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21.
Florent Jasinski Emeline Lobry Lénaïg Lefevre Abraham Chemtob Céline Croutxe‐Barghorn Xavier Allonas Adrien Criqui 《Journal of polymer science. Part A, Polymer chemistry》2014,52(13):1843-1853
The use of UV light to initiate emulsion polymerization processes is generally overlooked, whilst extensive literature exists on photocuring of monomer films. In this study, the unique potential of UV light to produce at ambient temperature polyacrylate latexes without initiator was exploited. Although radical initiators are utilized at low concentration, their cost, toxicity, and odor provide incentives for finding alternatives. Starting with concentrated (30 wt %) and low scattering acrylate miniemulsions (droplet diameter <100 nm), it was demonstrated that acrylate self‐initiation can promote an efficient and fast photopolymerization in micrometer‐scale reactor (spectrophotometric cell) and lab‐scale photoreactor. Herein, all kinetic, colloidal, and mechanistic aspects involved in the self‐initiation of acrylate miniemulsion were extensively examined to provide a complete picture. In particular, the effects of droplet size, initiating wavelength, optical path, and irradiance on the course of the polymerization were thoroughly discussed. A diradical self‐initiation pathway is the most likely mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1843–1853 相似文献
22.
Santhosh Kumar Podiyanachari Maciej Barłóg Marc Comí Salahuddin Attar Saeed Al-Meer Mohammed Al-Hashimi Hassan S. Bazzi 《Journal of polymer science. Part A, Polymer chemistry》2021,59(24):3150-3160
Ring-opening metathesis polymerization (ROMP)-derived poly(oxanorbornene imide)s bearing bay-linked mono - alkoxy -M1 and 1,7-di-alkoxy M2 functionalized perylene diimides (PDIs) were synthesized using Grubb's third ( G3 ) and Hoveyda-Grubbs second generation ( HG2 ) ruthenium-alkylidene metathesis initiators. The mono-alkoxy-derived PDI-based non-ladderphane polymer poly M1 displayed 67% to 77% of the trans olefin content in the polymer chain depending on the initiator used for the polymerization. When using the symmetrical 1,7-di-alkoxy-derived PDI-based polymer poly M2 having the ladderphane type-structure, this displayed a significant amount of cis and trans olefin contents in the polymer chains, irrespective of the type of initiators used for the polymerization. ROMP of both monomers M1 and M2 proceeded in a well-controlled manner with a linear dependence of molecular weight on the monomer/initiator ratio using G3 as initiator. Optical properties of the ladderphane-based poly M2 and non-ladderphane-based poly M1 were characterized in both solution and the film state. X-ray diffraction (XRD) analysis for all the polymers showed significant π-stacking in the thin film state with ordered molecular packing and closer values of d-spacing for both poly M1 and poly M2 . Film morphology examined by AFM elucidated homogenous smooth polymer surface for both polymers in general, but with some irregularities observed for poly M1 . In addition, CV analysis revealed both polymers could be good candidates as electron-accepting materials, with excellent film-forming ability, and thermal stability. 相似文献
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Formation, crystal structure, polymorphism, and transition between polymorphs are reported for M(thd)3, (M = Al, Cr, Mn, Fe, Co, Ga, and In) [(thd)– = anion of H(thd) = C11H20O2 = 2, 2, 6, 6‐tetramethylheptane‐3, 5‐dione]. Fresh crystal‐structure data are provided for monoclinic polymorphs of Al(thd)3, Ga(thd)3, and In(thd)3. Apart from adjustment of the M–Ok bond length, the structural characteristics of M(thd)3 complexes remain essentially unaffected by change of M. Analysis of the M–Ok, Ok–Ck, and Ck–Ck distances support the notion that the M–Ok–Ck–Ck–Ck–Ok– ring forms a heterocyclic unit with σ and π contributions to the bonds. Tentative assessments according to the bond‐valence or bond‐order scheme suggest that the strengths of the σ bonds are approximately equal for the M–Ok, Ok–Ck, and Ck–Ck bonds, whereas the π component of the M–Ok bonds is small compared with those for the Ok–Ck, and Ck–Ck bonds. The contours of a pattern for the occurrence of M(thd)3 polymorphs suggest that polymorphs with structures of orthorhombic or higher symmetry are favored on crystallization from the vapor phase (viz. sublimation). Monoclinic polymorphs prefer crystallization from solution at temperatures closer to ambient. Each of the M(thd)3 complexes subject to this study exhibits three or more polymorphs (further variants are likely to emerge consequent on systematic exploration of the crystallization conditions). High‐temperature powder X‐ray diffraction shows that the monoclinic polymorphs convert irreversibly to the corresponding rotational disordered orthorhombic variant above some 100–150 °C (depending on M). The orthorhombic variant is in turn transformed into polymorphs of tetragonal and cubic symmetry before entering the molten state. These findings are discussed in light of the current conceptions of rotational disorder in molecular crystals. 相似文献
25.
