Olefin cross metathesis and ring-closing metathesis in polymer chemistry

Sinclair, Fern; Alkattan, Mohammed; Prunet, Joëlle; Shaver, Michael P.

doi:10.1039/c7py00340d

Cited by 61 publications

(60 citation statements)

References 70 publications

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“…This will provide telechelic polyethylenes with two phosphonic acid functions per chain that have not been depicting so far. Already largely used in organic and polymer chemistry, metathesis has been used to produce telechelic polymers through depolymerization of polydienes and polyalkeneamers via ADMET using monoalkenes as functionalization agent or by ring‐opening metathesis polymerization of cycloalkene in the presence of CTA . However, coupling two preformed polymers carrying an alkene chain end by metathesis has not been explored .…”

Section: Resultsmentioning

confidence: 99%

Monofunctional and Telechelic Polyethylenes Carrying Phosphonic Acid End Groups

Ottou

Norsic

D’Agosto

et al. 2018

Macromol. Rapid Commun.

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Monofunctional or telechelic polyethylenes (PEs) carrying phosphonic acid end groups are obtained from functional PE produced by catalyzed chain growth (CCG) on magnesium. CCG is first used to produce iodo-end-functionalized PE (PE-I) that is efficiently turned into phosphonate end-functionalized PE (PE-P(O)(OEt) ) in the presence of triethylphosphite through the Michaelis-Arbuzov reaction. A simple treatment of the resulting PE-P(O)(OEt) with bromotrimethylsilane leads to the targeted phosphonic acid end-functionalized PE (PE-P(O)(OH) ) for the first time. Vinyl-end-functionalized analogs (Vin-PE-P(O)(OEt) ) are produced using vinyl-end-functionalized PE-I (Vin-PE-I) recently obtained through CCG. A cross-metathesis reaction is then employed to couple Vin-PE-P(O)(OEt) and produce after treatment with bromotrimethylsilane the corresponding unprecedented α-ω-(diphosphonic acid) telechelic PE ((OH) (O)P-PE-P(O)(OH) ).

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Section: Resultsmentioning

confidence: 99%

Monofunctional and Telechelic Polyethylenes Carrying Phosphonic Acid End Groups

Ottou

Norsic

D’Agosto

et al. 2018

Macromol. Rapid Commun.

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“…Moreover, the resulting multi-allyl branched polymers constitute valuable intermediates towards the preparation of surface-functionalized "nanocylinders", as the peripheral allyl branches enable a post-polymerization functionalization via a number of straightforward reactions (eg. thiol radical addition, [22] epoxidation, [23] olefin metathesis, [24] hydrosilylation [12]….). We indeed demonstrated the preparation of cylindrical-like particles covered by siloxane chains, perfluorinated chains or else by ethyleneglycol chains, leading all to unique properties.…”

Section: Introductionmentioning

confidence: 99%

Preparation of multi-allylic dendronized polymers via atom-transfer radical polymerization

Schwartz

Moingeon

Roeser

et al. 2019

European Polymer Journal

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Atom-transfer radical polymerization (ATRP) was investigated to polymerize a styrene monomer carrying carbosilane dendrons with 6 terminal allyl branches. Polymers with a monomodal molar mass distribution and low polydispersity have been produced, while by comparison the free-radical polymerization technique led to chain transfer early in the polymerization. Steric effect brought by the dendrons result in a slow polymerization rate, leading to an apparent saturation of the degree of polymerization. By pushing up the polymerization conditions (eg. increase of temperature or concentration), interchain couplings started to take place, most likely from reactions at the allyl branches. These results are very similar to the ones previously reported for the anionic polymerization of this same multiallylic dendronized monomer.

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“…In this contribution, our focus is on the use of olefin cross‐metathesis (CM) to prepare a family of new monomers. Examples of CM in post‐polymerization modification in the literature are growing . Most recently, we demonstrated the first successful double metathesis on copolymers of lactide and β‐heptenolactone through manipulation of olefin reactivity .…”

Section: Introductionmentioning

confidence: 99%

“…Examples of CM in post-polymerization modification in the literature are growing. [25][26][27][28][29][30][31][32] Most recently, we demonstrated the first successful double metathesis on copolymers of lactide and b-heptenolactone through manipulation of olefin reactivity. 33 However, its use in prepolymerization modification of monomers is scarce.…”

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confidence: 99%

Cross‐metathesis functionalized exo‐olefin derivatives of lactide

Sinclair

Shaver

2018

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

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Poly(lactic acid) is at the forefront of research into alternative replacements to fossil fuel derived polymers, yet preparation of derivatives of this key biodegradable polymer remain challenging. This article explores the use of two derivatives of lactide, each of which features an exocyclic olefin, and their pre‐polymerization modification by olefin cross‐metathesis. Methylenation of lactide with Tebbe's reagent generates a novel 5‐methylenated lactide monomer, (3S,6S)‐3,6‐dimethyl‐5‐methylene‐1,4‐dioxan‐2‐one, complementing the previously reported 3‐methylenated (6S)‐3‐methylene‐6‐methyl‐1,4‐dioxan‐2,5‐dione. While ring‐opening of each monomer is not productive, olefin cross‐metathesis can be used to functionalize each of the exocyclic olefins to produce a family of monomers. The ring‐opening polymerization of these new monomers, and their hydrogenated congeners, is facilitated by organo‐ and Lewis‐acid catalysts. Together, they offer a new strategy for derivatizing and altering the properties of poly(lactic acid). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 741–748

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Olefin cross metathesis and ring-closing metathesis in polymer chemistry

Abstract: The use of olefin cross metathesis in preparing functional polymers, through either pre-functionalisation of monomers or post-polymerisation functionalisation is growing in both scope and breadth, as discussed in this review article.

Cited by 61 publications

References 70 publications

Monofunctional and Telechelic Polyethylenes Carrying Phosphonic Acid End Groups

Monofunctional and Telechelic Polyethylenes Carrying Phosphonic Acid End Groups

Preparation of multi-allylic dendronized polymers via atom-transfer radical polymerization

Cross‐metathesis functionalized exo‐olefin derivatives of lactide

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