Synthesis and functionalization of vinylsulfide and ketone-containing aliphatic copolyesters from fatty acids

Beyazkiliç, Zeynep; Lligadas, Gerard; Ronda, Juan C.; Galià, Marina; Cádiz, Virgínia

doi:10.1016/j.polymer.2015.10.024

Cited by 9 publications

(9 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…More recently, Beyazkilic et al. [ 109 ] studied the homo and copolymerization of vinylsulfide‐containing hydroxyacid (VHSA) from 10‐undecenoic fatty acid, and ketone‐containing hydroxyester (KHE) from methyl oleate in diphenyl ether with immobilized CALB at 80 and 90 °C. For all the polymers, molecular weight increased as a function of time (until 48 h), and in the case of KHE and VHSA:KHE copolyester, the increase in temperature did not result in a significant difference in the obtained M w at any of the reaction times tested.…”

Section: Enzymes In Polymer Chemistrymentioning

confidence: 99%

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives

Hevilla

Sonseca

Echeverría

et al. 2021

Macromolecular Bioscience

View full text Add to dashboard Cite

This article reviews the most important advances in the enzymatic synthesis of polyesters. In first place, the different processes of polyester enzymatic synthesis, i.e., polycondensation, ring opening, and chemoenzymatic polymerizations, and the key parameters affecting these reactions, such as enzyme, concentration, solvent, or temperature, are analyzed. Then, the latest articles on the preparation of polyesters either by direct synthesis or via modification are commented. Finally, the main bioapplications of enzymatically obtained polyesters, i.e., antimicrobial, drug delivery, or tissue engineering, are described. It is intended to point out the great advantages that enzymatic polymerization present to obtain polymers and the disadvantages found to develop applied materials.

show abstract

Section: Enzymes In Polymer Chemistrymentioning

confidence: 99%

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives

Hevilla

Sonseca

Echeverría

et al. 2021

Macromolecular Bioscience

View full text Add to dashboard Cite

show abstract

“…As shown in Scheme 1, three commercial biobased monomers, including DEK, HDO, and DEA, were chosen. DEK, a ketone-containing diester monomer, can be prepared from furylacrylic acid (54), and renewable furfural derived from lignocellulosic biomass can be converted into furylacrylic acid by the Horner-Wadsworth-Emmons reaction (53). HDO and DEA can be obtained from renewable HMF (55) and FDCA (56), respectively.…”

Section: Enzymatic Synthesis Of the Phk Homopolymermentioning

confidence: 99%

“…Moreover, several bio-based functional polyesters including furan- (43,44), sorbitol-(45), glucose- (46), itaconate- (47,48), and castor oil-based polyesters (49,50) were obtained through the CALB-catalyzed polymerization. Nevertheless, only a few studies on the biocatalytic synthesis of PKEs are reported (51)(52)(53). Barrett and Yousaf tried to use Novozyme-435 to polymerize ketone-containing diesters/diacids and di(ethylene glycol), but only low molecular weight materials (below 1,000 Da) were obtained (51).…”

Section: Introductionmentioning

confidence: 99%

“…Barrett and Yousaf tried to use Novozyme-435 to polymerize ketone-containing diesters/diacids and di(ethylene glycol), but only low molecular weight materials (below 1,000 Da) were obtained (51). Recently, Galià and co-workers reported the amorphous PKEs containing ketone and sulphide functional groups from oleic acid by lipasecatalyzed polycondensation (52,53). Up to now, the enzymatic synthesis of bio-based semi-crystalline PKEs has never been studied.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters

2020

E-Polymers

View full text Add to dashboard Cite

AbstractA novel full bio-based ketone-containing aliphatic polyester was prepared by enzyme-catalyzed polycondensation of diethyl γ-ketopimelate (DEK) with 1,6-hexanediol (HDO) using immobilized lipase B from Candida antarctica (CALB). The influences of polymerization conditions such as temperature, time, enzyme amount, and solvent amount on the molecular weight of poly(hexamethylene γ-ketopimelate) (PHK) were investigated. New fully bio-based poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) (poly(HK-co-HA)) copolymers with narrow polydispersity and well-defined composition were synthesized by copolymerization of DEK, HDO, and diethyl adipate. The structures of PHK and poly(HK-co-HA) copolymers were characterized by nuclear magnetic resonance, and their thermal characterization was examined by thermogravimetric analysis and differential scanning calorimetry. The degradation of PHK and poly(HK-co-HA) copolymers was studied. The post-polymerization modification of these polyketoesters via oxime click chemistry was further demonstrated.

show abstract

“…Despite the well‐known advantages of biocatalysis for the manufacture of innovative polymeric materials, reports about the enzymatic synthesis of hydroxy‐fatty acids copolyesters are scarce. Random copolyesters were obtained from vegetable oil derivatives, a vinylsulfide‐containing hydroxy acid and a ketone‐containing hydroxy ester, in diphenylether, at temperatures up to 90 °C, using Novozym 435 lipase . The enzyme‐catalyzed copolymerization of ECL with hydroxy‐fatty acids was not yet reported, but it may be an interesting approach and a promising solution to improve the properties in relation to both homopolymer products, PCL and estolides.…”

Section: Introductionmentioning

confidence: 99%

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

et al. 2018

View full text Add to dashboard Cite

Developments of past years placed the bio-based polyesters as competitive substitutes for fossil-based polymers. Moreover, enzymatic polymerization using lipase catalysts has become an important green alternative to chemical polymerization for the synthesis of polyesters with biomedical applications, as several drawbacks related to the presence of traces of metal catalysts, toxicity and higher temperatures could be avoided. Copolymerization of ϵ-caprolactone (CL) with four hydroxy-fatty acids (HFA) from renewable sources, 10-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic acid, and 16-hydroxyhexadecanoic acid, was carried out using commercially available immobilized lipases from Candida antarctica B, Thermomyces lanuginosus, and Pseudomonas stutzeri, as well as a native lipase. MALDI-TOF-MS and 2D-NMR analysis confirmed the formation of linear/branched and cyclic oligomers with average molecular weight around 1200 and polymerization degree up to 15. The appropriate selection of the biocatalyst and reaction temperature allowed the tailoring of the non-cyclic/cyclic copolymer ratio and increase of the total copolymer content in the reaction product above 80%. The catalytic efficiency of the best performing biocatalyst (Lipozyme TL) is evaluated during four reaction cycles, showing excellent operational stability. The thermal stability of the reaction products is assessed based on TG and DSC analysis. This new synthetic route for biobased oligomers with novel functionalities and properties could have promising biomedical applications.

show abstract

Synthesis and functionalization of vinylsulfide and ketone-containing aliphatic copolyesters from fatty acids

Cited by 9 publications

References 25 publications

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives

Enzymatic Synthesis of Polyesters and Their Bioapplications: Recent Advances and Perspectives

Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

Contact Info

Product

Resources

About