Synthesis of Telechelic Oligomers via Atom Transfer Radical Polymerization, 3

Otazaghine, Belkacem; Boutevin, Bernard

doi:10.1002/macp.200400187

Cited by 21 publications

(14 citation statements)

References 16 publications

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“…Those poly(tert-butyl acrylate) (PtBA) molecules mostly observed as intact alkali adducts in MALDI were sampled in early stages of polymerization, that is, at monomer conversion of 36% (Bednarek, Biedron, & Kubisa, 1999), 36-56% (Bernaerts & Du Prez, 2005), and 66% (Zhang et al, 2008). Similarly, MALDI mass spectra displaying major distribution of intact polyisobornylacrylate (Dervaux et al, 2008), poly(3-ethyl-3-(acryloyloxy)methyloxetane) (Singha, de Ruiter, & Schubert, 2005a), poly(2-ethylhexylacrylate) (Vidts, Dervaux, & Du Prez, 2006), or poly(butyl a-fluoroacrylate) (Otazaghine & Boutevin, 2004) were obtained for polymers sampled at monomer conversion of 27%, 30%, 56%, and 63%, respectively. In contrast, intact dormant species were no longer mass-detected upon MALDI of polymers obtained at later stages of polymerization, as reported for example for ATRP copolymerization of MA with 1-octene (Venkatesh et al, 2004b).…”

Section: B Maldi Of Atrp Poly(acrylate)smentioning

confidence: 99%

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MALDI of synthetic polymers with labile end‐groups

Charles

2013

Mass Spectrometry Reviews

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Mass spectrometry is increasingly used in the field of synthetic polymers as a fast and accurate technique for end-group analysis. More particularly, matrix-assisted laser desorption/ionization (MALDI) has gained much popularity because it allows quite simple mass spectra to be obtained, displaying a single distribution for each polymeric species present in the sample, in contrast to electrospray ionization (ESI) which readily promotes multiple charging for most polymers. A soft ionization process, ensuring the integrity of the species upon transfer into gas phase ions, is however mandatory for polymer end-group analysis since information about the chain terminations mainly rely on the m/z values measured for polymer adducts. As compared to ESI, MALDI is sometimes suspected to be a quite "hard" ionization technique, leading to spontaneous dissociation of ionized species either in the source or during their flight time. This issue is of particular concern for polymers carrying so-called fragile end-groups arising from their mode of synthesis. In particular, controlled radical polymerization (CRP) processes, one of the most important advances in the field of polymer science during the last 20 years, allow the production of polymers with well-defined molecular distribution and low polydispersities, but they are all based on the low dissociation energy of the chemical bond between the last monomer and the terminating group. As a result, if macromolecules are activated while being ionized, this end-group is prone to fragmentation and ions measured in the mass spectra do no longer reflect the original chain composition. However, different results are reported in the literature about the ability of MALDI to generate intact ions from CRP synthetic polymers. This article reviews MALDI MS data reported for synthetic polymers produced by atom transfer radical polymerization (ATRP), reversible addition-fragmentation transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP), the three most studied CRP techniques. The general principle of each polymerization process, which defines the structure of the end-groups in both targeted macromolecules and species arising from eventual side-reactions, is first briefly presented. An overview of MALDI data reported for samples obtained upon polymerization of different monomers are then commented for each polymerization techniques with regards to the success of the ionization method to generate intact cationic adducts and its propensity to distinguish in-source fragments from polymerization side-products.

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Section: B Maldi Of Atrp Poly(acrylate)smentioning

confidence: 99%

“…CuBr/PMDETA/MBP DCTB/NaTFA ( Dervaux et al, 2008) Butyl α-fluoroacrylate CuBr/HMTETA/MBIB PFCA/NaI (Otazaghine & Boutevin, 2004)…”

Section: Isobornyl Acrylatementioning

confidence: 99%

MALDI of synthetic polymers with labile end‐groups

Charles

2013

Mass Spectrometry Reviews

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“…An alternative is to prepare an oligomer with the desired chain end at the a-end and then couple together the x-halide ends. This has recently been reported for the synthesis of ditelechelic polystyrene or butyl a-fluoroacrylate with ester end groups as exemplified in Scheme 5 for styrene [23,24].…”

Section: Atom Transfer Radical Polymerizationmentioning

confidence: 96%

The use of radical polymerization in the synthesis of telechelic oligomers

Rimmer

Collins

2006

Reactive and Functional Polymers

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“…[18] On the contrary, in the case of acrylate monomers, the coupling rate was weaker than for styrene. [19,20] However, it has been possible to get hydroxy-telechelic poly(methyl methacrylate) by ATRC which was, in that case, carried out in the presence of styrene. [21] The latter reacted with acrylate radicals produced in the presence of copper halide and formed styrene terminated macroradicals which combined in a manner similar to polystyrene chains.…”

Section: Full Papermentioning

confidence: 99%

Synthesis via ATRP and Anchoring Properties of Ammonium‐Terminated Monofunctional or Telechelic Polystyrenes

Toquer¹,

Monge²,

Antonova³

et al. 2007

Macro Chemistry & Physics

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Mono‐ and di‐(trimethylammonium)‐terminated polystyrenes with similar molar masses were synthesized. Bromopolystyrenes were first prepared by atom transfer radical polymerization (ATRP) using (N‐Boc‐propylamino)‐2‐bromoisobutyrate as initiator and Cu(I)Br/2,2′‐bipyridine as catalytic system in bulk at 110 °C. α,ω‐Telechelic polymer with double molecular weight with respect to the starting polystyrene was then obtained under atom transfer radical coupling process using 2,2′‐bipyridine and copper(0) mediated reductive conditions in anisole. Final (trimethylammonium)‐terminated polystyrenes were eventually obtained after removal of the tert‐butyloxycarbonyl group and permethylation reactions. Intermediate and final polymers were characterized by 1H NMR. The aligning properties of the obtained polymers for liquid crystals have been investigated. Pretilt and zenithal anchorings on ITO/glass substrates were measured. Finally, the possibility for the telechelic polystyrene to form a network in an inverted microemulsion was also considered.magnified image

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Synthesis of Telechelic Oligomers via Atom Transfer Radical Polymerization, 3

Cited by 21 publications

References 16 publications

MALDI of synthetic polymers with labile end‐groups

MALDI of synthetic polymers with labile end‐groups

The use of radical polymerization in the synthesis of telechelic oligomers

Synthesis via ATRP and Anchoring Properties of Ammonium‐Terminated Monofunctional or Telechelic Polystyrenes

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