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71.
Aqueous room temperature metal-catalyzed living radical polymerization of vinyl chloride 总被引:1,自引:0,他引:1
Percec V Popov AV Ramirez-Castillo E Monteiro M Barboiu B Weichold O Asandei AD Mitchell CM 《Journal of the American Chemical Society》2002,124(18):4940-4941
This paper describes the room-temperature living radical polymerization (LRP) of vinyl chloride in H2O/THF in the presence of Cu0 or CuI salts as catalysts, tren or PEI as ligands, and iodoform as initiator. The disproportionation reaction 2CuI + L --> Cu0 + CuII(L) is the crucial step, as it continuously provides the active species for both the initiation (Cu0) and the reversible termination step (CuII). Mn was found to increase linearly with conversion and is in good agreement with Mth, with the Mw/Mn being approximately 1.5. 相似文献
72.
Virgil Percec Bruce Hahn 《Journal of polymer science. Part A, Polymer chemistry》1989,27(7):2367-2384
The synthesis and characterization of polymethacrylate, polyacrylate, poly(methylsiloxane), and 1,3,5,7-tetramethylcyclotetrasiloxane containing chiral 4-[2-(S)-methyl-1- butoxy]-4′-(11-undecanyl-1-oxy)-α-methylstilbene side groups are described. All polymers exhibit an enantiotropic SA mesophase and side-chain crystallization. The 1,3,5,7-tetramethylcyclotetrasiloxane containing mesogenic side groups represents a mixture of four stereoisomers and displays a monotropic SA mesophase 相似文献
73.
Chang-Jyh Hsieh Chain-Shu Hsu Ging-Ho Hsiue Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》1990,28(2):425-435
The synthesis of side-chain liquid crystalline polysiloxanes containing oligooxyethylene spacers and 4-methoxyphenyl benzyl ether and 6-cyano-2-naphthyl benzyl ether based mesogenic groups is presented. The phase behavior of both monomeric and polymeric liquid crystals was characterized by differential scanning calorimetry and optical polarized microscopy. All synthesized polysiloxanes present smectic mesomorphism. The insertion of oxygen atoms into the flexible aliphatic spacers leads to decrease in both glass transition and isotropization temperatures of the resulting side-chain liquid crystalline polymers. 相似文献
74.
Jose M. Rodriguez-Parada Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》1987,25(8):2269-2279
The synthesis of three cyclic imino ethers containing mesogenic groups attached to the heterocyclic unit through flexible spacers is described. Cationic ring-opening isomerization polymerization of two of them, i.e., 2-[4-(4-methoxy-4′-biphenyloxy)butyl]-2-oxazoline (MeOBiph-4-Oxz) and 2-[6-(4-methoxy-4′-biphenyloxy)hexyl]-2-oxazoline (MeOBiPh-6-Oxz) provided thermotropic liquid crystalline (LC) poly(N-acylethyleneimine)s, whereas the polymerization of 2-[4-(4-phenylphenoxy)butyl]-2-oxazoline (BiPh-4-Oxz) led to a crystalline polymer. 相似文献
75.
John A. Enquist Jr. Dr. Scott C. Virgil Prof. Brian M. Stoltz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):9957-9969
A concise and versatile approach toward the preparation of the cyanthiwigin family of cyathane natural products is described. By leveraging a unique double asymmetric catalytic alkylation procedure it is possible to quickly establish two of the most critical stereocenters of the cyanthiwigin framework with high levels of selectivity and expediency. The synthetic route additionally employs both a tandem ring‐closing cross‐metathesis reaction, and an aldehyde‐olefin radical cyclization process, in order to rapidly arrive at the tricyclic cyathane core of the cyanthiwigin molecules. From this unifying intermediate, the preparations of cyanthiwigins B, F, and G are attained swiftly and without the need for protecting groups. 相似文献
76.
In this work we consider two integral operators. The integral operators were constructed on the basis of the fact that the number of functions from the composition of the operators is the entire part of a complex number modulus. 相似文献
77.
