Search results for "Branching"
showing 10 items of 918 documents
Use of two-dimensional thin-layer chromatography for the components study of poly(adenosine diphosphate ribose)
1990
Two-dimensional thin-layer chromatography on cellulose plates has been used for separating and quantifying the three adenosine derivatives: AMP, phosphoribosyl AMP (PRAMP), and (PR)2AMP obtained by venom phosphodiesterase digestion of poly(ADP-ribose). In vitro synthesized polymer, up to 300 derivatives in length were studied. Some parameters of the complexity of poly(ADP-ribose) could be deduced from our results: (i) The first branching point appears in fragments of approximately 21 derivatives in length. (ii) The branching points are located at regular distances of approximately 41 derivatives from each other.
Influence of the irradiation parameters on the molecular modifications of an isotactic polypropylene gamma-irradiated under vacuum
2000
Isotactic polypropylene was irradiated under vacuum in a complete set of experimental conditions. The influence of the irradiation parameters, total absorbed dose, D, and dose rate, I, was analysed in order to verify the theoretical predictions of a simple kinetic model, already presented (Sarcinelli L, Valenza A, Spadaro G. Polymer 1997;38:2307), based on the rates of the main reactions occurring during irradiation, i.e. β-scission, addition to double bonds and termination. The concentration of free radicals and double bonds formed during irradiation is detected together with a comparison to their dependence on the irradiation parameters. A quantitative determination of the “inversion curv…
A Facile Two-Step Route to Branched Polyisoprenes via ABn-Macromonomers
2007
A facile two-step synthesis for branched poly(isoprene)s (PI) based on polyaddition of AB n -type macromonomers is described. The synthesis of the macromonomers was achieved by anionic polymerization of isoprene and subsequent end-capping of the polymers by addition of chlorodimethylsilane to the living carbanions. This led to PI-based macromonomers with narrow polydispersity (M w /M n < 1.15) and molecular weights in the range of 1700 -22100 g mol -1 . Synthesis of the branched polymers was carried out by a hydrosilylation-based polymerization of the macromonomers. Characterization via SEC, SEC-MALLS, coupled SEC-viscosimetry and 1 H-NMR-spectroscopy supported the formation of branched str…
One-step synthesis of multi-alkyne functional hyperbranched polyglycerols by copolymerization of glycidyl propargyl ether and glycidol
2013
By copolymerization of glycidol with the alkyne-containing oxirane monomer glycidyl propargyl ether (GPE), hyperbranched polyglycerol (hbPG) with a defined number of alkyne functionalities (up to 38%) can be obtained in a one-step procedure. The number of alkynes can be adjusted by the glycidol/GPE ratio to provide multi-alkyne functional hbPGs, maintaining the highly branched polyether structure. Interestingly, the acidic proton of the alkyne moiety does not interfere with the proton exchange mechanism during the polymerization of glycidol. By specific modification of the synthesis procedure, crosslinking reactions can be suppressed. The polymers exhibit molecular weights ranging from 1800…
Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization of macroinimers
2000
The molecular weight averages and the degree of branching, DB, of a hyperbranched polymer obtained by self-condensing vinyl polymerization (SCVP) of a macroinimer A-(m)γ-B* is calculated by modifying the existing equations for SCVP. The polydispersity is lowered by a factor (γ + 1), where γ is the degree of polymerization of the macroinimer. DB decreases with γ, however, at full conversion the DB of the polymacroinimer is approximately 60% higher than expected from the “dilution” of an AB* inimer with linear m units. This is the result of the existence of a new kind of branched units. The structure of polymacroinimers is similar to the pattern of a highly branched copolymer obtained by self…
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…
Ion-Induced Stretching of Low Generation Dendronized Polymers with Crown Ether Branching Units
2009
Synthesis of the first (G1) and second generation (G2) dendronized macromonomers MG1 and MG2 with the dibenzo-24-crown-8 moiety as branching unit is reported. The corresponding dendronized polymers, the polymethacrylates PG1 and PG2, were synthesized by free radical polymerization using AIBN as initiator at 60−80 °C. Static and dynamic light scattering revealed a significant chain expansion upon complexation of these polymers’ crown ether side chains with K+ ions. It is concluded that electrostatic repulsion does not significantly contribute to the chain expansion because of excessive counterion binding even well below the Manning limit, as evidenced by 19F NMR and 1H−19F NOE experiments. R…
Hyperbranched methacrylates by self-condensing group transfer polymerization
1997
The synthesis of hyperbranched methacrylates was achieved by self-condensing group transfer polymerization of 2-(2-methyl-1-triethylsiloxy-1-propenyloxy)ethyl methacrylate (1). “Back-biting” is shown to be the predominant side reaction. In spite of this, the compact nature of the hyperbranched molecules was demonstrated through SEC-viscosity measurements and comparison with a linear analogue. The degree of branching can be controlled by copolymerization with conventional monomers, e.g. MMA, and the living polymers can be used as macroinitiators for star-shaped polymers.
Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface
2013
Abstract The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate…
Time-Resolved study of network self-organization from a biopolymeric solution
1991
Time-resolved studies of network self-organization from homogeneous solutions of the representative biostructural polymer agarose are presented. Solutions are temperature quenched and observed by several techniques. Consistent with previous suggestions by the authors, experiments at concentrations up to about 1.75% w/v provide direct kinetic evidence for the occurrence of at least two distinct processes, leading, in sequence, to self-assembly. These are as follows: (a) a liquid–liquid phase separation of the solution occurring via spinodal demixing and resulting in two sets of regions that have, respectively, higher and lower than average concentrations of random-coiled polymers; and (b) th…