The kinetics of anionic polymerization of styrene in 1,2-dimethoxiethane

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.

Mechanism of Anionic Polymerization of (Meth)acrylates in the Presence of Aluminum Alkyls, 6. Polymerization of Primary and Tertiary Acrylates

The kinetics of the polymerization of n-butyl acrylate initiated by lithiated ester enolates in the presence of aluminum alkyls was investigated in toluene and in toluene/Lewis base mixed solvents at −78 °C. In pure toluene, curved time−conversion plots, incomplete monomer conversion, and broad molecular weight distributions (Mw/Mn ≈ 2) are observedin the absence of aluminum alkyls the molecular weight distributions are significantly broader (Mw/Mn > 14). High monomer conversions and narrower molecular weight distributions (Mw/Mn ≈ 1.5) are obtained when using Lewis bases (e.g., methyl pivalate) as cosolvents. The polymerization of tert-butyl acrylate rapidly reaches full monomer conversion…

Energie- und Entropieparameter der Zustandsformen von Carbanionen aus der Polymerisationskinetik und aus Leitfähigkeitsmessungen an Polystyrylnatrium in polaren organischen Lösungsmitteln

Anionic Polymerization of (Meth)acrylates in the Presence of Cesium Halide−Trialkylaluminum Complexes in Toluene

The polymerization of methyl methacrylate and various acrylates initiated by ester enolates in the presence of cesium halide-trialkylaluminum complexes, Cs[Al n R 2n X] (n = 1, 2; R = Et, Bu'), in toluene has living and controlled character at -20 °C for methacrylates (X = Cl) and at -65 °C for n-butyl acrylate (X = F). Quantitative monomer conversions are usually reached, leading to polymers with narrow molecular weight distributions (M w /M n < 1.1). Kinetic investigations indicate a rather complex polymerization mechanism, and we assume an equilibrium between at least two active species. With this new initiating system, beside acrylate homopolymers, random and graft copolymers can be syn…

Zustände und Reaktionen des Carbanions bei der anionischen Polymerisation des Styrols

Anionic Polymerization of (Meth)acrylates in the Presence of Tetraalkylammonium Halide−Trialkyl Aluminum Complexes in Toluene. 3. Kinetic Investigations on Primary Acrylates

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.

NMR and Quantum-Chemical Study on the Structure of Ester Enolate−Aluminum Alkyl Complexes as Models of the Active Center in the Anionic Polymerization of Methacrylates in Toluene

6Li and 13C NMR on ethyl α-lithioisobutyrate (EiBLi) and quantum-chemical (DFT) calculations on methyl α-lithioisobutyrate (MiBLi) were used to elucidate the structure of the active center in the anionic polymerization of methacrylates in the presence of triethylaluminum (AlEt3) in toluene. This study reveals ester enolate/aluminum alkyl complexes with different degrees of association, (MiBLi·AlEt3)n (n = 1, 2, 4), and different stoichiometries, MiBLi·xAlEt3 (x = 1, 2). In the presence of methyl pivalate (MPiv), which is taken as a model compound for the monomer and polymer, complexes such as (MiBLi·MPiv·AlEt3)n (n = 1, 2) are formed. These complexes can dissociate into MiBLi·2AlEt3 and MPi…

Living and Controlled Anionic Polymerization of Methacrylates and Acrylates in the Presence of Tetraalkylammonium Halide-Alkylaluminum Complexes in Toluene

The size of both the cation and the anion of added NR4 X influences the rate of living polymerization of acrylates and methacrylates with alkylaluminum compounds. This controlled reaction, which occurs near to room temperature, provides unimodal polymers with narrow molecular-weight distributions. The complex shown to the right is suggested as a possible active species. R=Me, Et, nBu; R'=Me, Et; X=Cl, Br, I.

Novel initiating systems for the living polymerization of acrylates and methacrylates

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…