Search results for "Anionic addition polymerization"

1990

The anionic polymerization of tert-butyl acylate (tBuA) initiated by tert-butyl α-lithioisobutyrate was investigated in THF at 25°C. The individual oligomers were isolated and characterized by UV, IR and NMR spectroscopy. The distribution of products was determined in the range of reaction times 0,02 s ≤ t ≤ 1800 s. The oligomerization is extremely fast. Even after 0,02 s at -30°C, no residual monomer could be detected. After short reaction times the reaction mixture almost exclusively consists of linear oligomers of tBuA. This indicates that there is no termination reaction by Claisen condensation during polymerization. Nevertheless, the molecular weight distribution is rather broad (Mw/Mn…

Über die elementarprozesse bei der anionischen polymerisation des styrols in tetrahydropyran (THP)

1972

Kinetische und konduktometrische Messungen am System Polystyrl-Natrium in THP werden mit dem Ziel durchgefuhrt, alle in dem fruher vorgeschlagenen dreiteiligen Reaktionsschema vorkommenden thermodynamischen und kinetischen Parameter zu bestimmen und mit den in anderen Losungsmitteln gefundenen Werten zu vergleichen. Es zeigt sich, das die Geschwindigkeitskonstanten der Monomeraddition an das Kontaktionenpaar, das solvatgetrennte Ionenpaar und das freie Anion, die sich um Grosenordnungen unterscheiden, vom Losungsmittel nur geringfugig beeinflust werden. Der ungewohnlich grose Einflus der Losungsmittel auf die Polymerisationsgeschwindigkeit geschieht durch Verschiebung der Gleichgewichte zwi…

The kinetics of anionic polymerization of styrene in 1,2-dimethoxiethane

2007

Kinetic measurements in a flow apparatus in combination with conductance measurements, permit the determination of the two equilibrium constants Kes and Kdiss* and the three propagation rate constants k(±)c, k(±)s and k(−) as a function of temperature. The great differences in the polymerization rate in various solvents are mainly caused by their influence on the equilibrium constants. The influence of the solvent on the rate constants is not greater than in other chemical reactions.

Synthesis of Macromolecular Substances by Addition Polymerization

2001

As already explained, polymerization reactions can proceed by various mechanisms and can be catalyzed by initiators of different kinds. For addition polymerization of single compounds, initiation of chains may occur via radical, cationic, anionic, or so-called coordinative-acting initiators, but some monomers will not polymerize by more than one mechanism. Both thermodynamic and kinetic factors can be important, depending on the structure of the monomer and its electronic and steric situation. The most important initiators are summarized in Table 3.1.

1970

Two mechanisms are feasible in the anionic polymerization of virtually anhydrous formaldehyde initiated by uncharged LEWIS-bases such as tertiary amines and phosphines: 1. Direct initiation with formation of macrozwitterions the conventional mechanism in which an impurity such as water or methylene glycol acts as a cocatalyst. The investigations were carried out mainly by end group analysis. With triethyl amine as initiator the cocatalysis mechanism is the only or, at least, the predominant mechanism (at 20°C in dimethyl formamide). Quaternary ammonium ions – if any – are present in concentrations much below the concentrations of anionic chain ends. The latter were determined by termination…

Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

2019

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.

Amphiphilic Polyethers of Controlled Chain Architecture

2003

The amphiphilic polymers, polymers which contain in their macromolecules both hydrophilic and hydrophobic units1, are the base for valuable materials due to their diversified interaction with liquids. So they may act as emulsifiers, compatibilizers, “smart” materials (responding to external stimuli)2 and many others. In order to control their properties, the hydrophilic — hydrophobic balance in the macromolecules has to be controlled. This balance depends not only upon the constitution of the chain repeating units, but also upon the art of their distribution in the chains (copolymers of controlled unit sequences), the chain topology, the size of the chains and many others. So a careful engi…

Kinetics and Mechanisms in the Anionic Polymerization of Methacrylic Esters

1987

Under appropriate conditions the anionic polymerization of methacrylates proceeds in an ideal manner leading to polymers with narrow molecular weight distributions. From the kinetics of polymerization and from the microstructure of the polymers the existence of different active species is concluded, the most important one being a peripherally solvated contact ion pair. Depending on polymerization conditions two different modes of monomer addition can occur. Homo- and copolymerization experiments show that the influence of the ester group is mainly given by electronic effects. In non- polar solvents the polymerization of tert.-butyl methacrylate (in contrast to methyl methacrylate) leads to …

Kinetic Investigation on Metal Free Anionic Polymerization of Methyl Methacrylate Using Tetraphenylphosphonium as the Counterion in Tetrahydrofuran

1997

The anionic polymerization of methyl methacrylate using tetraphenylphosphonium triphenylmethanide as an initiator proceeds in a living manner even at room temperature. The rate constants of propagation were measured between -20 and +20 °C using a flow tube reactor. At 0 °C the reaction half-lives range from 0.3 to 1 s. The polymerization follows first-order kinetics with respect to monomer conversion (with a short induction period) and shows a linear dependence of the number-average degree of polymerization on conversion with high initiator efficiencies and narrow molecular weight distributions (M w /M n < 1.1). The dependence of the measured rate constants on the active center concentratio…