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See detailThe in situ formation of a new initiator system for the syndiotactic anionic polymerization of methyl methacrylate in toluene at 0°C
Zundel, Thomas; Teyssié, Philippe; Jérôme, Robert ULg

in Polymer (2002), 43(25), 7191-7193

This paper reports on an efficient 'in-situ' one pot synthesis of an initiatior/ligand adduct, which can be used to initiate the anionic polymerization of methyl methacrylate in toluene at 0 °C ... [more ▼]

This paper reports on an efficient 'in-situ' one pot synthesis of an initiatior/ligand adduct, which can be used to initiate the anionic polymerization of methyl methacrylate in toluene at 0 °C. Predominantly syndiotactic PMMA is formed. [less ▲]

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See detailRecent achievements in anionic polymerization of (meth)acrylates
Jérôme, Robert ULg; Teyssié, Philippe; Vuillemin, Bruno et al

in Journal of Polymer Science. Part A, Polymer Chemistry (1999), 37(1), 1-10

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 ... [more ▼]

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. [less ▲]

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See detailNew 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
Zune, Catherine; Zundel, Thomas; Dubois, Philippe ULg et al

in Journal of Polymer Science. Part A, Polymer Chemistry (1999), 37(14), 2525-2535

Copolymerization of binary mixtures of alkyl (meth)acrylates has been initiated in toluene by a mixed complex of lithium silanolate (s-BuMe2SiOLi) and s-BuLi (molar ratio > 21) formed in situ by reaction ... [more ▼]

Copolymerization of binary mixtures of alkyl (meth)acrylates has been initiated in toluene by a mixed complex of lithium silanolate (s-BuMe2SiOLi) and s-BuLi (molar ratio > 21) formed in situ by reaction of s-BuLi with hexamethylcyclotrisiloxane (D3). 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-BuMe2SiOLi 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). [less ▲]

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See detailNew ligands for the living high-molecular-weight anionic (co)polymerization of acrylates in toluene at 0°C.1,2 3. Ligation of sec-butyllithium by lithium silanolates
Zundel, Thomas; Teyssié, Philippe; Jérôme, Robert ULg

in Macromolecules (1998), 31(17), 5577-5581

sec-Butyllithium combined with a new family of ligands, (i.e., lithium silanolates), has been used to initiate the ligated anionic polymerization of n-butyl acrylate (BuA) in toluene at low temperature ... [more ▼]

sec-Butyllithium combined with a new family of ligands, (i.e., lithium silanolates), has been used to initiate the ligated anionic polymerization of n-butyl acrylate (BuA) in toluene at low temperature. Compared to other μ-ligands, sBuMe2SiOLi is a more efficient stabilizer of the active centers. Thus, under selectively chosen reaction conditions, the polymerization proceeds quantitatively at −40 °C, producing a high-molecular-weight polymer with narrow-molecular-weight distribution (Mw/Mn < 1.2). When the copolymerization of BuA is initiated by a living {PMMALi, 5·sBuDLi} in toluene at −78 °C, the experimental data agree with a well-controlled block copolymerization reaction, since the final molecular-weight distribution is very narrow (Mw/Mn ≤ 1.1) and the polymerization efficiency very high. [less ▲]

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See detailLiving anionic polymerization of (meth)acrylic esters : new mechanistic concepts and resulting materials
Teyssié, Philippe; Baran, Janusz; Dubois, Philippe ULg et al

in Macromolecular Symposia (1998), 132

As an illustration of the frantic development of (meth)acrylic esters anionic polymerization during the last decade, three significant breakthroughs will be presented and analyzed: - extension of the LAP ... [more ▼]

As an illustration of the frantic development of (meth)acrylic esters anionic polymerization during the last decade, three significant breakthroughs will be presented and analyzed: - extension of the LAP (ligated anionic polymerization) concept to the practical synthesis of both high iso- or syndio high MW PMMA; - the production of "perfect" hydrocarbon gels from tailored PMMA-polybutadiene-PMMA triblock copolymers; - the use of reactivity "boosters" allowing to climb back up the nucleophilic reactivity scale, i.e. initiating styrene, dienes and (meth)acrylates polymerization with alcoholates and silanolates. [less ▲]

