Structure and morphology of poly(?-hydroxybutyrate) synthesized by ring-opening polymerization of racemic (R,S)-?-butyrolactone with distannoxane derivatives

Arcana, I Made; Giani‐Beaune, O; Schué, François; Amass, W; Amass, Allan J.

doi:10.1002/1097-0126(200011)49:11<1348::aid-pi491>3.0.co;2-h

Cited by 26 publications

(6 citation statements)

References 28 publications

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“…The observed maximum of MS = 21.5 deviates largely from the value predicted from the BL/pyranose in‐feed ratio of 40, implying that there is a substantial upper limit in the efficiency for introducing BL monomers as side‐chains of CA. These results suggest that the ring‐opening graft copolymerization of BL with distannoxane is not ‘living‐like’, as has been pointed out by Arcana et al,8 in contrast to the situation with the polymerization of LLA catalyzed by Sn(II)Eht 13…”

Section: Resultsmentioning

confidence: 65%

“…Preliminary experiments revealed that BL did not polymerize in the presence of Sn(II)Eht, unlike the other cyclic esters used in this work. Therefore, the graft copolymerization of BL onto CA was carried out with distannoxane, which is known to be an effective catalyst for the chemical synthesis of PHB 5–8. As can be seen from the data in Table 1, the MS of CA‐ g ‐PHB rose abruptly until a reaction time of 240 min at which time the value reached a maximum of 21.5.…”

Section: Resultsmentioning

confidence: 99%

“…The analysis may be of significance not only from the standpoint of scientific generalization as is suggested in the opening paragraph, but also from a practical point of view, since the results should give an indication of whether the individual drawbacks of the thermal properties of the cellulose ester and PHAs can be overcome. In the present work, the synthesis of a new series of CA‐ g ‐PHAs was conducted with reference to earlier reports on the polymerization of BL5–8 and VL 9. Graft copolymerization of CA with CL, as another series, has already been investigated in our laboratory,10 and the transition data are cited here.…”

Section: Introductionmentioning

confidence: 99%

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Cellulose Acetate‐graft‐Poly(hydroxyalkanoate)s: Synthesis and Dependence of the Thermal Properties on Copolymer Composition

Teramoto

Ama

Higeshiro

et al. 2004

Macro Chemistry & Physics

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Summary: Several different series of cellulose acetate‐graft‐poly(hydroxyalkanoate)s (CA‐g‐PHAs) were synthesized over a wide range of compositions by the graft copolymerization of lactic acid, L‐lactide, (R,S)‐β‐butyrolactone, δ‐valerolactone and ε‐caprolactone onto the residual hydroxyl positions of CA, by virtue of a suitable catalyst, solvent and procedure for each individual case. To achieve a diversity of molecular architectures of the respective graft copolymer series, the degree of acetyl substitution (acetyl DS) of the CA starting material was also varied, resulting in different levels of the intramolecular density of grafts. The CA‐g‐PHAs thus obtained were subjected to differential scanning calorimetric measurements and the relationship between their molecular structure and thermal transition behavior was estimated, in comparison with some semi‐empirical equations available for polymer blends or comb‐like polymers. In particular, the composition dependence of the Tgs of the graft copolymers was represented well in terms of a formula proposed by Reimschuessel for comb‐like polymers, when CAs of acetyl DS ≈2 were employed as a trunk polymer. The deviation of the glass transition data from the model function was discussed in connection with the manner of graft modification.

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Section: Resultsmentioning

confidence: 65%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cellulose Acetate‐graft‐Poly(hydroxyalkanoate)s: Synthesis and Dependence of the Thermal Properties on Copolymer Composition

Teramoto

Ama

Higeshiro

et al. 2004

Macro Chemistry & Physics

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“…Numerous reports appear in the literature where 13 C NMR spectroscopy was used to identify the stereoregularity of the polyester . The carbonyl peak around 167 ppm is a particularly sensitive and effective signal, which provides the stereo information …”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterizations of new isotactic homopolyesters, statistical and block copolyesters derived of poly((S)‐3,3‐dimethylmalic acid) via the lactone route

Belibel

Azzouz

Barbaud

2015

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

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This article presents the synthesis of a new family of synthetic isotactic polyesters derived from poly((S)‐3,3‐dimethylmalic acid) (PDMMLA). These polyesters are prepared via the lactone route bearing functionalized groups in its main or side chain. The aim of this work is twofold: metabolism and stereochemistry. First, the synthesis of these new polyesters is chosen to provide biodegradable polyesters biocompatible and bioassimilable by the human body. Next, the molecular chain of this family contains a stereogenic center in the aim to provide 100% isotactic homopolymers and copolymers (statistical and block). Finally, these polymers have been characterized by several analytical techniques: FTIR, 1H and 13C NMR, SEC, DSC, and TGA. The greatest importance will be given to the 13C NMR and DSC to principally confirm the stereoregularity and crystallinity of these stereopolyesters. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1495–1507

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“…The polymerization was carried out with Bu 3 SnOMe to give low molecular weight PHB enriched in syndiotactic dyads ( P r = 0.70). More recently, Hori and Giani-Beaune reported a distannoxane catalyst that affords a predominantly syndiotactic PHB ( P r = 0.67) by a chain-end control mechanism. A better control of the polymerization allowed achieving higher molecular weight PHB at 40 °C within 95 h.…”

Section: Introductionmentioning

confidence: 99%

Syndiotactic-Enriched Poly(3-hydroxybutyrate)s via Stereoselective Ring-Opening Polymerization of Racemic β-Butyrolactone with Discrete Yttrium Catalysts

et al. 2009

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The mechanism of the ring-opening polymerization of rac-β-butyrolactone using yttrium complexes supported by dianionic aminoalkoxybis(phenolate) ligands as initiators has been investigated by NMR and shown to occur via a coordination-insertion pathway. The microstructure of the resulting syndiotactic-enriched poly(3-hydroxybutyrate)s (PHBs, P r up to 0.94) has been studied by 13C NMR spectroscopy, enabling a detailed assignment of resonances at the diad and triad levels. On this basis, a statistical Bernoullian analysis has been performed which evidenced that syndioselectivity originates from a chain-end control. Some thermal properties of these PHBs have been studied by WAXD and thermoanalytical techniques and shown to be markedly affected by the syndiotacticity degree. This is especially the case for the melting temperature which raises up to 183 °C for P r = 0.94, a temperature higher than that of pure isotactic PHB (ca. 180 °C).

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Structure and morphology of poly(?-hydroxybutyrate) synthesized by ring-opening polymerization of racemic (R,S)-?-butyrolactone with distannoxane derivatives

Cited by 26 publications

References 28 publications

Cellulose Acetate‐graft‐Poly(hydroxyalkanoate)s: Synthesis and Dependence of the Thermal Properties on Copolymer Composition

Cellulose Acetate‐graft‐Poly(hydroxyalkanoate)s: Synthesis and Dependence of the Thermal Properties on Copolymer Composition

Synthesis and characterizations of new isotactic homopolyesters, statistical and block copolyesters derived of poly((S)‐3,3‐dimethylmalic acid) via the lactone route

Syndiotactic-Enriched Poly(3-hydroxybutyrate)s via Stereoselective Ring-Opening Polymerization of Racemic β-Butyrolactone with Discrete Yttrium Catalysts

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