells. In addition, sinuleptolide and 5-epi-sinuleptolide exerted the effects to inhibit NO production in RAW264.7 macrophage cells, in addition to the activation of ARE and the inhibition of NF-κB expression. 相似文献
88.
Iuliu O. Marian Nicolae Bonciocat Cecilia Cristea Robert Săndulescu Monica Bucşa Mircea Vlassa 《Electroanalysis》2010,22(5):542-548
The electrochemical and spectroelectrochemical behavior of 9‐substituted with ? CN and ? COOH acridine N‐oxides with potential antitumor activity was investigated. In SER spectra of the investigated compounds, the ring stretching vibration at 1568 cm?1 for 9‐CN‐substituted compound respectively 1639 cm?1 for 9‐COOH‐substituted compound was analyzed. Cyclic voltammograms indicates that the reduction potential ?0.766 V for ? CN substituted compound increase towards ?0.745 V for ? COOH substituted compound. The proposed theoretical method in the electrochemical impedance spectroscopy uses a reference redox dielectrode and a multielectrode containing the compound. To account for the change of electrochemical impedance we have considered two theoretical quantities: a pseudocapacitance and a pseudo inductance. Two possible arrangements of them: in series, respective in parallel can be used like criteria of drug classification. 相似文献
89.
Four novel diorganotin(IV) complexes with general formula R2SnL (R = nBu, PhCH2) were synthesized from diorganotin dichlorides and binary Schiff‐bases (H2L) containing N2O2 donor atoms in the presence of sodium ethoxide. The Schiff bases were prepared by reactions of o‐phenylenediamine with 3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzaldehyde (H2L1) and salicylaldehyde (H2L2) respectively. The compounds were characterized by elemental analyses, IR, and NMR spectroscopy. The solid‐state crystal structure of the compound nBu2SnL1 was determined by single‐crystal structural analysis. 相似文献
90.
我国天然药物和中药资源丰富,种类繁多,可作为先导化合物进行修饰以提高可成药性。其中,黄酮类化合物是自然界中一种常见的天然多酚类化合物,在抗肿瘤方面具有其独特的生物活性;对其进行结构修饰与改造,可提高黄酮类化合物的生物利用度和抗肿瘤活性。本文通过查阅并整理近几年国内外的黄酮类化合物的相关文献,对黄酮类化合物的母核位点进行结构修饰与改造所得的101个黄酮类衍生物及其抗肿瘤活性及作用机制进行综述,同时讨论了构效关系,以期为黄酮类衍生物的结构修饰和抗肿瘤研究提供参考和帮助。 相似文献