Catherine Zune

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Abstract Ligation of the anionic species responsible for the polymerization (LAP) of alkyl(meth)acrylates has much contributed to improve polymerization control. This ligated anionic polymerization has been firstly studied by using model compounds, such as low molecular weight lithium ester enolates. Recently, effort has been devoted to the direct analysis of the species that propagate the anionic polymerization of (meth)acrylates. In addition to IR, multinuclear NMR spectroscopy has been very instrumental in the elucidation of the structure and aggregation of the active species and how these characteristic features are modified by the addition of various types of ligands. This substantial progress in the characterization of the polyalkyl(meth)acrylate anions, ligated or not, is reported in this review.

Recent achievements in anionic polymerization of (meth)acrylates

The constant progress of the anionic polymerization of (meth)acrylates is discussed from both the fundamental and practical points of view. A special attention is paid to the improved macromolecular engineering of (meth)acrylate-based (co)polymers. The resulting most important materials and the scaling-up process needed for their production are also emphasized. The recent developments witness for the healthy state of the anionic polymerization of these polar monomers.

New initiator system for the anionic polymerization of (meth)acrylates in toluene. IV. Random copolymerization of (meth)acrylates in toluene initiated by s‐BuLi ligated by lithium silanolates

Copolymerization of binary mixtures of alkyl (meth)acrylates has been initiated in toluene by a mixed complex of lithium silanolate -(s-BuMe 2 SiOLi)- and s-BuLi (molar ratio > 21) formed in situ by reaction of s-BuLi with hexamethylcyclotrisiloxane (D 3 ). Fully acrylate and methacrylate copolymers, i.e., poly(methyl acrylate-co-n-butyl acrylate), poly(methyl methacrylate-co-ethyl methacrylate), poly(methyl methacrylate-co-n-butyl methacrylate), poly(methyl methacrylate-co-n-butyl methacrylate), poly(isobornyl methacrylate-co-n-butyl methacrylate), poly(isobornyl methacrylate-co-n-butyl methacrylate) of a rather narrow molecular weight distribution have been synthesized. However, copolymerization of alkyl acrylate and methyl methacrylate pairs has completely failed, leading to the selective formation of homopoly(acrylate). As result of the isotactic stereoregulation of the alkyl methacrylate polymerization by the s-BuLi/s-BuMe 2 SiOLi initiator, highly isotactic random and block copolymers of(alkyl) methacrylates have been prepared and their thermal behavior analyzed. The structure of isotactic poly(ethyl methacrylate-co-methyl methacrylate) copolymers has been analyzed in more detail by Nuclear Magnetic Resonance (NMR).

Anionic synthesis of cyclic anhydride end-capped poly(methyl methacrylate)

This paper reports on the anionic synthesis of poly(methyl methacrylate) chains end-capped by cyclic anhydride. The method is based on the chemical derivatization of a precursor tert-butyl diester end-group. Compared to the thermal modification, which was previously used, this method allows intermolecular coupling and polymer degradation to be avoided. But up to now, the final anhydride content remains moderate and has still to be improved

Anionic synthesis of [1,4-poly(diene)-b-syndiotactic poly(methyl methacrylate)] diblock copolymers: 7Li NMR study of the intermediate reaction of lithium poly(diene) anion with 1,1-diphenylethylene

The end-capping with 1,1-diphenylethylene (DPE) of living 1,4-poly(diene) lithiated anions prepared in cyclohexane (Chx) and toluene is a major but poorly controlled step in the synthesis of syndiotactic poly(methyl methacrylate) (sPMMA) containing block copolymers. The kinetics of the reaction have been studied by means of 7 Li NMR not only in Chx and toluene but also in their mixtures with polar solvents. since the solvent polarity must be increased for MMA to be predominantly converted into sPMMA. Although the addition of a polar solvent (tetrahydrofuran (THF), diethyl ether) to Chx and toluene is known to increase the reactivity of living polymeric anions, contaminating lithium salts, such as lithium hydroxide, slow down the end-capping reaction even when 10 vol.-% polar solvent is added. Moreover, the polymeric diphenylalkyllithium anions are unstable in 1/9 (v/v) THF/Chx mixture, as a result of the nucleophilic attack of THF. On the basis of all these observations, new experimental conditions are proposed for improving the control of the anionic block copolymerization of 1,3-dienes and MMA to yield 1,4-poly(diene) and sPMMA containing block copolymers.

Anionic polymerization of (meth)acrylic monomers: anionic polymerization of tert-butyl methacrylate in toluene

The anionic polymerization of tBMA initiated by an organolithium compound in toluene at low temperature (−78 °C and 0 °C) has been revisited. Under these experimental conditions, no ‘livingness’ is reported, consistently with formation of an important fraction of oligomers (Mn = 650). © 1999 Society of Chemical Industry

Analysis of living tert-butyl methacrylate oligoanions in tetrahydrofuran by NMR spectroscopy, viscosity and light scattering

Previous kinetic studies concluded on the aggregation of the anionic chain ends of living tert-butyl methacrylate oligomers [PtBMA - , Li + ] in THF at low temperature. This aggregation has been confirmed by viscosimetry, light scattering and gradient field NMR techniques in a range of temperature from 253 K to 298 K. These techniques have been systematically used for the analysis of both the living oligomers and the same chains recovered after hydrolysis of the anionic end groups. The structure of the growing anionic species was analyzed by means of 13 C and 7 Li NMR spectroscopy. 13 C NMR required the selective labeling of the last monomer units by 13 C atoms.