Search results for "solution"
showing 10 items of 5638 documents
Development of a Chiral DMAP Catalyst for the Dynamic Kinetic Resolution of Azole Hemiaminals
2017
A new catalyst for the dynamic kinetic resolution of azole hemiaminals has been developed using late-stage structural modifications of the tert-leucinol-derived chiral subunit of DMAP species.
Solubilization by polysoaps
1994
The aqueous solubilization power of several series of micellar homopolymers and copolymers (''polysoaps'') is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect to the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes.
Cyclodextrins in Polymer Synthesis: Influence of Acrylate Side Groups on the Initial Rate of Radical Polymerization of Various Acrylate/Methylated β…
2001
Methylated β-cyclodextrin was used to complex the hydrophobic monomers n-propyl acrylate (1), n-butyl acrylate (2), n-pentyl acrylate (3), n-hexyl acrylate (4), and cyclohexyl acrylate (5) respectively yielding the corresponding water-soluble host/guest-complexes 1a−5a. The complexes were polymerized in water by free radical mechanism and the initial polymerization rates (v0) determined. We found that v0 increases as follows: 1a (12.5), 2a (27.5), 3a (44.2), 5a (49.4), 4a (75.8 × 10-6 mol·L-1·s-1). To investigate the influence of the hydrophobic character of the guest monomers on the reaction rate, the water solubilities of the uncomplexed monomers 1−5 were determined by HPLC measurements.…
Synthesis and characterization of well-defined poly(tert-butyl acrylate) star polymers
2009
Abstract Star polymers with different numbers and lengths of poly(tert-butyl acrylate) (PTBA) arms were obtained via atom transfer radical polymerization. Aliphatic alcohols with different number of hydroxyl groups varying from 3 to 6 and calix[4]arenes based on pyrogallol with 12 and 16 phenol groups were transformed to bromoester derivatives to prepare multifunctional ATRP initiators used as the cores of the stars. The star polymers were characterized by GPC with refractive index, multiangle laser light scattering and viscosimetric detectors. The molar masses of the stars reached 70,000 g/mol and the molar mass dispersities did not exceed 1.2. To elucidate the compact structure of the sta…
Transfer to Polymer and Long-Chain Branching in PLP-SEC of Acrylates
2009
Pulsed laser polymerization (PLP) combined with size exclusion chromatography (SEC) is the method of choice for determining propagation rate coefficients. The influence of the long-chain branching in PLP-SEC is investigated using multiple-detection SEC and a recently developed method to detect long-chain branching [P. Castignolles, R. Grab, M. Parkinson, M. Wilhelm, M. Gaborieau, Polymer 2009, 50, 2373.] While little or no long-chain branching is detected in poly(n-butyl acrylate), the error in relevant molecular weights of poly(2-ethylhexyl acrylate) is large (30-100%) due to long-chain branching. Possible variations of propagation rate coefficient with alkyl groups in alkyl acrylates or w…
Synthesis of CO2-responsive polymers by post-polymerization modification
2014
Abstract We describe a general method to synthesize a double responsive polymer, exhibiting a temperature and CO 2 responsive behavior. The polymer derived from a controlled radical polymerization technique of pentafluorophenyl acrylate (PFPA), followed by a sequential post-polymerization modification of a CO 2 responsive- and thermo-responsive amines. Utilizing this approach three double responsive copolymers were synthesized, poly(3- N′,N′ -dimethylaminopropyl acrylamide- co - N -isopropyl acrylamide) (poly(DMPA- co -NIPAM)), poly( L -Arginine methyl ester acrylamide- co - N -isopropyl acrylamide) (poly(AME- co -NIPAM)) and poly( L -Arginine methyl ester acrylamide- co - N -cyclopropyl ac…
Anionic Polymerization of (Meth)acrylates in the Presence of Tetraalkylammonium Halide−Trialkyl Aluminum Complexes in Toluene. 3. Kinetic Investigati…
2001
The polymerization of n-butyl acrylate initiated by ester enolates in the presence of tetraalkylammonium halide−trialkylaluminum complexes, R4N[AlnR‘3nX] (n = 1, 2), in toluene has a controlled character at −78 °C only for selected combinations of the complex. Quantitative monomer conversions are usually reached with Me4N[AlnBui3nCl] leading to polymers with narrow molecular weight distributions (Mw/Mn < 1.2). Kinetic investigations show a complex mechanism of the polymerization, implying an equilibrium between at least two active species. Besides, various acrylate homopolymers and block copolymers (PMMA-b-polyacrylate) can be synthesized with this new initiating system.
Thermodynamic studies of octyltrimethylammonium chloride in water
1992
Densities, heat capacities, enthalpies of dilution at 298 K and osmotic coefficients at 310 K of octyltrimethylammonium chloride were measured as functions of concentration. From the experimental data, the partial molar volumes, heat capacities, relative enthalpies, nonideal free energies and entropies at 298 K were derived as functions of concentration. A comparison between the above data and those of dodecyltrimethylammonium chloride reported in the literature shows that the increase of the alkyl chain length shifts the apparent molar volumevs. concentration curves towards greater values and the heat capacity, relative enthalpy and free energyvs. concentration curves towards smaller value…
Small angle scattering study of poly(methylmethacrylate)-blockpoly(ethylene oxide) block co-polymer in aqueous solution
2005
A combined Small Angle X ray (SAXS) and Neutron (SANS) Scattering study of aqueous solutions of a symmetric block copolymer consisting of poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) moieties is presented. The polymer forms slightly polydisperse spherical micelles in a wide range of concentration (0.03 – 6.7 w/V) and temperature (20°C ≤ T ≤ 65°C). A good description of the SANS data is obtained using a polydisperse core-shell model with a structure factor for a modified hard sphere potential. By increasing the concentration at constant T we observed a decrease of the aggregation number and an increase of solvation of PEO groups in the shell, opposite to what happens by in…
Continuum-uniform approach calculations of the solubility of hydrocarbons in water
1993
Abstract The ransfer free energies from gas phase to water for some hydrocarbons are calculated by means of a continuum-uniform model of the solvent. For the calculation of the cavitation energy a model based on the surface tension is proposed. The calculated values are compared with the experimental free energies obtained with and without a corrective factor that accounts for the difference in the solute—solvent sizes. Good agreement between the theoretical free energies and the corrected experimental data is obtained. Our calculations seem to show that the hydrophobic effect is directly related to the molecular surface area.