Search results for "Chain length"

Kinetic Analysis of “Living” Polymerization Processes Exhibiting Slow Equilibria. 5. Effect of Monomer Transfer in Cationic Polymerization and Simila…

1996

This work deals with the kinetics of polymerization processes with chain transfer to monomer and reversible formation of dormant species. Such a mechanism is typical for cationic polymerization in the presence of Lewis acids as co-initiators. The expressions of number- and weight-average degrees of polymerization and polydispersity index are derived rigorously for a mechanism with free ions as the active species, but it is also applied to other mechanisms, e.g., ion pairs as active species. Plots of polydispersity index versus monomer conversion can be easily computed on a PC computer even though the expressions for the weight-average degree of polymerization and the concentration of residu…

Reaktionskinetik der Polymerisationshemmung durch molekularen Sauerstoff

1957

Die Polymerisationshemmung geschieht bei Styrol nach demselben Mechanismus wie er kurzlich fur Methylmethacrylat berichtet wurde1. Wahrend der Inhibierungsperiode findet streng alternierende Copolymerisation zwischen molekularem Sauerstoff und dem monomeren Styrol statt. Die fur die Anlagerung von O2 an das Radikal RM · masgebende Konstante kMO2 ist etwa von der Grosenordnung 106–107, d. h. die Reaktionsfahigkeit des Sauerstoffs in dieser Reaktion entspricht der eines Radikals. Bruttogeschwindigkeit und kinetische Kettenlange wahrend der Inhibierungsperiode werden auf Grund des Reaktionsmechanismus berechnet und experimentell bestatigt. The inhibition mechanism in the polymerization of styr…

Solid-state polymerization of oxetanes. I. Lattice parameters and packing properties of the monomers

1973

The crystallographic unit cells of melt-crystallized 3,3-bischloromethyloxetane and 3,3-bisbromomethyloxetane were determined by the Weissenberg method. The two isomorphous lattices are triclinic with two molecules in the unit cell. 3,3-Bisfluoromethyloxetane forms plastic crystals in the temperature range between −36°C and +22°C, as shown by differential calorimetry and NMR broad-line spectroscopy. The Debye-Scherrer diagram and the general physical properties indicate the formation of a face-centered cubic lattice. No correlation between the lattice parameters of the monomer and polymer can be found On the basis of these results, the question is raised as to whether a topochemical polymer…

The calculation of the number-average degree of polymerization starting from intrinsic viscosity and overall rate

1962

The relation between the intrinsic viscosity [η] and the number-average degree of polymerization Pn is a function of the molecular weight distribution of the polymer. In a polymer in which the termination of polymer radicals occurs partly by combination of two growing chains, this molecular weight distribution depends on number and extent of additional reactions such as chain transfer; i.e., it is variable. Therefore Pn of such polymers cannot be obtained from intrinsic viscosity measurements by means of an equation of the type [η] = KPna. A new method is proposed which allows the evaluation of Pn in these cases, without necessity of osmotic (or related) measurements or fractionation. The v…

1980

Using a bifunctional initiator such as the tetrameric dianion of α-methylstyrene for the anionic polymerization of methyl methacrylate the rate constant is found to increase with conversion approaching that observed with a monofunctional initiator while the tacticity of the polymers obtained changes from that of an almost ideally atactic to a highly syndiotactic polymer. The results are explained by the assumption of an intramolecular association of the two terminal ion pairs yielding a new active species and gradually dissociating with increasing degree of polymerization of the chain. Using a polymeric dianion of α-methylstyrene as an initiator the association phenomenon is not observed.

Some kinetic effects in the polymerization of 1,3,5-trioxane

1960

Frictional Forces between Strongly Compressed, Nonentangled Polymer Brushes: Molecular Dynamics Simulations and Scaling Theory

2010

By means of molecular dynamics simulations and scaling theory we study the response of opposing polymer brushes to constant shear motion under good solvent conditions. Model systems that contain explicit solvent molecules (Lennard-Jones dimers) are compared to solvent-free systems while varying of the distance between the grafted layers and their molecular parameters, chain length and grafting density. Our study reveals a power-law dependence of macroscopic transport properties on the Weissenberg number, W, beyond linear response. For instance, we find that the kinetic friction constant scales as μ ∼ W0.57 for large values of W. We develop a scaling theory that describes our data and previo…

1,2,4-Triazolium ions as flexible scaffolds for the construction of polyphilic ionic liquid crystals

2018

A novel scaffold for the construction of self-organised ionic liquids and ionic liquid crystals bearing both perfluorocarbon and hydrocarbon moieties has been developed. The phase behaviour and physical properties of these materials can be tuned as a function of chain length and fluorine content and significant structural elaboration is possible, giving a highly flexible system.

Particle Penetration into Polydisperse Polymer Brushes: A Theoretical Analysis

2017

Based on theoretical analysis, the effect of polydispersity on particle penetration into polydisperse polymer brushes is investigated. Three different polydispersities representing sharp, moderate, and extremely wide chain length distributions are chosen, since the corresponding explicit expressions of brush density at these polydispersities are available. To simplify the discussion, this study is restricted to spherical particles of small size which ensure that the particle insertion only causes local conformational perturbations. By analyzing the particle distribution, it is found that polydispersity always facilitates particle penetration. This prediction is confirmed by analyzing the su…

Escape Transition of a Grafted Polymer Chain

2000

The escape transition of a flexible polymer chain of chain length N, end-grafted at a hard wall and compressed by a piston of radius R in good solvent conditions, is studied by Monte Carlo simulation and by phenomenological arguments. In contrast to previous theories which have predicted a jump in the force f at a critical value H t of the height H of the piston above the wall, we find that the transition (which is sharp only for N → ∞) is characterized by a flat region of f in the f — H isotherm, i. e. a jump in the height occurs at the transition from H esc , t to H imptt , with (H imp , t — H esc , t )/H esc , t ≈ 0.26. At the transition the constant force f t is predicted and observed t…