Search results for "Molar"

Molecular Parameters of Hyperbranched Copolymers Obtained by Self-Condensing Vinyl Copolymerization, 2. Non-Equal Rate Constants

2001

The kinetics, molecular weight averages, and the average degree of branching, DB, are calculated for the self-condensing vinyl copolymerization (SCVCP) of a vinyl monomer M with an "inimer" AB* in the case of different reactivities of active species. Emphasis is given to two limiting cases: formation of "macroinimers" occurs if the monomer M is more reactive than the vinyl groups of inimers or polymer, and "hyperstars" are formed in the opposite case. It is shown that the kinetics, the molecular weight averages, and the average degree of branching strongly depend on the relative reactivities of monomer and inimer. Comparison with experimental data shows that consistent fits of the reactivit…

Polymerizations of Cyclic Esters Catalyzed by Titanium Complexes Having Chalcogen-Bridged Chelating Diaryloxo Ligands

2002

A series of titanium complexes having tellurium-bridged chelating bis(aryloxo) ligands, [TiX2{2,2‘-Te(4-Me-6-tBu-C6H2O)2}]2 (5:  X = Cl; 6:  X = OiPr), catalyzed the ring-opening polymerization of cyclic esters such as e-caprolactone, δ-valerolactone, and l-lactide. The strong dependence of polymerizations on the solvent was observed in this catalytic system. When the polymerizations of e-caprolactone and l-lactide were carried out in toluene at 100 °C, tellurium-bridged bis(aryloxo)titanium complex 5 was found to give polymers with rather broad molecular weight distribution due to back-biting. When the polymerizations of e-caprolactone and l-lactide was carried out in anisole or in dioxane…

1982

The molecular weight distribution (MWD) of a high polymer is calculated from a weakly perturbed Zimm-plot of the classical light scattering on dilute solutions of Gaussian polymer coils (theta state). A typical Zimm-plot is simulated corresponding to the measurements of high accuracy as would be obtained by using the laser photometer described by Hack and Meyerhoff. The accuracy as published by these authors for small dissymmetries is used. Two inversion procedures are described in detail and tested, both of them avoiding the use of an empirical formula for the Laplace image of the calculated MWD. A complete numerical analysis of the results is given. The results are compared with those of …

A Monte Carlo study of diffusion in "living polymers"

1996

We report the first numeric experiments on diffusion in living polymers (polymers that can break and recombine reversibly, and are characterized by an exponential molecular weight distribution). In the simulation we use a modification of the bond fluctuation model which is known to reproduce the correct Rouse dynamics of polymer chains. The diffusion coefficient D reveals a Rouse-type behaviour D ∝ 1/L, where L is the average chain length of the polydisperse system. We also find a D ∝ exp [ − V/2kBT] dependence on the bond energy V, whereas at constant temperature the diffusion coefficient turns out to be inversely proportional, D ∝ ρ−1, to the monomer density of the system ρ in agreement w…

Polymer-Polymer Interaction: Consistent Modeling in Terms of Chain Connectivity and Conformational Response

2006

An approach developed for the modeling of polymer solutions is extended to polymer blends. It accounts explicitly for the fact that the segments of a given macromolecule cannot spread out over the entire volume of the system (chain connectivity) and that the space a polymer molecule occupies may change after contact formation between the components of a mixture (conformational response ζ). The validity of the equation obtained for the Flory-Huggins interaction parameter between polymers is tested by means of critical data published for the system PVME/PS. The measured phase diagrams can be modeled equally well by two limiting assumptions concerning the temperature dependence of the conforma…

Phase Behavior of the System Linear Polyglycerol + Methanol + Carbon Dioxide

2011

To compare the phase behavior of linear and hyperbranched polymers, the phase envelopes of the ternary system linear polyglycerol + methanol + carbon dioxide were determined for polymers of varying molar mass. Phase changes were detected by a static synthetic method using the Cailletet setup for temperatures between 331 K and 421 K and pressures up to 13.1 MPa. Besides the vapor–liquid and liquid–liquid equilibria, also the vapor–liquid to vapor–liquid–liquid and vapor–liquid–liquid to liquid–liquid phase boundaries are reported. The experimental results are similar to systems with hyperbranched polymers (rather than linear polymers). For the systems with linear polymers, however, the bubbl…

Prediction of maxima and minima in the curve of total sorption parameter in ternary polymer systems. Influence of ternary interaction parameter

1993

Flory-Huggins theory modified by Pouchly has been applied to predict maxima and minima in the curve of total sorption in ternary polymer systems formed by a polymer and two liquids. In this work, different diagrams based on experimental magnitudes easily obtained such as the difference in affinities of liquids, solvents and non solvents, and the solvent molar volume ratio. Total sorption parameter has been considered to be the decisive magnitude to define extrema conditions in both cosolvent and cononsolvent ternary polymer systems. The theoretical prediction is not altered by the inclusion of ternary interactions. Different examples of ternary systems dealing with vinyl polymers and polydi…

Influence of gamma-irradiation on thermally-induced mesoscopic gelation of degalactosylated xyloglucans

2014

Thermoresponsive degalactosylated xyloglucans have been already proposed as in situ gelling scaffolds for tissue engineering, due to their reversible macroscopic thermal gelation at body temperature and biodegradability. The highly branched, hydroxyl group-rich molecular structure renders xyloglucans interesting raw materials also in the form of micro/nanoparticles for application as nanoscalar drug delivery devices in cosmetic and pharmaceutical formulations. Owing to their natural source, xyloglucans show high average molecular weight, broad molecular weight distribution and poor water solubility, as large and compact aggregates usually form via inter-molecular hydrogen bonding. Co-60 gam…

γ-radiation-initiated polymerization of vinylidene fluoride in dense carbon dioxide

2002

The γ-ray-initiated batch polymerization of vinylidene fluoride (VF2) has been investigated in dense carbon dioxide under relatively mild operative conditions (T ≤ 40 °C and P < 25 MPa). When the initial VF2 molar concentration was increased from 3.4 to 6.4 mol/L, monomer conversion increased from 20 to 73%; a similar trend was observed for the number-average molecular weight and the molecular complexity of synthesized poly(vinylidene fluoride) (PVDF) as determined from rheological measurements. Under all adopted experimental conditions, a synthesized PVDF polymer was collected in the form of a white powder. Despite the inherent heterogeneous character of the polymerization process, a homog…

Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C Bond of Ortho-palladated Primary and Secondary Arylalkylamines

2009

The ortho-metalated complex [Pd2{κ2(C,N)-C6H4CH2CH2NHMe-2}2(μ-Br)2] (1) can be prepared by refluxing a 1:1 mixture of Pd(OAc)2 and N-methylphenethylamine in acetonitrile, followed by addition of an excess of NaBr. Complex 1 reacts with PPh3 to give the mononuclear derivative [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}Br(PPh3)] (2). The cationic complex [Pd{κ2(C,N)-C6H4CH2CH2NHMe-2}(py)2]ClO4 (3) can be obtained by reacting 1 with AgClO4 and pyridine. The previously reported complex [Pd2{κ2(C,N)-C6H4CH2NHCH2Ph-2}2(μ-Br)2] (A) reacts with PhC≡CCO2R (R = Me, Et) to give the monoinserted derivatives [Pd2{κ2(C,N)-C(Ph)═C(CO2R)C6H4CH2NHCH2Ph-2}2(μ-Br)2] (R = Me (4a), Et (4b)). These dimers react with neutral l…