Anionic Polymerization of Pivalolactone Initiated by Alkali Metal Alkoxides

Jedliński, Zbigniew; Kurcok, Piotr; Kowalczuk, Marek; Matuszowicz, Andrzej; Dubois, Philippe; Jérôme, Robert; Kricheldorf, Hans R.

doi:10.1021/ma00125a035

Cited by 20 publications

(21 citation statements)

References 7 publications

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“…However, it can be postulated that the molar mass distribution of such samples synthesized at high temperatures is close to 2 because of some interchain transesterification reactions and whatever their molar mass. Such result was already observed for ε‐caprolactone, L ‐lactide, or ester cyclics polymerized in bulk or in solution conditions at temperature above the melting temperature 33, 34. Figure 7 shows the dependence of the zero shear viscosity versus M n .…”

Section: Resultssupporting

confidence: 72%

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Gautier

Fuertès

Cassagnau

et al. 2009

J. Polym. Sci. A Polym. Chem.

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Ring-opening polymerization (ROP) of glycolide was studied in melt conditions and in the presence of two different initiators: 1-dodecanol and 1,4-butanediol and tin(II) 2-ethylhexanoate as catalyst. Its subsequent polymerization provided poly (glycolic acid) with controlled molar masses ranging from 2000 to 42,000 g/mol with well-defined structures characterized by NMR. Their thermal properties were evaluated by DSC analysis, and a glass transition temperature at infinite molar mass (T g1 ) of 44.8 C was thus calculated. From rheological data, the critical molar mass for entanglement, M c , was estimated to be near 11,000 g/mol. Furthermore, in situ polymerizations were also performed between the plates of the rheometer within a same temperature range from 210 to 235 C. The variation of the storage and loss moduli during the polymerization step have been monitored by time sweep oscillatory experiments under an angular frequency x ¼ 10 rad/s. Finally, the development of an inverse rheological method allowed to calculate the bulk polymerization kinetics in the temperature range 200-230 C.

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Section: Resultssupporting

confidence: 72%

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Gautier

Fuertès

Cassagnau

et al. 2009

J. Polym. Sci. A Polym. Chem.

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“…Metal alkoxides are very effective initiators for ring‐opening polymerization of lactones. Sodium and potassium alkoxides are well known to promote anionic‐type polymerization but often lead to significant side reactions 37–39. Metal alkoxides containing free p‐, d‐ or f‐orbitals (e.g.…”

Section: Homogeneous Catalyst Systemsmentioning

confidence: 99%

Heterogeneous ring‐opening polymerization of lactones for biomedical applications

Khan

Schué

George

2009

Polymer International

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Catalysis of the ring‐opening reaction of L‐lactide and ε‐caprolactone to form the corresponding biodegradable polyesters is frequently performed using organometallic compounds such as tin(II) 2‐ethylhexanoate, which operates by a living, coordination insertion mechanism. For biomedical applications, non‐toxic calcium salts have been researched but these rarely approach the same efficiency. The use of heterogeneous immobilized catalysts offers an alternative approach, but competing reactions such as transesterification affect the final molecular weight and polydispersity. The formation of hybrid materials by using silica as the initiation site offers the prospect of biomaterials with novel properties. Copyright © 2009 Society of Chemical Industry

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“…The initiator attack occurs at carbonyl carbon C2 and the ring opens in the acyl-oxygen position ( a in Figure 1). However, the polymer chain growing center type (alcoholate or carboxylate) strongly depends on the β -lactone structure, i.e., the presence of substituents at the C3 carbon of the lactone ring [32,33]. In the case of β -butyrolactone, the crotonate and 3-hydroxybutyrate salts generated in the preinitiation step are the real initiators in this anionic ROP.…”

Section: Introductionmentioning

confidence: 99%

Anionic Polymerization of β-Butyrolactone Initiated with Sodium Phenoxides. The Effect of the Initiator Basicity/Nucleophilicity on the ROP Mechanism

et al. 2019

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It was shown that selected sodium phenoxide derivatives with different basicity and nucleophilicity, such as sodium p-nitrophenoxide, p-chlorophenoxide, 1-napthoxide, phenoxide and p-methoxyphenoxide, are effective initiators in anionic ring-opening polymerization (AROP) of β-butyrolactone in mild conditions. It was found that phenoxides as initiators in anionic ring-opening polymerization of β-butyrolactone behave as strong nucleophiles, or weak nucleophiles, as well as Brønsted bases. The resulting polyesters possessing hydroxy, phenoxy and crotonate initial groups are formed respectively by the attack of phenoxide anion at (i) C2 followed by an elimination reaction with hydroxide formation, (ii) C4 and (iii) abstraction of acidic proton at C3. The obtained poly(3-hydroxybutyrate) possesses carboxylate growing species. The ratio of the observed initial groups strongly depends on the basicity and nucleophilicity of the sodium phenoxide derivative used as initiator. The proposed mechanism of this polymerization describes the reactions leading to formation of observed end groups. Moreover, the possibility of formation of a crotonate group during the propagation step of this polymerization is also discussed.

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Anionic Polymerization of Pivalolactone Initiated by Alkali Metal Alkoxides

Cited by 20 publications

References 7 publications

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Synthesis and rheology of biodegradable poly(glycolic acid) prepared by melt ring‐opening polymerization of glycolide

Heterogeneous ring‐opening polymerization of lactones for biomedical applications

Anionic Polymerization of β-Butyrolactone Initiated with Sodium Phenoxides. The Effect of the Initiator Basicity/Nucleophilicity on the ROP Mechanism

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