排序方式: 共有41条查询结果,搜索用时 31 毫秒
1.
Coates GW Hustad PD Reinartz S 《Angewandte Chemie (International ed. in English)》2002,41(13):2237-2257
Coordination-insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal-based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(alpha-olefins), to end-functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted. 相似文献
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Polymerization of 1,5-hexadiene with a bis(phenoxyimine) titanium catalyst system is reported. The microstructure of the polymer contains the expected methylene-1,3-cyclopentane units as well as the unexpected 3-vinyl tetramethylene units. A mechanism for formation of this polymer is proposed. This unusual reaction is also employed in the synthesis of vinyl-functional polypropylene copolymers and block copolymers with low polydispersity indices. 相似文献
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The authors have obtained rotationally resolved vacuum ultraviolet pulsed field ionization-photoelectron (vuv-PFI-PE) spectrum of HD in the photon energy range of 15.29-18.11 eV, covering the ionization transitions HD+(X 2Sigmag+,v+=0-21,N+)<--HD(X 1Sigmag+,v"=0,J"). The assignment of rotational transitions resolved in the vuv-PFI-PE vibrational bands for HD+(X 2Sigmag+,v+=0-20) and their simulation using the Buckingham-Orr-Sichel (BOS) model are presented. Rotational branches corresponding to the DeltaN=N+-J"=0, +/-1, +/-2, +/-3, and +/-4 transitions are observed in the vuv-PFI-PE spectrum of HD. The BOS simulation shows that the perturbation of vuv-PFI-PE rotational line intensities due to near resonance autoionization is very minor at v+>or=5 and decreases as v+ is increased. Thus, the rotationally resolved PFI-PE bands for HD+(v+>or=5) presented here provide reliable estimates of state-to-state cross sections for direct photoionization of HD, while the rotationally resolved PFI-PE bands for HD+(v+<5) are useful data for fundamental understanding of the near resonance autoionizing mechanism. On the basis of the rovibrational assignment of the vuv-PFI-PE bands, the ionization energies for the formation of HD+(X 2Sigmag+,v+=0-20,N+) from HD(X 1Sigmag+,v"=0,J") and the vibrational constants (omegae, omegaechie, omegaeye, and omegaeze), the rotational constants (Be and alphae), the vibrational energy spacings, and the dissociation energy for HD+(X 2Sigmag+) are determined. As expected, these values are found to be in excellent agreement with high level theoretical predictions. 相似文献
4.
Suzuki N Zakaria MB Chiang YD Wu KC Yamauchi Y 《Physical chemistry chemical physics : PCCP》2012,14(20):7427-7432
The colloidal mesoporous silica nanoparticles with small particle sizes (namely, CMS) are used as inorganic fillers of polymers (i.e. epoxy and silicone). From simple calculation, almost all polymers are estimated to be confined in the mesopores. To clarify the superiority of CMS over nonporous silica particles and mesoporous silica particles with much larger size (TMPS-4) as inorganic fillers, a systematic study on mechanical strength and transparency of polymer-silica nanocomposites was conducted. Compared with nonporous silica particles, similar to TMPS-4, CMS shows a greater effect on lowering the CTE. In addition, obtained polymer-CMS nanocomposites show improved transparency than polymer-TMPS-4 nanocomposites. 相似文献
5.
Lian HY Hu M Liu CH Yamauchi Y Wu KC 《Chemical communications (Cambridge, England)》2012,48(42):5151-5153
Highly biocompatible coordination polymer (Prussian Blue) nanoparticles (LC(50) > 1000 μg mL(-1)) with a hollow interior and a microporous framework (denoted as HPB) are utilized as an anticancer drug (i.e. cisplatin) capsule for chemotherapy of bladder cancer T24 cells. 相似文献
6.
BP Bastakoti HS Huang LC Chen KC Wu Y Yamauchi 《Chemical communications (Cambridge, England)》2012,48(73):9150-9152
Porous α-Ni(OH)(2) microflowers are successfully synthesized via a one-step aqueous-phase reaction assisted by block copolymers under mild conditions. The electrochemical measurement demonstrates that the α-Ni(OH)(2) microflowers calcined at 200 °C are capable to deliver a specific capacity of 1551 F g(-1) in 6 M KOH solution, suggesting their high potential as a novel electrochemical pseudocapacitor. 相似文献
7.
