Search results for "Ionic"
showing 10 items of 2016 documents
Spectroscopic and structural characterization of pure and FeCl3-containing tri-n-butyl phosphate
2014
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3 − n ] n+ and FeCl4 − complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attri…
Reactions of Maleisomides with Alcohols
2004
Abstract New surfactants (surfmers) with various amide and ester groups next to C˭C double bonds have been obtained. Maleic acid amidesters (AE) with different hydrophobic groups at the nitrogen atom and hydrophilic substituents at oxygen atoms were synthesized starting with maleic isoimides. 1H KMR and IR spectra were used for their characterization. Some were further characterized for their critical micellar concentration (CMC). A few cationic and zwitterionic surfmers were also prepared from isoimide precursors and characterized. All these surfmers were applied in batch emulsion polymerization of styrene, and in core‐shell seeded copolymerization of styrene and butylacrylate to give late…
Double-Hydrophilic Linear-Hyperbranched Block Copolymers Based on Poly(ethylene oxide) and Poly(glycerol)
2008
A convenient 4-step (2-pot) approach for the synthesis of biocompatible, double hydrophilic linear-hyperbranched block copolymers based on poly(ethylene oxide) (PEO) and poly(glycerol) (PG) is described. The polymers consisting exclusively of an aliphatic polyether structure were prepared from linear PEO-b-(l-PG) precursor block copolymers, obtained via anionic polymerization of ethylene oxide and subsequently ethoxyethyl glycidyl ether (EEGE). In order to generate initiating functionalities for glycidol, the protected hydroxyl groups of the P(EEGE) block were recovered by hydrolysis with hydrochloric acid. Partial deprotonation of the linear poly(glycerol) block with cesium hydroxide permi…
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…
Comparison of living polymerization systems
1994
Recent developments in the field of living polymerization are surveyed. Comparison of the available mechanistic and kinetic information is made for living anionic, cationic, free radical, group transfer, ring-opening metathesis, Ziegler-Natta and immortal polymerizations. This evaluation indicates that the majority of living polymerizations involve quasiliving equilibrium between active (propagating) and dormant (nonpropagating) polymer chains. On the basis of the kinetics of a general model for quasiliving and ideal living polymerizations it is concluded that ideal living polymerization is a special subclass of quasiliving polymerizations. Classification of living polymerization systems is…
Rapid Synthesis and MALDI-ToF Characterization of Poly(ethylene oxide) Multiarm Star Polymers
2009
Multiarm PEO star polymers with a purely aliphatic polyether structure have been synthesized using hyperbranched polyglycerol (PG) with different molecular weights as a multifunctional initiator. Different degrees of deprotonation of the initiator were studied with respect to molecular weight control. The results show that the degree of deprotonation is a crucial parameter for the synthesis of well-defined polymers with controlled molecular weights. Partial deprotonation of the PG hydroxyl groups (5-8%) was proven to represent an optimum for the synthesis of star polymers with molecular masses close to the theoretical values. Molecular weights of the stars ranged between 9 000 and 30000g · …
Hyperbranched Polyglycerols with Elevated Molecular Weights: A Facile Two-Step Synthesis Protocol Based on Polyglycerol Macroinitiators
2009
Hyperbranched polyglycerol (PG) is established as one of the few hyperbranched polymers that offer the possibility to control molecular weight up to Mn = 6000 g/mol. This work introduces a facile 2-step strategy that relies on the use of a low molecular weight PG (Mn = 500 and 1000 g/mol) as a macroinitiator for the slow addition of glycidol, permitting to overcome previous limitations concerning molecular weights and molecular weight control. A systematic investigation of the effect of the degree of deprotonation on the control of the polymerization reaction has been carried out. A series of hyperbranched PGs with molecular weights up to Mn = 24000 g/mol has been obtained under fully contr…
Cationic copolymers of ?,?-poly-(N-2-hydroxyethyl)-DL-aspartamide (PHEA) and ?,?-polyasparthylhydrazide (PAHy): synthesis and characterization
2000
In the present study the derivatization of two water-soluble synthetic polymers, α,β-poly(N-2-hydroxyethyl)-DL-aspartamide (PHEA) and α,β-polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introdu…
The role of association/complexation equilibria in the anionic polymerization of (meth)acrylates
1992
The kinetics of the anionic polymerization of methacrylates and acrylates in THF as well as the MWD of the polymers formed depend on the concentration of active centres and of additives, such as lithium halides and lithium alkoxides. These results are discussed on basis of multiple equilibria between non-associated, associated, and complexed ion pairs which are supported by viscosity measurements. The position of these equilibria determines the rate of polymerization, whereas the dynamics of interconversion determine the polydispersity. In the absence of additives the rate of monomer addition to non-associated ion pairs competes with the rate of association. Addition of lithium chloride mai…
A road less traveled to functional polymers: epoxide termination in living carbanionic polymer synthesis.
2010
Functional polymers possess tremendous potential both in academia and in industry. In particular, oxiranes offer manifold possibilities for the introduction of single hydroxyl or multiple orthogonal functionalities in carbanionic polymerization. Here, we present a brief overview of the fascinating possibilities arising from the employment of common as well as individually designed epoxide derivatives for the synthesis of end-functional polymers. Continuous flow techniques can be utilized for the rapid generation and screening of precisely defined hydroxyl-modified polymers. The utilization of functionalized polymers as precursors for the formation of complex macromolecular architectures (e.…