Depending on the solvothermal reaction conditions, we obtained three different metal-organic frameworks with yttrium(III) as metal component and 2,5-dihdyroxyterepthalic acid (H4dhtp) as bifunctional organic linker: Y2(H2dhtp)3(dmf)4 · (dmf)2 (CPO-29) contains dinuclear, paddle-wheel like inorganic secondary building units (SBUs) connected by the organic linker to a network with α-Po topology, while Y2(H2dhtp)(dhtp)(dmf)2 (CPO-30) and Y2(H2dhtp)(dhtp)(dmf)2(H2O)2 · (H2O)4 (CPO-31) contain one-dimensional inorganic SBUs that differ in how the half- and fully deprotonated ligands are connected to and arranged around them. Only the carboxylic acid groups of the organic linker are deprotonated in CPO-29, while CPO-30 and CPO-31 contain both 2,5-dihydroxyterephthalate (H2dhtp2–) linkers and fully deprotonated 2,5-dioxidoterephthalate (dhtp4–) linkers. All three compounds contain large volumes filled with solvent, but we were able to demonstrate permanence of porosity only for CPO-30. Variable temperature powder X-ray diffraction reveals that CPO-29 and CPO-31 undergo discontinuous phase transitions upon heating, and the flexibility of the framework structure indicated by these might be the reason for the inability to access the pore volume. Desolvated CPO-30 and CPO-31 are polymorphs, whose network structures differ in whether the H2dhtp2– and dhtp4– linkers are located in cis or trans arrangement around the inorganic SBU. 相似文献
26.
Phosphonic acid functional polymers are currently of interest because of their high proton conductivity in humidified and anhydrous systems. In addition, heterocyclic compounds are used in anhydrous proton conducting polymer membranes. In that study, a new copolymer based on 1‐vinyl‐1,2,4‐triazole (VTri) and diisopropyl‐p‐vinylbenzyl phosphonate (VBP) was synthesized, and their thermal, chemical, and proton conducting properties were investigated. The copolymers were synthesized by free radical copolymerization of the corresponding monomers at several monomer feed ratios to obtain P(VTri‐co‐VBP) copolymers. The copolymer samples were then hydrolyzed to produce poly(vinyl triazole‐co‐vinyl phosphonic acid) copolymers. The composition of the copolymers was determined by elemental analysis. The copolymerization and hydrolysis reactions were verified by Fourier transform infrared spectroscopy and ion exchange capacity measurements. Thermogravimetry analysis indicates that the copolymers are thermally stable up to 300°C. In order to increase the proton conductivity, the copolymers were doped with H3PO4 at several stoichometric ratios. The proton conductivity increases with triazole and phosphoric acid content. In the absence of humidity, the copolymer electrolyte, P(VTri‐co‐VBPA)1:0.5 X = 2, showed a proton conductivity of 0.005 S/cm at 150°C. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Palladium‐Catalyzed Stereoselective Intramolecular Oxidative Amidation of Alkenes in the Synthesis of 1,3‐ and 1,4‐Amino Alcohols and 1,3‐Diamines 下载免费PDF全文
Prof. Dr. Andrei V. Malkov Dr. Darren S. Lee Dr. Maciej Barłóg Dr. Mark R. J. Elsegood Prof. Dr. Pavel Kočovský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):4901-4905
An efficient and practical Pd‐catalyzed intramolecular oxidative allylic amidation provides facile access to derivatives of 1,3‐ and 1,4‐amino alcohols and 1,3‐diamines. The method operates under mild reaction conditions (RT) with molecular oxygen (1 atm) as the sole reoxidant of Pd. Excellent diastereoselectivities were attained with substrates bearing a secondary stereogenic center 相似文献
29.
Photonic crystal behavior of a rotating Bose-Einstein condensate with a triangular vortex lattice is reviewed and a scheme for getting much wider band gaps is proposed. It is shown that photonic band gaps can be widened an order of magnitude more by using a Raman scheme of index enhancement, in comparison to previously considered upper level microwave scheme. 相似文献
30.
We give a closed formula for topological K-theory of the homogeneous space N/, where is the standard integer lattice in the simply connected Heisenberg Lie group N of dimension 2n+1, n
. The main tools in our calculations are obtained by computing diagonal forms for certain incidence matrices that arise naturally in combinatorics. 相似文献