Suppression du Stade d'Initiation dans une Polycondensation du Second Type: Ouverture des β‐Lactones par les Bétaïnes

Etienne, Y.; Soulas, R.

doi:10.1002/polc.5070040224

Cited by 17 publications

(5 citation statements)

References 43 publications

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“…Before the 1980s, the ROP of b-substituted b-lactones was promoted by acidic compounds through a cationic reaction, assuming that the steric hindrance of the substituent at the bposition prevailed over the role of the initiator. 92 Lewis acids such as FeCl 3 and AlEt 3 showed, in toluene at 50 C, similar activities (turnover frequency: TOF ¼ 0.2 h À1 ) for the ROP of rac-MLABe leading to PMLABe (no molar mass values were reported), as described by Vert and Lenz. stereoselectivity in line with that claimed for the ROP of other alkyl b-lactones (no further studies have yet conrmed these results).…”

Section: Cationic Rop Of Mlabesupporting

confidence: 64%

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Benzyl β-malolactonate polymers: a long story with recent advances

Jaffredo

Guillaume

2014

Polym. Chem.

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International audiencePoly (-benzyl malolactonate) (PMLABe) is an aliphatic renewable, biocompatible, biodegradable, hydrophobic polyester of the poly(hydroxyalkanoate) (PHA) family. Along with the hydrophilic parent poly(-malic acid) (PMLA), PMLABe and PMLA have been studied as materials for biomedical applications. Herein, advances on the synthesis of benzyl -malolactonate (MLABe) and the related alkyl -malolactonates (MLARs), PMLABe homopolymers and copolymers, are reviewed. Focus is placed on the ring-opening polymerization (ROP) of MLABe and on copolymers of MLABe, with relevant data on the performances of the initiating systems and on the PMLABes molecular characteristics, along with detailed mechanistic insights, being reported

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Section: Cationic Rop Of Mlabesupporting

confidence: 64%

“…Prior to the 1980s, the ROP of -substituted -lactones was promoted by acidic compounds through a cationic reaction, then assuming that the steric hindrance of the substituent at the -position was prevailing over the role of the initiator. 92 Lewis acids such as FeCl3 and AlEt3…”

Section: Cationic Rop Of Mlabementioning

confidence: 99%

Benzyl β-malolactonate polymers: a long story with recent advances

Jaffredo

Guillaume

2014

Polym. Chem.

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“…β‐Lactones, such as β‐propiolactone and β‐pivalolactone, were polymerized by pyridine‐based nucleophilic initiators more than 50 years ago . All the accumulated data suggest zwitterionic ring‐opening polymerization (ZROP).…”

Section: Zwitterionic and Anionic Metal‐free Rops Of β‐Lactonesmentioning

confidence: 99%

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Khalil

Cammas‐Marion

Coulembier

2019

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

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Organocatalysis offers a number of prospects in the polymer community and presents advantages over metal based and bio‐organic methods. The use of organic molecules for performing chemical reactions is not a new concept, and any research into organocatalytic reactions builds on a respected history. Compared to the organocatalysis of large lactones, which began in the early 2000s, the examples presented here will demonstrate that few metal‐free initiating systems had been applied to β‐lactones well before the beginning of the current millennium. These metal‐free initiating systems present indisputable advantages over metal‐based processes. In the following paper, ring‐opening polymerizations (ROPs) of various β‐lactones for the preparation of poly(hydroxyalkanoate)s will be presented, as will the types of mechanisms involved, that is, zwitterionic and anionic, and cationic or supramolecular‐based ROPs. The advantages and drawbacks of the different technics will be discussed in the domain, which, for us, is important in the overall production of bioplastics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 657–672

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“…More than 50 years ago, b-lactones such as b-propiolactone and bpivalolactone started to be polymerized by pyridine-based nucleophilic initiators. [13][14][15][16] For several reasons, the course of such ZROP was very complex, involving chain growth and step growth kinetics as well as elimination reactions regarding the type of initiator and monomer used. When moderate bases 17 such as pyridine, 4-methylpyridine and 4-(N,N-dimethylamino)pyridine (DMAP) were used for the ZROP of pivalolactone, 16 linear chains having one pyridinium ion and a carboxylate ion as end groups were observed by 1 H NMR and MALDI-ToF analyses.…”

Section: Pyridine-based Initiationmentioning

confidence: 99%