Search results for "Chain-growth polymerization"

Kinetic Analysis of “Living” Polymerization Processes Exhibiting Slow Equilibria. 5. Effect of Monomer Transfer in Cationic Polymerization and Simila…

1996

This work deals with the kinetics of polymerization processes with chain transfer to monomer and reversible formation of dormant species. Such a mechanism is typical for cationic polymerization in the presence of Lewis acids as co-initiators. The expressions of number- and weight-average degrees of polymerization and polydispersity index are derived rigorously for a mechanism with free ions as the active species, but it is also applied to other mechanisms, e.g., ion pairs as active species. Plots of polydispersity index versus monomer conversion can be easily computed on a PC computer even though the expressions for the weight-average degree of polymerization and the concentration of residu…

Some kinetic effects in the polymerization of 1,3,5-trioxane

1960

Surfactant-Free Emulsion Polymerization of Various Methacrylates: Towards Monodisperse Colloids for Polymer Opals

2004

A systematic investigation of the surfactant-free emulsion polymerization (SFEP) on three different methacrylates (MMA, tert-butyl methacrylate and 2,2,2-trifluoro ethyl methacrylate) is described to obtain monodisperse colloids for the preparation of artificial polymer opals. The experimental results are in agreement with a model, in which seed particles are formed very early during the polymerization process. The particles are formed very early during the polymerization process. The particles grow afterwards into the colloids until all monomer is consumed. This gives rise to a linear relationship between the volume of the colloids and the ratio of monomer to water in the reaction batch. T…

Macromonomers on the basis of 2-phenyl-2-oxazoline

1988

By initiation of the ring-opening polymerization of 2-phenyl-2-oxazoline (1) with p-iodomethylstyrene a macromonomer with a styrene end-group (2) is obtained. The degree of polymerization was varied between 10 and 16. The radical copolymerization of 2 with styrene is described. 1 forms with methyl triflate a very stable oxazolinium salt which is a good initiator for the bulk polymerization of 1 at temperatures of 50–70°C. It was conclusively proved that under these conditions the polymerization proceeds by a living mechanism. By termination with N, N-dimethylaminopropylmeth-acrylamide a macromonomer (5) was obtained. 5 can be radically homopolymerized. This comb-like polymer 6 has the typic…

A contribution to the kinetics of the polymerization of styrene with CF3SO3H as catalyst

1978

The time dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst can be formally described as being first-order with respect to monomer concentration [M]0. The reaction rate shows a third-order dependence in catalyst concentration [C]0. A high polymer and a low polymer polystyrene fraction are found at [M]0>0.2 mole · l−. The reaction rate of the high polymer fraction is proportional to [C] 0 3 , that of the low polymer fraction probably proportional to [C] 0 2 . The polymerization active species may thus be triple ions in the first and ion pairs in the second case.

Polymerization of styrene

1979

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…

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.