New initiator system for the living anionic polymerization of tert-alkyl acrylates

Fayt, Roger; Forte, R.; Jacobs, Christian; Jérôme, Robert; Ouhadi, T.; Teyssié, Ph.; Varshney, Sunil K.

doi:10.1021/ma00172a058

Cited by 225 publications

(146 citation statements)

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“…The really efficient ligands discovered to date in this field may be classified into three groups, the structure of the most representative ones being shown in Scheme 2: 1. µ-type ligands, that form polycentric bonding with the metal ester enolate: metal alkoxides [38][39][40][41][42], aluminum alkyls [43][44][45], and inorganic salts [46][47][48][49]. 2. σ-type ligands, that form coordinative complexes with the metal counterion of the active species: crown ethers [50] and kryptands [51].…”

Section: Incentives To the Ligated Anionic Polymerization Of Polar Momentioning

confidence: 99%

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Zune

Jérôme

1999

Progress in Polymer Science

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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.

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Section: Incentives To the Ligated Anionic Polymerization Of Polar Momentioning

confidence: 99%

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Zune

Jérôme

1999

Progress in Polymer Science

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“…The mass spectrum exhibited four distinct ion distributions: one major one, (BuOPBA n O H)(GlyGlyGly)H ϩ ); and three with lower abundance, (BuOPBA n OH)Na ϩ (from residual sodium), (CH 3 OO PBA n O126-OCH 3 )(GlyGlyGly) 2 (H ϩ ) 2 (where 126 is an unsaturated BA unit (C 7 H 10 O 2 ), and the methoxy groups come from the terminator (CH 3 OH) used in the synthesis [12] and PBA ionized with GlyGlyGlyH ϩ and terminated with an unidentified 80-Da end group (this end group likely originates from the alkyl lithium initiator system used to make PBA [12,13]. As for PMMA, we were able to generate proton-bound complexes of PBA oligomers with different peptides and amino acids, represented by the generic formula (PBA n )(AA)H ϩ .…”

Section: Poly(butyl Acrylate)mentioning

confidence: 99%

Protonating polymer oligomers in the gas phase to change fragmentation pathways

Alhazmi

Mayer

2009

J. Am. Soc. Mass Spectrom.

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Ionization of polymers in mass spectrometry is usually achieved by forming metal ion adducts. The metal ion has been shown by Wesdemiotis to often play a spectator role in the collision-induced dissociation (CID) chemistry of these species, wherein they fragment according to a free-radical mechanism similar to that found in their pyrolysis. The result is a predominance of low-mass ions in the CID mass spectrum. We have changed this behavior by generating protonated oligomers in the gas phase by first forming proton-bound complexes of the oligomers with amino acids or peptides by electrospray ionization. These complexes dissociate first by loss of the amino acid/peptide to form protonated oligomers, which then undergo a unique fragmentation chemistry. In this article we discuss the results for poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA). Initially, protonated PMMA and PBA lose methanol and butanol, respectively, from the side chains of the respective monomers. The resulting PMMA-derived ion then undergoes a series of neutral losses corresponding to 32 and 28 Da, methanol and carbon monoxide. This continues as collision energy increases until a final, carbon-rich backbone ion is formed, which then undergoes a classic hydrocarbon fragmentation pattern. The PBA-derived ions are proposed to fragment by the loss of butylether molecules to form anhydride rings along the oligomer chain. The number of ether molecules lost corresponded to half the number of available side chains in the oligomer. The resulting poly-anhydride ion dissociates by small molecule loss. A though the predominant mode of ionization for peptides and proteins in mass spectrometry is protonation in solution, the same cannot be said for synthetic polymers. Typically, synthetic polymers such as poly(methyl methacrylate) (PMMA) are not basic enough in solution to acquire a proton from an added acid. To overcome this limitation, salts incorporating metal ions are usually added to the polymer/ solvent solution before electrospray ionization (ESI) (or to the polymer/matrix solution before ionization by matrix-assisted laser desorption/ionization). This generates gas-phase polymer oligomers ionized by the metal ion. This has consequences for the analysis of these oligomers by collision-induced dissociation (CID) mass spectrometry. For example, Jackson and Scrivens studied poly(alkyl methacrylates) (PAMAs), i.e., PMMA and poly(n-butyl methacrylate) (PBMA) by different mass spectrometry techniques [1][2][3][4][5][6][7]. In each case the CID mass spectrum was dominated by low mass-to-charge ratio (m/z) fragment ions. In the case of PMMA the fragments were proposed to be generated mainly by homolytic cleavage and 1,5 hydrogen rearrangement reactions along the polymer backbone [2,7]. Low-intensity peaks at high m/z were assumed to be formed by neutral losses and fragmentation along the polymer backbone [5]. The end result was a variety of fragment ion progressions each differing by one monomer unit. Bowers et al. proposed a mechanism that rat...

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“…As soon as the system was quenched, poly( 2) started to lose the protecting group [ / CH(CH 3 )-Teyssie and co-workers 37,38 demonstrated that the OOCCH 3 ] and the generated poly(HEMA) precipaddition of LiCl can be effective in the living anitated. The precipitation lasted 3 to 4 h. Figure 1 ionic polymerization of the acrylic monomers, bedepicts the 1 H-NMR spectra of the monomer (A) cause a m-type complex 39 is formed between LiCl and of its precipitated polymer (B).…”

Section: Anionic Polymerization Ofmentioning

confidence: 99%

A novel route to poly(2-hydroxyethyl methacrylate) and its amphiphilic block copolymers

Ruckenstein

Zhang

1998

J. Polym. Sci. A Polym. Chem.

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New initiator system for the living anionic polymerization of tert-alkyl acrylates

Cited by 225 publications

References 0 publications

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Protonating polymer oligomers in the gas phase to change fragmentation pathways

A novel route to poly(2-hydroxyethyl methacrylate) and its amphiphilic block copolymers

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