Enzymic polymerisation of an unactivated diol/diacid system

Binns, Falmai; Roberts, Stanley M.; Taylor, A.; Williams, Charles F.

doi:10.1039/p19930000899

Cited by 71 publications

(36 citation statements)

References 8 publications

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“…[104] Lipase catalyzed the dehydration polycondensation using dicarboxylic acids, for example, a dehydration polycondensation of adipic acid and butane-1,4-diol in di-isopropyl ether gave a polyester with a degree of polymerization (DP) of 20 (m ¼ p ¼ 4, in Scheme 24). [105] Higher molecular weight polyesters were enzymatically obtained by polycondensation of sebacic acid and 1,4-butanediol (m ¼ 8, p ¼ 4 in Scheme 24) under vacuum. In the Mucor miehei lipase-catalyzed polymerization in hydrophobic solvents of high boiling point, such as diphenyl ether and veratrole, the molecular weight of polyesters from various combinations of diacids and glycols was more than than 40 000.…”

Section: Esterification (Dehydration) Polycondensationmentioning

confidence: 99%

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Kobayashi

2009

Macromol. Rapid Commun.

258

205

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Polyester synthesis by lipase catalyst involves two major polymerization modes: i) ring-opening polymerization of lactones, and, ii) polycondensation. Ring-opening polymerization includes the finding of lipase catalyst; scope of reactions; polymerization mechanism; ring-opening polymerization reactivity of lactones; enantio-, chemo- and regio-selective polymerizations; and, chemoenzymatic polymerizations. Polycondensation includes polymerizations involving condensation reactions between carboxylic acid and alcohol functional groups to form an ester bond. In most cases, a carboxylic acid group is activated as an ester form, such as a vinyl ester. Many recently developed polymerizations demonstrate lipase catalysis specific to enzymatic polymerization and appear very useful. Also, since lipase-catalyzed polyester synthesis provides a good opportunity for conducting "green polymer chemistry", the importance of this is described.

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Section: Esterification (Dehydration) Polycondensationmentioning

confidence: 99%

Recent Developments in Lipase‐Catalyzed Synthesis of Polyesters

Kobayashi

2009

Macromol. Rapid Commun.

258

205

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“…Section of the MALDI-ToF-MS spectra of poly(1,8-octanediol-cosorbitol adipate) (entry b, Table 1). End-groups belonging to the several distribution are indicated in the figure. and loosely bound water without depleting the crystallization water from the tridimensional structure of the enzyme, which would deactivate it [41]. Following a literature report, Novozyme 435 Ò was dried under reduced pressure (10 mbar) at 25°C for 24 h [15].…”

Section: Polymer Functionality: Determination Of the Sorbitol Contentmentioning

confidence: 99%

Enzymatic synthesis and preliminary evaluation as coating of sorbitol-based, hydroxy-functional polyesters with controlled molecular weights

Gustini

Noordover

Gehrels

et al. 2015

European Polymer Journal

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(2015). Enzymatic synthesis and preliminary evaluation as coating of sorbitol-based, hydroxy-functional polyesters with controlled molecular weights. European Polymer Journal, 67, 459-475. DOI: 10.1016/j.eurpolymj.2014 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. By using a combination of bio-based monomers (sorbitol, 1,10-decanediol and a range of dicarboxylic acids), a series of novel sorbitol-based polyesters was prepared by solvent-free enzymatic polycondensation using an immobilized form of Candida antarctica lipase B (Novozyme 435). The aim was to prepare linear polyesters with pendant, curable hydroxyl groups along the polymer backbone. To achieve this, the polyester molecular weight was controlled by tuning the reaction time, enzyme loading and reaction stoichiometry. Extensive molecular and thermal characterization was performed, showing that the obtained polyesters were semi-crystalline materials with a low T g . The presence of sorbitol in the polyesters was confirmed through a qualitative investigation using MALDI-ToF-MS. The quantification of the sorbitol content in the polymers was achieved by inverse-gated decoupling 13 C NMR spectroscopy, while 31 P NMR provided information regarding the selectivity of CALB for the primary vs. the secondary hydroxyl groups. Moreover, 31 P NMR and potentiometric titration were utilized for the quantitative determination of the amount of carboxylic groups and hydroxyl functional groups present in the polyesters. The obtained hydroxyl-functional polyesters had suitable properties to be applied as solvent-borne coatings in terms of their molecular weight, functionality and thermal characteristics. Cross-linked coatings were prepared using different conventional curing agents, including two renewable diisocyanates (ethyl ester L-lysine diisocyanate and dimer fatty acid-based diisocyanate). The resulting poly(ester urethane) coatings were tested in terms of solvent resistance, hardness and resistance against rapid deformation, showing the beneficial effect of the implemented sorbitol on network formation.

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“…Various methods have been employed to remove the reaction by-product, water or alcohol, in order to displace the equilibrium toward the formation of polyester: addition of molecular sieve, 328,332 Dean-Stark distillation of toluene-water azeotrope, 329 or bubbling inert gas in reaction medium. 336 In the case of reactions carried out without solvent, vacuum can be applied to distill off reaction water or alcohol.…”

Section: Scheme 235mentioning

confidence: 99%