Composite hollow fibers membranes were prepared by coating poly(phenylene oxide) (PPO) and polysulfone (PSf) hollow fibers with high molecular polyvinylamine (PVAm). Two procedures of coating hollow fibers outside and respective inside were investigated with respect to intrinsic PVAm solution properties and hollow fibers geometry and material.The influence of operating mode (sweep or vacuum) on the performances of membranes was investigated. Vacuum operating mode gave better results than using sweep because part of the sweep gas permeated into feed and induced an extra resistance to the most permeable gas the CO2. The composite PVAm/PSf HF membranes having a 0.7–1.5 μm PVAm selective layer, showed CO2/N2 selectivity between 100 and 230. The selectivity was attributed to the CO2 facilitated transport imposed by PVAm selective layer. The CO2 permeance changed from 0.006 to 0.022 m3(STP)/(m2 bar h) in direct correlation with CO2 permeance and separation mechanism of the individual porous supports used for membrane fabrication. The multilayer PVAm/PPO membrane using as support PPO hollow fibers with a 40 nm PPO dense skin layer, surprisingly presented an increase in selectivity with the increase in CO2 partial pressure. This trend was opposite to the facilitated transport characteristic behaviour of PVAm/porous PSf. This indicated that PVAm/PPO membrane represents a new membrane, with new properties and a hybrid mechanism, extremely stable at high pressure ratios. The CO2/N2 selectivity ranged between 20 and 500 and the CO2 permeance from 0.11 to 2.3 m3(STP)/(m2 bar h) depending on the operating conditions.For both PVAm/PSf and PVAm/PPO membranes, the CO2 permeance was similar with the CO2 permeance of uncoated hollow fiber supports, confirming that the CO2 diffusion rate limiting step resides in the properties of the relatively thick support, not at the level of 1.2 μm thin and water swollen PVAm selective layer. A dynamic transfer of the CO2 diffusion rate limiting step between PVAm top layer and PPO support was observed by changing the feed relative humidity (RH%). The CO2 diffusion rate was controlled by the PPO support when using humid feed. At low feed humidity the 1.2 μm PVAm top layer becomes the CO2 diffusion rate limiting step. 相似文献
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Direct access to functional (Meth)acrylate copolymers through transesterification with lithium alkoxides
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Carolin Fleischmann Athina Anastasaki Will R. Gutekunst Alaina J. McGrath Phillip D. Hustad Paul G. Clark David S. Laitar Craig J. Hawker 《Journal of polymer science. Part A, Polymer chemistry》2017,55(9):1566-1574
A straightforward and efficient synthetic method that transforms poly(methyl methacrylate) (PMMA) into value‐added materials is presented. Specifically, PMMA is modified by transesterification to produce a variety of functional copolymers from a single starting material. Key to the reaction is the use of lithium alkoxides, prepared by treatment of primary alcohols with LDA, to displace the methyl esters. Under optimized conditions, up to 65% functionalization was achieved and copolymers containing alkyl, alkene, alkyne, benzyl, and (poly)ether side groups could be prepared. The versatility of this protocol was further demonstrated through the functionalization of both PMMA homo and block copolymers obtained through either radical polymerization (traditional and controlled) or anionic procedures. The scope of this strategy was illustrated by extension to a range of architectures and polymer backbones. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1566–1574 相似文献
10.
Chen HW Liang CP Huang HS Chen JG Vittal R Lin CY Wu KC Ho KC 《Chemical communications (Cambridge, England)》2011,47(29):8346-8348
A film of mesoporous TiO(2) nanoparticles (MTNs) consisting of anatase nanocrystallites was electrophoretically deposited and compressed on a plastic substrate for the corresponding DSSC that gave an excellent conversion efficiency (η) of 5.25% under illumination of 100 mW cm(-2). 相似文献