Sven Fleischmann Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2010,48(10):2236-2242
Single electron transfer‐living radical polymerization (SET‐LRP) represents a robust and versatile method for the rapid synthesis of macromolecules with defined architecture. The present article describes the polymerization of methyl methacrylate by SET‐LRP in protic solvent mixtures. Herein, the polymerization process was catalyzed by a straightforward Cu(0)wire/Me6‐TREN catalyst while initiation was obtained by toluenesulfonyl chloride. All experiments were conducted at 50 °C and the living polymerization was demonstrated by kinetic evaluation of the SET‐LRP. The process follows first order kinetic until all monomer is consumed which was typically achieved within 4 h. The molecular weight increased linearly with conversion and the molecular weight distributions were very narrow with Mw/Mn ~ 1.1. Detailed investigations of the polymer samples by MALDI‐TOF confirmed that no termination took place and that the chain end functionality is retained throughout the polymerization process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2236–2242, 2010 相似文献
78.
Sebastiano Guerra Julien Iehl Michel Holler Mihai Peterca Daniela A. Wilson Benjamin E. Partridge Shaodong Zhang Robert Deschenaux Jean-Fran?ois Nierengarten Virgil Percec 《Chemical science》2015,6(6):3393-3401
Twelve chiral and achiral self-assembling dendrons have been grafted onto a [60]fullerene hexa-adduct core by copper-catalyzed alkyne azide “click” cycloaddition. The structure adopted by these compounds was determined by the self-assembling peripheral dendrons. These twelve dendrons mediate the self-organisation of the dendronized [60]fullerene into a disc-shaped structure containing the [60]fullerene in the centre. The fullerene-containing discs self-organise into helical supramolecular columns with a fullerene nanowire-like core, forming a 2D columnar hexagonal periodic array. These unprecedented supramolecular structures and their assemblies are expected to provide new developments in chiral complex molecular systems and their application to organic electronics and solar cells. 相似文献
79.
Percec V Glodde M Peterca M Rapp A Schnell I Spiess HW Bera TK Miura Y Balagurusamy VS Aqad E Heiney PA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(24):6298-6314
Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce pi-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal domains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals. 相似文献
80.
Michael W. Lufaso Terrell A. Vanderah Ileana M. Pazos Robert S. Roth Virgil Provenzano 《Journal of solid state chemistry》2006,179(12):3900-3910
Subsolidus phase relations have been determined for the Bi2O3-Fe2O3-Nb2O5 system in air (900-1075 °C). Three new ternary phases were observed—Bi3Fe0.5Nb1.5O9 with an Aurivillius-type structure, and two phases with approximate stoichiometries Bi17Fe2Nb31O106 and Bi17Fe3Nb30O105 that appear to be structurally related to Bi8Nb18O57. The fourth ternary phase found in this system is pyrochlore (A2B2O6O′), which forms an extensive solid solution region at Bi-deficient stoichiometries (relative to Bi2FeNbO7) suggesting that ≈4-15% of the A-sites are occupied by Fe3+. X-ray powder diffraction data confirmed that all Bi-Fe-Nb-O pyrochlores form with positional displacements, as found for analogous pyrochlores with Zn, Mn, or Co instead of Fe. A structural refinement of the pyrochlore 0.4400:0.2700:0.2900 Bi2O3:Fe2O3:Nb2O5 using neutron powder diffraction data is reported with the A cations displaced (0.43 Å) to 96g sites and O′ displaced (0.29 Å) to 32e sites (Bi1.721Fe0.190(Fe0.866Nb1.134)O7, Fd3¯m (#227), ). This displacive model is somewhat different from that reported for Bi1.5Zn0.92Nb1.5O6.92, which exhibits twice the concentration of small B-type cations on the A-sites as the Fe system. Bi-Fe-Nb-O pyrochlores exhibited overall paramagnetic behavior with large negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. The single-phase pyrochlore with composition Bi1.657Fe1.092Nb1.150O7 exhibited low-temperature dielectric relaxation similar to that observed for Bi1.5Zn0.92Nb1.5O6.92; at 1 MHz and 200 K the relative permittivity was 125, and above 350 K conductive effects were observed. 相似文献