Search results for " polymerization"
showing 10 items of 1054 documents
Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization
2020
International audience; Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-cataly…
Polystyrene nanoparticles in the presence of (ethylene oxide)13(propylene oxide)30(ethylene oxide)13, N,N-dimethyloctylamine-N-oxide and their mixtur…
2008
Polystyrene nanoparticles were synthesized by emulsion polymerization of styrene. They were functionalized using the conventional surfactant N,N-dimethyloctylamine-N-oxide (ODAO), the tri-block copolymer (ethylene oxide)13(propylene oxide)30(ethylene oxide)13 (L64) and their mixtures. To this purpose, dynamic light scattering and calorimetric experiments were carried out and provided information consistent to each other. The L64 adsorption is Langmuir-type in the copolymer dilute regime and generates complex structures at larger concentrations. In the region where ODAO is in the unimeric state, the adsorption process is cooperative leading to hemi-micelle formation at the polystyrene nanopa…
Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation.
2015
The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazen…
Secondary structure of peptides. 4:13C-Nmr CP/MAS investigation of solid oligo- and poly(L-alanines)
1983
Primary and tertiary amine-initiated polymerizations of L-alanine-N-carboxyanhydride (L-Ala-NCA) were conducted at 20 or 100°C in a variety of solvents. The 75.5-MHz 13C-nmr CP/MAS spectra of the resulting poly(L-alanines) revealed that all samples contain both α-helix and pleated-sheet structures. Depending on the reaction conditions the α-helix content varied between ca. 1 and 99%. Reprecipitation from aprotic nonsolvents does not change the α-helix/β-sheet ratio, indicating that this ratio is thermodynamically controlled. Since relatively large amounts of oligopeptides of degree of polymerization (DP) 4–6 can be extracted by means of acetic acid, it is concluded that (a) most poly(L-alan…
Glycidyl Tosylate: Polymerization of a “Non‐Polymerizable” Monomer permits Universal Post‐Functionalization of Polyethers
2019
Abstract Glycidyl tosylate appears to be a non‐polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer‐activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7–25 % incorporated tosylate‐moieties. The microstructure of the copolymers was investigated via in situ 1H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate‐moiety is demonstrated for several examples. This new structure provides access to a librar…
Introducing an amine functionality at the block junction of amphiphilic block copolymers by anionic polymerization strategies
2011
A series of block copolymers bearing a single amino in-chain functionality was synthesized via anionic polymerization of styrene and ethylene oxide. By means of both a conventional and a continuous setup, living polystyrene was quantitatively end functionalized with an oxirane (DBAG) prior to the polymerization of the poly(ethylene oxide) segment. The in-chain amine was conjugated with a fluorescent dye.
Sol–gel material as a support of organometallic catalyst for ethylene polymerization
2008
Abstract The sol–gel procedure was applied to obtain powdery materials with different structures and morphology. It was possible to produce almost non-porous silica powder, with an extremely low surface area (ca. 4 m 2 /g) and very high uniformity of spherical particles as well as materials with various uniformity of particles and different porosity, most likely associated with increasing pore volume. Dependent on the properties of the carrier, the resulting supported vanadium catalysts (VOCl 3 /AlEt 2 Cl) showed significant differences concerning activity and stability. It was confirmed that improved hydrophobicity of the carrier’s surface may be useful and improve the activity of the syst…
Effect of silica-type sol–gel carrier’s structure and morphology on a supported Ziegler–Natta catalyst for ethylene polymerization
2006
Abstract Silica xerogels with different structures and morphology, synthesized using a sol–gel procedure, were used as a carrier of vanadium catalysts (VOCl 3 /AlEt 2 Cl) for ethylene polymerization. Two techniques of catalyst synthesis were applied: slurry impregnation and gas-phase adsorption and the relevant polymerization methods were then employed. The effect of the carrier structure and morphology on the vanadium loading in the catalysts, the catalyst’s activity and kinetic stability were investigated.
Tritylpyridinium tetrakis(pentafluorophenyl)borate as an efficient activator for “constrained-geometry” catalysts in ethylene polymerization
2004
Abstract Ethylene polymerization with linked amido-cyclopentadienyl or “constrained-geometry” titanium catalysts, Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 N t Bu)X 2 (X=Me, Bz, Cl), activated by tritylpyridinium tetrakis(entafluorophenyl)borate, [Ph 3 C(NC 5 H 5 )] [B(C 6 F 5 ) 4 ], and silica-supported tritylpyridinium tetrakis(entafluorophenyl)borate (PySTB) was found to proceed with high activity. 1 H NMR spectra in CD 2 Cl 2 suggest that ([Ti(η 5 :η 1 -C 5 Me 4 ,SiMe 2 N t Bu)Me (NC 5 H 5 )] + is formed as the main cationic species. Using the heterogeneous cocatalyst PySTB in hexane, unexpectedly high ethylene polymerization activity was achieved, giving high molecular weight polyethylenes with exc…