Kinetic studies of biocatalyzed copolyesters of poly(butylene succinate) (PBS) containing fully bio-based dilinoleic diol

Sonseca, Águeda; McClain, Andrew; Puskás, Judit E.; Fray, Mirosława El

doi:10.1016/j.eurpolymj.2019.04.038

Cited by 19 publications

(19 citation statements)

References 47 publications

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“…CALB-catalyzed polycondensation in solution for 24 h at 70 °C proved to achieve PBA with molar masses higher than reported in the literature [18][19][20]61] up to Mw of 60,000 g/mol, comparable to conventional PBA, while melt polycondensation resulted in a moderate decrease of molar mass to Mw ~31,000. The molar masses of PBS achieved with CALBcatalyzed melt polycondensation were higher than those reported in the literature and were in the range of those reported for solution polycondensates [39,45,47]. They will be increased when the catalyst is not removed by dissolving/precipitation work-up procedures necessary for molar mass analysis.…”

Section: Discussionmentioning

confidence: 63%

“…The polymer-supported CALB N435 was chosen for the study because it has frequently been mentioned as successful catalyst for enzymatic polycondensation [15,39,45,65]. Three samples of immobilized CALB N435 with different age were employed in the study.…”

Section: Activity Of the Lipasesmentioning

confidence: 99%

“…The lipase-catalyzed polycondensation reactions under solvent-less conditions have been carried out also for synthesis of polyesters from adipic acid and sebacic acid with different diols [12,[40][41][42][43] yielding different molar masses from 10 3 -to 10 4 g/mol. Aliphatic building blocks with unsaturated units can also be converted without crosslinking [25,[44][45][46][47][48]. Aliphatic-aromatic polyesters were prepared enzymatically as well [49].…”

Section: Introductionmentioning

confidence: 99%

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Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

et al. 2021

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Application of lipases (preferentially Candida antarctica Lipase B, CALB) for melt polycondensation of aliphatic polyesters by transesterification of activated dicarboxylic acids with diols allows to displace toxic metal and metal oxide catalysts. Immobilization of the enzyme enhances the activity and the temperature range of use. The possibility to use enzyme-catalyzed polycondensation in melt is studied and compared to results of polycondensations in solution. The experiments show that CALB successfully catalyzes polycondensation of both, divinyladipate and dimethylsuccinate, respectively, with 1,4-butanediol. NMR spectroscopy, relative molar masses obtained by size exclusion chromatography, MALDI-TOF MS and wide-angle X-ray scattering are employed to compare the influence of synthesis conditions for poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS). It is shown that the enzymatic activity of immobilized CALB deviates and influences the molar mass. CALB-catalyzed polycondensation of PBA in solution for 24 h at 70 °C achieves molar masses of up to Mw~60,000 g/mol, higher than reported previously and comparable to conventional PBA, while melt polycondensation resulted in a moderate decrease of molar mass to Mw~31,000. Enzymatically catalyzed melt polycondensation of PBS yields Mw~23,400 g/mol vs. Mw~40,000 g/mol with titanium(IV)n-butoxide. Melt polycondensation with enzyme catalysis allows to reduce the reaction time from days to 3-4 h.

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Section: Discussionmentioning

confidence: 63%

Section: Activity Of the Lipasesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

et al. 2021

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“…Moreover, the addition of DLS soft segments contributed to the reduction in melting enthalpy (from 81 to 49,52 J/g) and Tm (from 110 to 98 °C) which also indicate that quality, perfection and degree of crystalline phase decreases due to the weaker intermolecular interactions [13]. Tg-glass transition temperature; ΔHm-melting enthalpy of the hard segments; Tm-melting temperature; Tc-crystallization temperature; Xc-crystalline phase content in the copolymer a numerical values obtained from [14].…”

Section: Results and Siscussionmentioning

confidence: 99%

“Green” Poly(Butylene Succinate-co-Dilinoleic Succinate) Copolymers Synthesized Using Candida antarctica Lipase B (CAL-B) as Biocatalyst

