Search results for "ionic"

Mechanism of Anionic Polymerization of (Meth)acrylates in the Presence of Aluminium Alkyls IV. Formation of a Co-ordinative Polymer Network via the L…

1996

The polymerization of methyl methacrylate in the presence of aluminium alkyls in toluene deviates from conventional kinetics. This results predominantly from the formation and precipitation of a co-ordinative polymer gel or network. Due to the lower reactivity and accessibility of the living chains in the gel, they are regarded as ’dormant’ and thus the concentration of active species decreases during polymerization. The network formation occurs via co-ordination of the living aluminate chain end group with in-chain ester carbonyl groups. Part of the chains are deactivated by a termination process but they are free of cyclic β-ketoesters which would result from the common ’back-biting’ reac…

Polymerization of styrene

1979

Graft Copolymers with Complex Polyether Structures: Poly(ethylene oxide)-graft-Poly(isobutyl vinyl ether) by Combination of Living Anionic and Photoi…

2014

Hydroxyfunctional oxetane-inimers with varied polarity for the synthesis of hyperbranched polyether polyols via cationic ROP

2014

Novel initiating systems for the living polymerization of acrylates and methacrylates

1998

The polymerization of methyl methacrylate with lithiated initiators in the presence of aluminium alkyls in toluene has living character but it deviates from conventional first-order kinetics and the polymers have fairly broad molecular weight distributions. This results from the formation and precipitation of a coordinative polymer network in which the lithium ions of the living chain ends are coordinated to the in-chain ester carbonyl groups. Thus, the network formation can be prevented by adding Lewis bases like methyl pivalate which coordinate to the living chain ends instead ofthe polymer. Alternatively, one can introduce tetraalkylammonium salts aiming at an exchange of the lithium ion…

Relaxation and charge transport in mixtures of zwitterionic polymers and inorganic salts

2009

Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly(3-[N-(omega-methacryloyloxyalkyl)-N, N-dimethylammonio]propanesulfonate) with sodium iodide in the frequency range of 10(2) Hz-10(7) Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arr…

Polyether Core-Shell Cylinder-Polymerization of Polyglycidol Macromonomers

2005

The synthesis and polymerization of macromonomers containing a polymerizable styrene head group and a tail of ethylene oxide derivatives of different character were investigated. The synthesis of macromonomers was based on living anionic polymerization of oxiranes. Two monomers were used: 1-ethoxyethyl glycidyl ether (glycidol acetal), which after hydrolysis forms hydrophilic glycidol blocks and glycidyl phenyl ether forming hydrophobic blocks. Polymerizable double bonds were introduced by terminating the living chain with p-(chloromethyl)styrene. The radical polymerization of the macromonomers was carried out in water with addition of a non-polar solvent (benzene) and AIBN as initiator. Co…

Polymeric mesoions, 4. Synthesis of polymerizable mesoionic 4,6-dioxo-1,3-diazines derived from vinylbenzylmalonic acid

2000

Vinylbenzylmalonic acid (4) was condensed with N,N'-diphenylformamidine (5a), N,N'-diphenylacetamidene (5b), S-propyl-1,3-diphenylisothiourea (6) and anilinopyridine (7) in the presence of dicyclohexylcarbodiimide (DDC). The resulting new mesoionic monomers 8a-d were polymerized with 2,2'-azoisobutyronitrile (AIBN) as an initiator and dodecanethiol as a chain transfer agent. The low molecular weight model compounds 5-benzyl-pyrido[1,2-a]pyrimidine-2,4-dione (9a) and 5-hexadecyl-4,6-dioxo-1,3-diphenyl-2-hexadecylthio-1,3-diazine (9b) were prepared for X-ray diffraction analysis and comparison of spectrospical data.

Cyclodextrins in polymer synthesis: polymerization of methyl methacrylate under atom-transfer conditions (ATRP) in aqueous solution

2000

Host guest complexes of methyl methacrylate (MMA) and randomly methylated β-cyclodextrin (m-β-CD, 1 a) were polymerized in aqueous medium using atom-transfer radical polymerization. Ethyl 2-bromoisobutyrate (EBIB) was used as an initiator, copper(I) bromide as the catalyst, and bipyridine (bipy) or 4,4′-di-(5-nonyl)-2,2´-bipyridine (dNbipy) as ligands. The unthreading of m-β-CD during the polymerization led to water-insoluble poly(methyl methacrylate) (PMMA). It was found that using dNbipy resulted in higher monomer conversion than using bipy as the ligand under similar conditions. Furthermore, it is shown that the polymerization of MMA under these conditions has a living character. The pol…

Group transfer and anionic polymerization: A critical comparison

1990

The mechanism of group transfer polymerization (GTP) of methacrylates in THF is investigated by using data on kinetics of homo- and copolymerization, polymer microstructure and molecular weight distribution. By comparison with corresponding data on anionic polymerization it is concluded that the mechanisms of monomer addition to the active chain end is very similar for both anionic and group transfer polymerization and that GTP is ionic in character. On the other hand, GTP uniquely is characterized by the existence of a catalyst exchange equilibrium. The position of this equilibrium determines the rates of polymerization, and the dynamics determine the molecular weight distribution.