Counterion and solvent effects on the anionic polymerization of β-butyrolactone initiated with acetic acid salts

Kawalec, Michał; Śmiga-Matuszowicz, Monika; Kurcok, Piotr

doi:10.1016/j.eurpolymj.2008.09.008

Cited by 25 publications

(24 citation statements)

References 60 publications

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“…In 2008, Kurcok et al demonstrated that the reaction rates of anionic ROPs of BL from various carboxylate salts are strongly dependent on both the solvent polarity and the size of the counterion . Studies were undertaken comparing various metal‐based carboxylates, activated by crown‐ether (or not), to tetrabutylammonium acetate (TBAA) in benzene, THF and DMSO.…”

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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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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“…Therefore, several attempts to use a catalyst based on much less toxic metal compounds are being undertaken [2,6,11,[22][23][24][25][26][27]. The anionic polymerization of β-butyrolactone had been widely studied [27][28][29][30][31][32][33][34][35][36][37][38][39][40], and in general polymers with low molecular weight were obtained. Relatively low toxic alkali metal hydrides are among the initiators used for this purpose [27], nevertheless, they have not been used so far for the synthesis of copolymers of (R,S)-BL and CL.…”

Section: Introductionmentioning

confidence: 99%

Ring-opening copolymerization of (R,S)-β-butyrolactone and ε-caprolactone using sodium hydride as initiator

Monsalve¹,

Contreras²,

Laredo³

et al. 2010

Express Polym. Lett.

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Abstract. Copolymers of racemic β-butyrolactone ((R,S)-BL) and ε-caprolactone (CL), were synthesized by ring-opening polymerization initiated by sodium hydride (NaH). The initiator exhibited a satisfactory catalytic activity, producing copolymers whose yields are greatly influenced by the feed monomer ratio, CL/BL. All polymers obtained were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide angle X-rays scattering, WAXS. The molar composition of copolyesters determined by 1 H-NMR spectra, showed that the incorporation of CL is favoured over the incorporation of (R,S)-BL. Gel permeation chromatography and 13 C-NMR spectra indicated that CL/BL copolymers had block sequence distribution. The TGA analysis of copolymers showed that these copolymers are stable up to temperatures near 200°C, followed by a decomposition process in two steps; the first one is attributed to the (R,S)-BL block degradation and the second to the remaining PCL block. The crystallization process of these copolymers was studied by DSC and WAXS showing that the amorphous (R,S)-BL segments chains did not affect the crystallinity of the PCL blocks.

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“…In contrast to unsubstantiated four membered β-propiolactone, β-butyrolactone (BL) is not polymerized by common anionic initiators. However, these initiators, when activated by the addition of macrocyclic ligands such as crown ethers or cryptands, are able to initiate the polymerization of BL to PHB, i.e., the simplest PHA analogue [20,21]. The same effect may be achieved by using bulky counterions or suitable highly polar aprotic solvents, e.g., DMSO [22,23].…”

Section: Bioactive Oligomers Of Phb Analoguementioning

confidence: 99%

Bioactive oligomers from natural polyhydroxyalkanoates and their synthetic analogues

2017

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Contemporary reports on the bioactive oligomers derived from natural aliphatic co-polyesters (PHA) and their synthetic analogues, formed through anionic ring-opening polymerization (ROP) of β-substituted β-lactones are presented. Synthetic routes for such oligomers, developed mostly by Polish authors, are discussed. The described approaches enable design of novel biodegradable and bioactive oligomers for diverse applications in medicine, cosmetic industry and agrochemistry. Otrzymywanie bioaktywnych oligomerów z naturalnych biopoliestrów i ich syntetycznych analogówStreszczenie: Przedstawiono przegląd aktualnych wyników badań dotyczących bioaktywnych oligomerów otrzymywanych z naturalnych alifatycznych ko-poliestrów (PHA) oraz ich syntetycznych analogów, uzyskanych na drodze anionowej polimeryzacji z otwarciem pierścienia (ROP) β-podstawionych β-laktonów. Omówiono ścieżki syntezy tych oligomerów opracowane głównie przez polskich badaczy. Zaprezentowane metody umożliwiają projektowanie nowych biodegradowalnych, a zarazem bioaktywnych oligomerów mogących znaleźć różnorodne zastosowania w medycynie, przemyśle kosmetycznym i agrochemii.Słowa kluczowe: poliester alifatyczny, anionowa polimeryzacja, oligomer bioaktywny, β-podstawiony β-lakton.

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Counterion and solvent effects on the anionic polymerization of β-butyrolactone initiated with acetic acid salts

Cited by 25 publications

References 60 publications

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

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

Ring-opening copolymerization of (R,S)-β-butyrolactone and ε-caprolactone using sodium hydride as initiator

Bioactive oligomers from natural polyhydroxyalkanoates and their synthetic analogues

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