Search results for "Addition polymer"

Universal Concept for the Implementation of a Single Cleavable Unit at Tunable Position in Functional Poly(ethylene glycol)s

2013

Poly(ethylene glycol) (PEG) with acid-sensitive moieties gained attention particularly for various biomedical applications, such as the covalent attachment of PEG (PEGylation) to protein therapeutics, the synthesis of stealth liposomes, and polymeric carriers for low-molecular-weight drugs. Cleavable PEGs are favored over their inert analogues because of superior pharmacodynamic and/or pharmacokinetic properties of their formulations. However, synthetic routes to acetal-containing PEGs published up to date either require enormous efforts or result in ill-defined materials with a lack of control over the molecular weight. Herein, we describe a novel methodology to implement a single acetalde…

Capitalizing on Protecting Groups to Influence Vinyl Catechol Monomer Reactivity and Monomer Gradient in Carbanionic Copolymerization

2017

everal vinyl catechol-based monomers with systematically varied acetal protecting groups suitable for carbanionic polymerization are introduced. All monomers are based on the 4-vinyl benzodioxole or 5-vinyl benzodioxole structure and differ in the nature of the protecting group for the catechol functionalities. Different symmetric ketones are used for the protection of the diol functionality. Polymers with average molecular weight from 2500 to 25 000 g mol−1 (Mw/Mn < 1.15) are obtained from homopolymerization of the protected monomers. All monomers are examined regarding the influence of the protecting group on the copolymerization behavior with styrene, using in situ 1H NMR kinetic studies…

1987

ESR spectroscopic analyses of the deep-green solutions of living poly(2-isopropenylnaphthalene) [poly(2-IPN)] in THF at −80°C provided no evidence of the presence of radical anions as long as butyllithium (BuLi) was used as initiator. In contrast to this finding, radicals could indeed be detected if the polymerization was performed with metallic potassium in THF. These radicals were found to be only stable at low temperatures. UV/VIS spectra of solutions of 2-IPN in THF or toluene and of catalytic quantities of BuLi were recorded at temperatures between −45 and +20°C. On heating to >0°C, the colour of the deep-green solution changes irreversibly to reddish-brown, and this colour change is a…

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.