Polyester obtained from dimethylketene and acetone: synthesis and characterization

Brestaz, Marc; Désilles, Nicolas; Lê, Guillaume; Bunel, Claude

doi:10.1007/s10965-012-0012-5

Cited by 4 publications

(3 citation statements)

References 57 publications

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“…127 The preparation of copolymers from ketenes and ketones has been pursued since the early days of ketene chemistry, and a recent example based on classic work of Natta is polyester synthesis from dimethylketene and acetone with initiation by n-BuLi. 128 A schematic representation with a possible initiation step and successive addition of acetone and dimethylketene monomers is shown (Scheme 22). 128 Modern spectroscopic examination confirms the perfectly alternating structure of the product polymer.…”

Section: Ketenes In Polymer Chemistrymentioning

confidence: 99%

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Ketenes and Other Cumulenes as Reactive Intermediates

2013

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Section: Ketenes In Polymer Chemistrymentioning

confidence: 99%

“…128 A schematic representation with a possible initiation step and successive addition of acetone and dimethylketene monomers is shown (Scheme 22). 128 Modern spectroscopic examination confirms the perfectly alternating structure of the product polymer.…”

Section: Ketenes In Polymer Chemistrymentioning

confidence: 99%

Ketenes and Other Cumulenes as Reactive Intermediates

2013

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“…In general, ketenes are very unstable products that cannot be stored and must be handled very carefully. The chemistry of ketenes is dominated by addition reactions with reagents having labile hydrogen atoms, nucleophiles or electrophiles, and they characteristically undergo cycloadditions with several types of compounds …”

Section: Introductionmentioning

confidence: 99%

Effect of tetra‐n‐butylammonium bromide salt on the cationic polymerization of dimethylketene and on the thermal properties of the obtained polyketones

Wang

Désilles

Burel

2014

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

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The cationic polymerization of dimethylketene is achieved in dichloromethane at −30 °C, using a stoichiometric mixture of aluminum bromide (AlBr3) and tetra‐n‐butylammonium bromide (n‐Bu4N+Br−) as initiator. Characterizations by 1H and 13C NMR show that the resulting polymers have a perfect polyketonic microstructure. Capillary viscosity, DSC, and SEC analysis show that for a constant monomer/initiator ratio, polymers synthesized in the presence of tetra‐n‐butylammonium bromide are more crystalline and have better properties than those produced only with AlBr3. Melting temperatures, inherent viscosities and average molecular weights are systematically higher. A good linearity is observed between ln (inherent viscosity) versus ln Mn true¯theory for the system with n‐Bu4N+Br−, showing a good control of the molecular weight by the initial feed ratio. The effect of this compound suggests a reversible equilibrium between active and dormant species, which limits the transfer and/or termination reactions, and enables a better control of the cationic polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1493–1499

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High Molecular Weight Polyester Obtained by Polymerization of Dimethylketene Using Metallocene Initiators: A Step toward Ziegler–Natta Supporting Application in Non‐Olefin Systems

Jiang

Désilles

Burel

2019

Macromol. Rapid Commun.

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In this report, highly active metallocene initiators are used for the polymerization of a ketene monomer, dimethylketene, which typically contains two adjacent double bonds (R2CCO). By using the methylzirconocene methyltriarylborate complex (Cp2ZrMe+MeB(C6F5)3−) as the activation system, associated with the possible cleavage of CC and CO bonds in ketene monomers, a structure‐specific and high‐molecular‐weight polyester (Mntrue¯ > 300 000 g mol−1) can be afforded. The resulting polyester structure, comprehensively characterized by NMR, indicates a significant reactive selectivity of the “bent‐sandwich” cationic site Cp2ZrMe+. It reveals that the positively charged zirconium (Zr+) prefers to coordinate with a negatively charged oxygen (O−) when it is already bonded to the carbon, while a negatively charged carbon (C−) will be assigned in priority if the oxygen–zirconium bond exists. This report allows for broadening the application field of metallocene initiators in non‐olefin reactions and deepening our insight into the mechanism of the living insertion/Ziegler–Natta polymerization.

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Polyester obtained from dimethylketene and acetone: synthesis and characterization

Cited by 4 publications

References 57 publications

Ketenes and Other Cumulenes as Reactive Intermediates

Ketenes and Other Cumulenes as Reactive Intermediates

Effect of tetra‐n‐butylammonium bromide salt on the cationic polymerization of dimethylketene and on the thermal properties of the obtained polyketones

High Molecular Weight Polyester Obtained by Polymerization of Dimethylketene Using Metallocene Initiators: A Step toward Ziegler–Natta Supporting Application in Non‐Olefin Systems

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