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1.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers 下载免费PDF全文
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
2.
Debendra K. Mohapatra Dhananjoy Mondal Mukund S. Chorghade Mukund K. Gurjar 《Tetrahedron letters》2006,47(52):9215-9219
The non-proteinogenic amino acid 3-hydroxy-4-methylproline (HMP) is an active constituent of some potent antimicrobials including echinocandins, nostopeptins, pneumocandins, sporiofungin and mulundocandins. A synthesis has been achieved in 10 steps with 29% overall yield; the Evans’ aldol reaction using Crimmins’ modified method was pivotal to the success of the strategy. 相似文献
3.
Peter Nesvadba Lucienne Bugnon Rosemarie Sift 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3332-3341
The synthesis of new 7‐membered diazepanone alkoxyamines [2,2,7,7‐tetramethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 3 ) and 2,7‐diethyl‐2,3,7‐trimethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 8 )] through the Beckmann rearrangement of piperidin‐4‐one alkoxyamines was developed. Both 3 and 8 were evaluated as initiators and regulators for the nitroxide‐mediated radical polymerization of styrene and n‐butyl acrylate. 8 , a sterically highly hindered alkoxyamine readily available as a crystalline solid, allowed the fast and controlled polymerization and preparation of polymers with low polydispersity indices (1.2–1.4) up to a degree of polymerization of about 100. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3332–3341, 2004 相似文献
4.
Fengping Yu Junpo He Xiaojun Wang Guangzheng Gao Yuliang Yang 《Journal of polymer science. Part A, Polymer chemistry》2007,45(17):4013-4025
A combination of nitroxide‐mediated radical polymerization and living anionic polymerization was used to synthesize a series of well‐defined graft (co)polymers with “V‐shaped” and “Y‐shaped” branches. The polymer main chain is a copolymer of styrene and p‐chloromethylstyrene (PS‐co‐PCMS) prepared via nitroxide‐mediated radical polymerization. The V‐shaped branches were prepared through coupling reaction of polystyrene macromonomer, carrying 1,1‐diphenylethylene terminus, with polystyryllithium or polyisoprenyllithium. The Y‐shaped branches were prepared throughfurther polymerization initiated by the V‐shaped anions. The obtained branches, carrying a living anion at the middle (V‐shaped) or at the end of the third segment (Y‐shaped), were coupled in situ with pendent benzyl chloride of PS‐co‐PCMS to form the target graft (co)polymers. The purified graft (co)polymers were analyzed by size exclusion chromatography equipped with a multiangle light scattering detector and a viscometer. The result shows that the viscosities and radii of gyration of the branched polymers are remarkably smaller than those of linear polystyrene. In addition, V‐shaped product adopts a more compact conformation in dilute solution than the Y‐shaped analogy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4013–4025, 2007 相似文献
5.
6.
Kejian Bian Michael F. Cunningham 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):414-426
Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ~1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006 相似文献
7.
电泳中介微分析法测定超氧化物歧化酶 总被引:1,自引:0,他引:1
基于超氧化物歧化酶(SOD)对邻苯三酚自氧化的抑制作用和电泳中介微分析(EMMA)技术建立了一种测定SOD的新方法。采用“三明治”式不同pH缓冲液部分填充法,有利于邻苯三酚的自氧化反应,便于观察SOD的抑制作用,有利于反应产物与反应物的分离。对溶液填充模式、反应条件等实验参数进行了优化。在最优条件下,邻苯三酚自氧化反应的抑制率I与SOD浓度C在1.00×102~6.00×102μg/L范围内呈良好的线性关系,回归方程为:I(%)=0.0895C(μg/L) 17.633(r=0.9973)。 相似文献
8.
Guido Barone Bruno Bove Giuseppina Castronuovo Vittorio Elia 《Journal of solution chemistry》1981,10(11):803-809
The excess enthalpies of aqueous solutions of nine polyols were determined at 25°C and reported in the virial form. The most interesting and new feature of this family of solutes is that the sign of the enthalpic pair interaction coefficients hxx is positive for the first members of the series and negative for the higher homologues. Other points are the large differences found among the values of hxx for stereoisomers, whereas pairs of enantiomers show the same values within experimental errors. An application of the group additivity method is also discussed. 相似文献
9.
Subhasis Chakrabarti Ashim K. Maity T. N. Misra 《Journal of polymer science. Part A, Polymer chemistry》1992,30(8):1625-1631
Raman spectroscopy has been used to study solid-state photopolymerization reactions in dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid (p-CPAMe) and diethyl ester of p-phenylenediacrylic acid (p-PDAEt). The reactants and products were characterized by infrared and Raman spectroscopy. Excitation and emission spectra suggest that in p-CPAMe exciton–phonon coupling is strong, but in the other monomer it is very weak. Raman phonon spectroscopic study reveal that in both the samples the reaction mechanism is homogeneous in the initial stages. However, in the later stages the reaction becomes heterogeneous in p-PDAEt. In p-CPAMe the lattice becomes disordered with the progress of polymerization and finally becomes amorphous whereas in p-PDAEt the lattice remains highly ordered. © 1992 John Wiley & Sons, Inc. 相似文献
10.
The carrier mediated transport of cations using model compounds of the verdinoid and rubinoid bile pigment structural type as ionophores is studied. Verdinoid bile pigments turn out to be very effective carriers for cations exhibiting a pronounced selectivity for certain transition metal ions like Cr+-+, Fe++, Cu++ and Zn++. The scope of this behaviour of verdinoid bile pigments is compared to [18]-crown-6 and meso-tetraphenylporphin and is discussed with regard to structural, biological, analytical and technical implications. 相似文献