Search results for "Ionic"
showing 10 items of 2016 documents
Multihydroxyl-Functional Polystyrenes in Continuous Flow
2010
We describe the synthesis of end-functionalized polystyrenes by living anionic polymerization in a microstructured reactor via termination by acetal-protected functional epoxides. Initiation of styrene polymerization by alkyllithium takes place in a micromixing device with efficient heat and mass transfer properties. A newly developed continuous polymerization−termination sequence enabled quantitative functionalization of the living carbanions by nucleophilic displacement with different, specifically designed glycidyl ethers (ethoxy ethyl glycidyl ether (EEGE), 1,2-isopropylidene glyceryl glycidyl ether (IGG), and trans-2-phenyl-1,3-dioxane glycidyl ether (PDGE)). Upon acidic hydrolysis the…
Biphasic ethylene polymerisation using 1-n-alkyl-3-methylimidazolium tetrachloroaluminate ionic liquid as a medium of the Cp2TiCl2 titanocene catalyst
2008
Abstract A systematic analysis was performed on a series of 1- n -alkyl-3-methylimidazolium tetrachloroaluminates (where alkyl = ethyl, butyl, hexyl, and octyl), applied as a medium of the Cp 2 TiCl 2 titanocene catalyst, to evaluate the influence of the physical properties of the ionic liquids on the polymerisation reaction carried out in the biphasic ionic liquid/hexane mode. Two alkylaluminium compounds, AlEtCl 2 and AlEt 2 Cl, were used as activators. The influence of the activator/catalyst molar ratio on the performance of the ethylene polymerisation was determined for each ionic liquid studied. The best results were obtained using 1- n -octyl-3-methylimidazolium tetrachloroaluminate. …
Metal-free anionic polymerization of methyl methacrylate in tetrahydrofuran using bis(triphenylphosphoranilydene)ammonium (PNP+) as counterion
2000
Bis(triphenylphosphoranilydene)ammonium (PNP + ) triphenylmethanide (Ph 3 C - ) is a new metal-free initiator for the living polymerization of methyl methacrylate (MMA). The kinetics of the polymerization strongly depend on the metal counterion the initiator precursor. When the initiator is made from the metathesis reaction of Ph 3 CK and PNPCl, the polymerization follows first-order kinetics up to 0°C with half-lives below 0.1 s. The propagation rate constants are much higher than those obtained with tetraphenylphosphonium (TPP + ) cations, indicating a smaller fraction of dormant ylides. When the initiator is synthesized from Ph 3 CLi, polymerization proceeds much slower and molecular wei…
Anionic polymerization of methyl methacrylate using tetrakis[tris(dimethylamino)phosphoranylidenamino] phosphonium (P5+) as counterion in tetrahydrof…
2000
A novel metal-free initiator, i.e. the salt of the tetrakis[tris(dimethylamino)phosphoranylidenamino]phosphonium (P5+) cation with the 1,1-diphenylhexyl (DPH–) anion was prepared by cation metathesis. It initiates a very fast and controlled anionic polymerization of methyl methacrylate in THF. Kinetic investigations between –20 and +20°C using a flow tube reactor provide nearly linear first-order time-conversion plots with half-lives below 0.1 s, a linear dependence of the number-average degree of polymerization, and rather narrow molecular weight distributions (Mw/Mn ≈ 1.2). 13C NMR measurements on a model of the active chain end (the P5+ salt of ethyl isobutyrate) in THF-d8 show 15 and 25…
Anionic Polymerization of Alkyl (Meth)acrylates Using Metal-Free Initiators: Effect of Ion Pairing on Initiation Equilibria
1999
Metal-free anionic polymerizations of alkyl (meth)acrylates using tetrabutylammonium salts of diethylphenylmalonate, fluorene, and 9-ethylfluorene as initiators were performed in THF at 30 °C. A poor control of molecular weights, inconsistent initiator efficiencies, and broad or bimodal molecular weight distributions were obtained. The effect of counterion nature was studied from the polymerization of methyl methacrylate using the 1,1-diphenylhexyl anion with tetrabutylammonium, tetramethyldiethylguanidinium, and lithium as counterions under otherwise identical conditions. Metal-free initiators resulted in incomplete initiation which is attributed to the fact that the initiation is an equil…
Living Anionic Polymerization Celebrates 60 Years: Unique Features and Polymer Architectures
2017
Structural variations in amphiphiles: Discoidal multivalent cations
1986
Fourteen cationic multipolar amphiphiles have been synthesized with pyridinium or trimethylammonium head groups. The hydrophobic cores are planar ring systems (benzene or triphenylene) to which two, three, four, or six decylene or undecylene alkyl chains are attached by ester linkages. The hydrophilic head groups are bound to the outer ends of the alkyl chains.
ABA Triblock Copolymers Based on Linear Poly(oxymethylene) and Hyperbranched Poly(glycerol): Combining Polyacetals and Polyethers
2013
The synthesis of hyperbranched-linear-hyperbranched ABA triblock copolymers based on a linear poly(oxymethylene) (POM) block and hyperbranched poly(glycerol) (hbPG) blocks is described. The polymers containing a polyacetal polyether structure were prepared from linear bishydroxy-functional POM macroinitiators, obtained by cationic ring-opening polymerization of trioxane and 1,3-dioxolane as a comonomer with formic acid as a transfer agent and subsequent hydrolysis of the formate group. Partial deprotonation of the resulting hydroxyl groups permitted “hypergrafting” of glycidol by anionic ring-opening multibranching polymerization (ROMBP). With respect to the hyperbranched blocks, the obtain…
Ion pair association in isodielectric mixtures at 25�C
1974
Conductance measurements of potassium perchlorate and iodide have been carried out on the following mixtures: methanol-ethylene carbonate, acetone-ethylene carbonate, acetonitrile-ethylene carbonate, sulfolane-ethylene carbonate, isodielectric with water; and in benzene-sulfolane, benzene-acetonitrile, ethanol-sulfolane, isodielectric with methanol. The extent of ionic association at a given concentration in two solvents of the same dielectric constant is greater in the aprotic solvent.