Sokołowska

Fray

2020

The First International Conference on &Amp;ldquo;Green” Polymer Materials 2020

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Considering the rising demand to diminish energy consumption and CO2 emissions, the biobased segmented block copolymer, poly(butylene succinate-co-dilinoleic succinate) (PBS-DLS) with 70:30 (wt %) ratio of hard to soft segments was obtain using Candida antarctica lipase B (CAL-B) as a biocatalyst. Throughout two-step synthesis in diphenyl ether, biobased diethyl succinate was polymerized with renewable 1,4–butanediol and dimer linoleic diol to obtain “green” copolyester as a sustainable alternative to petroleum-based materials. Proton nuclear magnetic resonance (1H NMR) analysis confirmed that, using enzyme as a catalyst, we were able to produce multiblock copolymer and gel permeation chromatography (GPC) measurements revealed number-averaged molecular mass to be 25,000 g/mol. Additionally, differential scanning calorimetry (DSC) analysis revealed low-temperature glass transition (Tg) of soft segments and high melting point (Tm) of hard segments which indicate on two-phase morphology. Furthermore, cytotoxicity test using L929 murine fibroblasts was conducted on extracts of obtained PBS-DLS copolymer, indicating excellent biocompatibility in vitro.

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“…6 Catalani and co-workers described azeotropic polymerization of 1,4:3,6-dianhydro-D-glucitol-based polyesters using CAL-B as catalyst. 14 In fact, lipases have been widely used to obtain other biobased materials such as 2,5-bis(hydroxymethyl)furan-based polyesters, 15 glucose-based polyesters, 16 dimer fatty acid-based polyesters 17 and polyamides. 18,19 Among all the advantages of CAL-B as a catalyst, the most powerful attribute is the high selectivity of this enzyme.…”

Section: Introductionmentioning

confidence: 99%

Effect of enzymatic versus titanium dioxide/silicon dioxide catalyst on crystal structure of ‘green’ poly[(butylene succinate)‐co‐(dilinoleic succinate)] copolymers

Sokołowska

Stachowska

Czaplicka

et al. 2020

Polymer International

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Focusing on an eco-friendly approach, biodegradable poly[(butylene succinate)-co-(dilinoleic succinate)] (PBS-DLS) copolymers with 70:30 (wt%) ratio of hard to soft segments were successfully synthesized via various processes and catalytic systems. In this approach, biobased succinate was polymerized with renewable 1,4-butanediol and dimer linoleic diol to obtain 'green' copolyesters as sustainable alternatives to petroleum-based materials. In the first procedure, a two-step synthesis in diphenyl ether was performed using Candida antarctica lipase B (CAL-B) as a biocatalyst. A second material was produced via two-step melt polycondensation in the presence of heterogeneous titanium dioxide/silicone dioxide (C-94) catalyst. The obtained PBS-DLS copolyesters were further characterized in regard to their number-average molecular weight (M n ), chemical structure, thermal transition temperatures and crystallization behavior. Here, digital holographic microscopy was used to study the crystallization behavior of synthesized segmented copolyesters for the first time. Using this technique, it was possible to reveal the twisting of crystalline regions in formed spherulites and observe the differences in crystallization behavior of copolyesters depending on the type of catalyst used in their synthesis. Structural characterization indicated random and blocky structure of copolymers depending on the type of catalyst. M n was noticeably higher in the case of PBS-DLS 70:30 copolymer catalyzed using C-94 than PBS-DLS 70:30 synthesized with the use of CAL-B. However, the degree of crystallinity was lower for polymer catalyzed with the heterogeneous catalyst. Furthermore, differential scanning calorimetric thermal analysis revealed that synthesized copolyesters exhibit low glass transition temperature as well as high melting point which are typical for thermoplastic elastomers.

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Kinetic studies of biocatalyzed copolyesters of poly(butylene succinate) (PBS) containing fully bio-based dilinoleic diol

Cited by 19 publications

References 47 publications

Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

“Green” Poly(Butylene Succinate-co-Dilinoleic Succinate) Copolymers Synthesized Using Candida antarctica Lipase B (CAL-B) as Biocatalyst

Effect of enzymatic versus titanium dioxide/silicon dioxide catalyst on crystal structure of ‘green’ poly[(butylene succinate)‐co‐(dilinoleic succinate)] copolymers

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