Pseudohalogens in atom transfer radical polymerization of methyl methacrylate

Singha, Nikhil K.; German, Anton L.

doi:10.1002/app.25491

Cited by 15 publications

(13 citation statements)

References 44 publications

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“…Apart from the case reported by Haddleton et al for polymers obtained at very low monomer conversion (<10%) and mainly generated as intact adducts in the gas phase (Haddleton et al, ), MALDI mass spectra of ATRP PMMA were usually shown to exhibit up to three distributions in addition to the expected (pseudo)halogen‐terminated one. PMMAs with a H end‐group were reported as minor species, either assigned to a disproportionation product, when detected together with oligomers with an unsaturated termination (Singha, Rimmer, & Klumperman, ; Jackson et al, ), or arising from hydrogen abstraction (Nonaka et al, ; Venkatesh & Klumperman, ; Singha & German, ). Radical termination is indeed well‐known to take place when targeting functionality close to 100%, particularly for low molecular weight PMMA polymers (Shipp, Wang, & Matyjaszewski, ; Zhang & Matyjaszewski, ).…”

Section: Maldi‐ms Of Atrp Polymersmentioning

confidence: 99%

“…The reaction proposed for its formation was supported by evolved gas GC‐MS and 13 C NMR analyses, respectively showing production of methyl bromide and concomitant formation of terminal ring formation upon heating (150°C) of PMMA‐Br samples (Borman et al, ). While the lactone‐terminated by‐product was observed to largely dominate MALDI mass spectra of brominated‐terminated PMMA (Borman et al, ; Jackson et al, ; Singha & German, ), its relative abundance as compared to the intact species was observed to decrease in MALDI data obtained for PMMA‐Cl (Singha, Rimmer, & Klumperman, ; Venkatesh & Klumperman, ; Jackson et al, ), suggesting that the carbon‐to‐chlorine bond is stronger than the carbon‐to‐bromine bond (Jackson et al, ). Figure illustrates typical relative intensities measured for distributions observed in MALDI mass spectra of ATRP PMMA.…”

Section: Maldi‐ms Of Atrp Polymersmentioning

confidence: 99%

“…CuBr/HMTETA/EBIB DHB (Singha et al, 2005) together with oligomers with an unsaturated termination (Singha, Rimmer, & Klumperman, 2004;Jackson et al, 2006), or arising from hydrogen abstraction (Nonaka et al, 2001;Venkatesh & Klumperman, 2004c;Singha & German, 2007). Radical termination is indeed well-known to take place when targeting functionality close to 100%, particularly for low molecular weight PMMA polymers (Shipp, Wang, & Matyjaszewski, 1998;Zhang & Matyjaszewski, 1999).…”

Section: -Ethyl-3-(acryloyloxy)methyloxetanementioning

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: Maldi‐ms Of Atrp Polymersmentioning

confidence: 99%

Section: Maldi‐ms Of Atrp Polymersmentioning

confidence: 99%

Section: -Ethyl-3-(acryloyloxy)methyloxetanementioning

confidence: 99%

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MALDI of synthetic polymers with labile end‐groups

Charles

2013

Mass Spectrometry Reviews

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“…Figure shows the TGA curves of st ‐PFMA, at ‐PFMA, and it ‐PFMA homopolymers prepared by the current anionic polymerization reactions. The degradation process involved in the FMA polymers or in the PFMA–BM crosslinked polymers occurs at several stages, as a result of scission of the vinylic ends and random scission of the polymer chain . During our investigation into the thermal properties of homopolymers through combined DSC and TGA analysis, we discovered an interesting phenomenon.…”

Section: Resultsmentioning

confidence: 88%

Anionic polymerization of biomass‐derived furfuryl methacrylate: Controlling polymer tacticity and thermoreversibility

Zhang

Chen

2013

J. Polym. Sci. Part A: Polym. Chem.

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Biomass‐derived furfuryl methacrylate (FMA) has been successfully polymerized for the first time by anionic polymerization to produce atactic (at‐), isotactic (it‐), or syndiotactic (st‐) poly(furfuryl methacrylate) (PFMA), depending on initiator structure and reaction conditions. Thermal properties of the PFMA materials are strongly affected by the polymer tacticity. Most notably, while both isotactic and syndiotactic polymers can undergo inter‐ or intrachain crosslinking reactions when heated to 290 °C, there is no evidence for the atactic polymer to perform the same reaction. Furthermore, the PFMA tacticity also greatly affects the amount of stable carbonaceous materials it produces when heated to 650 °C, with st‐PFMA forming the largest amount of such materials (26.9%), as compared to only 5.6% by at‐PFMA. Using the Diels–Alder (DA) “click reaction” between the reactive furfuryl group within the PFMA polymers as the diene equivalent and a bismaleimide as the dienophile, thermoreversible smart polymers have been successfully prepared. Thermoreversibility of the preformed crosslinked polymers has been demonstrated, thanks to the facile retro‐DA reaction upon heating and the DA reaction upon cooling of such self‐healing materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2793–2803

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“…The pyrolysis of PMBTFVB 2 homopolymer and PMBTFVB‐Br 3b macroinitiator processed in a one‐stage decomposition pattern and T d of PMBTFVB 2 and PMBTFVB‐Br 3b are recorded at 431 and 364 °C respectively. However, the thermolysis of PMBTFVB‐ g ‐PMMA 4f graft copolymer shows a multi‐step degradation process around about 169 and 500 °C, which corresponded to the weight loss of PMMA branches90, 91 and PMBTFVB backbone, respectively.…”

Section: Resultsmentioning

confidence: 99%

A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

Líu

Zhang

et al. 2010

J. Polym. Sci. A Polym. Chem.

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A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2p þ 2p] step-growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2-methyl-1,4-bistrifluorovinyloxybenzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether-based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N-bromosuccinimide and benzoyl peroxide. The grafting-from strategy was finally used to obtain the novel poly(2-methyl-1,4-bistrifluorovinyloxybenzene)-g-poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M w /M n 1.46) via ATRP of methyl methacrylate at 50 C in anisole initiated by the Br-containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine-containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether-based backbone.

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Pseudohalogens in atom transfer radical polymerization of methyl methacrylate

Cited by 15 publications

References 44 publications

MALDI of synthetic polymers with labile end‐groups

MALDI of synthetic polymers with labile end‐groups

Anionic polymerization of biomass‐derived furfuryl methacrylate: Controlling polymer tacticity and thermoreversibility

A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

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