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See detailNew ligands for the living isotactic anionic polymerization of methyl methacrylate in toluene at 0°C. 2. 7Li NMR analysis of sec-butyllithium ligated by lithium silanolates
Zundel, Thomas; Zune, Catherine; Teyssié, Philippe et al

in Macromolecules (1998), 31(13), 4089-4092

The mixed associated species {xsBuLi, (y − x)sBuMe2SiOLi} formed by reaction of sec-Butyllithium (sBuLi) with octamethylcyclotetrasiloxane (Me2SiO)4 in toluene have been used to initiate the anionic ... [more ▼]

The mixed associated species {xsBuLi, (y − x)sBuMe2SiOLi} formed by reaction of sec-Butyllithium (sBuLi) with octamethylcyclotetrasiloxane (Me2SiO)4 in toluene have been used to initiate the anionic polymerization of methyl methacrylate (MMA) in that solvent at 0 °C. The active species generated by this new type of initiator have been characterized by 7Li NMR at 0 °C. The 7Li NMR spectra of sBuLi and sBuMe2SiOLi mixtures in toluene show that only one single type of {sBuLi, 5sBuMe2SiOLi} mixed species prevails at [sBuMe2SiOLi]/[sBuLi] molar ratios higher than ca. 21, as result of a large excess of {6sBuMe2SiOLi} species. The 7Li NMR has also concluded to the formation of {PMMALi, 5sBuMe2SiOLi} species upon the addition of MMA to that initiator solution, supporting the theory that only one type of ionic species is active during the MMA conversion. These active centers are stable for at least 1 h at 0 °C as confirmed by 7Li NMR. [less ▲]

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See detailClimbing back up the nucleophilic reactivity scale. Use of cyclosila derivatives as reactivity boosters in anionic polymerization
Zundel, Thomas; Baran, Janusz; Mazurek, Mieczyslaw et al

in Macromolecules (1998), 31(9), 2724-2730

It has been well-known for a very long time that, for anionic homo-polymerization or sequential copolymerization to occur, it is mandatory that the relative nucleophilic reactivity of the initiating ... [more ▼]

It has been well-known for a very long time that, for anionic homo-polymerization or sequential copolymerization to occur, it is mandatory that the relative nucleophilic reactivity of the initiating species be equal to or larger than the one of the (co)monomer. However, the results described in this paper demonstrate that such a classic rule can be circumvented in some cases. Indeed, it is reported for the first time that potassium trimethylsilanolate, and “living” potassium poly(ethylene oxide), both of which are unable to initiate styrene or methyl methacrylate (MMA) polymerization, can be converted from oxyanionic active ends to silyl anionic ones by reacting with cyclic disila derivatives, so allowing the homopolymerization and sequential (co)polymerization of styrene or MMA to proceed in a controlled manner. [less ▲]

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See detailNew ligands for the living isotactic anionic polymerization of methyl methacrylate in toluene at 0°C. 1. Ligation of butyllithium by lithium silanolates
Zundel, Thomas; Teyssié, Philippe; Jérôme, Robert ULg

in Macromolecules (1998), 31(8), 2433-2439

sBuLi and tBuLi have been combined with a new family of ligands, i.e. lithium silanolates, and used as initiators for the ligated anionic polymerization (LAP) of methyl methacrylate (MMA) in toluene at 0 ... [more ▼]

sBuLi and tBuLi have been combined with a new family of ligands, i.e. lithium silanolates, and used as initiators for the ligated anionic polymerization (LAP) of methyl methacrylate (MMA) in toluene at 0 °C. Compared to other known μ-ligands, the accordingly formed Bu(Me2)SiOLi are more efficient stabilizers for the active centers. Under appropriate reaction conditions, a fast polymerization proceeds quantitatively without self-termination at 0 °C and leads to high molecular weight polymer of narrow molecular weight distribution (Mw/Mn < 1.2) and high isotacticity (90% isotactic triads). [less ▲]

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