Synthesis of levulinic acid based poly(amine-<i>co</i>-ester)s

Bernhard, Yann; Pagies, Lucas; Pellegrini, Sylvain; Bousquet, Till; Favrelle, Audrey; Pélinski, Lydie; Gerbaux, Pascal; Zinck, Philippe

doi:10.1039/c8gc03264e

Cited by 19 publications

(9 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides the above-mentioned dicarboxylic acids, recently, levulinic acid has drawn special attention due to its biobased origin, availability, and relatively low price. − In addition, this molecule has been classified, by the United States Department of Energy, as one of the top-12 promising biomass-derived building blocks, and it is considered to be a key intermediate for the synthesis of a wide range of chemicals with applications in fuels, fragrances, solvents, pharmaceuticals, polymer additives, and surfactants . The preparation of these compounds is possible due to the bifunctional nature of this acid, which bears both carboxylic and keto groups.…”

Section: Introductionmentioning

confidence: 99%

Biobased Ketal–Diester Additives Derived from Levulinic Acid: Synthesis and Effect on the Thermal Stability and Thermo-Mechanical Properties of Poly(vinyl chloride)

Sinisi

Esposti

Toselli

et al. 2019

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

A new class of biobased plasticizers is herein proposed as a replacement of the currently used additives. The molecules were synthesized by a selective protecting-group-free route, which was developed in order to produce valuable asymmetrical ketal–diester derivatives from the renewable levulinic acid, overcoming the typical drawbacks of these types of reactions. Five molecules with different side chains were successfully obtained and fully characterized by means of NMR and FT-IR spectroscopies. These ketal–diester additives were then tested in poly(vinyl chloride) (PVC) as the model polymer. Their compatibility and plasticizing effect were evaluated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic-mechanical thermal analysis (DMTA), and thermogravimetric analysis (TGA). The emerged trend showed a clear correlation between the structural features of the ketal–ester and the thermal and mechanical properties of the material. In particular, the best results in terms of glass transition temperature reduction were achieved when the isobutyl- and benzyl-terminated additives were used. Leaching tests in both hydrophilic and hydrophobic environments were also performed. No significant aqueous leaching was found; despite the aggressive treatment in hexane, the extraction for all additives was remarkably low. Importantly, when compared to commercial plasticizers such as di-2-ethylhexyl phthalate (DEHP), 1,2-cyclohexane dicarboxylic acid diisononyl ester (Hexamoll DINCH), acetyl tributyl citrate (ATBC), and diethylhexyl adipate (DEHA), the proposed ketal–diester additives performed comparably and, in some cases, even better. In particular, it was observed that the plasticizing effect already starts at lower concentrations, permitting one to use significantly less additive to obtain a similar effect to the one achieved with the nowadays available plasticizers.

show abstract

Section: Introductionmentioning

confidence: 99%

Biobased Ketal–Diester Additives Derived from Levulinic Acid: Synthesis and Effect on the Thermal Stability and Thermo-Mechanical Properties of Poly(vinyl chloride)

Sinisi

Esposti

Toselli

et al. 2019

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…Levulinic acid (LA) has been generally accepted as one of the top 12 value-added platform chemicals from biomass conversion. Because of the bifunctional keto and carboxylic groups, LA has wide applications and can be converted into a variety of downstream fine chemicals, including ethyl levulinate (flavor substance), 5-bromolevulinic acid (pharmaceutical agent), δ-aminolevulinic acid (herbicide), 5-nonanone (fuel), succinic acid (plasticiser), γ-valerolactone (solvent), nylon-6,6 (polymer), and so on. − Thereby, biomass conversion to LA has become one of the key transformations in biorefinery. − Recently, we applied acidic ILs to convert chitosan and chitin to produce LA, with yields up to 64 and 67%, respectively. A one-step conversion of crustacean shells to LA product has not been reported yet.…”

Section: Introductionmentioning

confidence: 99%

One-Step Conversion of Crab Shells to Levulinic Acid Catalyzed by Ionic Liquids: Self-Healing of Chitin Fraction

Zhao

Liu

2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

A highly selective route to produce levulinic acid (LA) from raw crab shells in one step has been provided by the catalysis of the ionic liquid (IL) 1-methyl-3-(3-sulfopropyl)imidazolium hydrogen sulfate ([C 3 SO 3 Hmim]HSO 4 ), resulting in the LA yield up to 77.9%. The relationship between the structure of ILs and the yield of LA was investigated, demonstrating both the acidity and hydrogen-bonding ability of ILs dictate their catalytic activity. Furthermore, by means of IR, scanning electron microscopy, elemental analysis, solid-state 13 C NMR, X-ray diffraction, and determination of the degree of acetylation, the self-healing of chitin fraction driven by hydrogenbond interactions was discovered upon the removal of CaCO 3 and protein for the first time. In the presence of a strong and interlocked hydrogen-bond network, direct depolymerization and consecutive deacetylation/depolymerization take place alternatively on the outer surface, whereas the interior crystalline structure of chitin remains intact.

show abstract

“…Because many of these materials are non-biodegradable or have relatively stable amide bonds or exhibit highly positive charge density, they allow only a partial elimination of the polycations or create stronger binding interactions with the loaded RNA . Besides, the high positive charge density of the polymers produces substantial cytotoxicity. , Incorporating ester bonds to the cationic polymer backbones can address these challenges because it does not only decrease the positive charge density but also facilitate the biodegradation of polymers, thus avoiding their accumulation in the human body, therefore decreasing the cytotoxicity while accelerating the release of RNA. − Poly(amine- co -ester)s are the ideal biodegradable gene delivery polymers generally synthesized by step-growth polymerizations. − It is worth noting that these step-growth polymerizations do not offer control over molecular weight and dispersity. Thus, ring-opening polymerization (ROP) of functionalized monomers is an ideal alternative approach to acquire well-defined poly(amine- co -ester)s, as it allows excellent control over numerous parameters …”

Section: Introductionmentioning

confidence: 99%

Poly(amine-co-ester)s by Binary Organocatalytic Ring-Opening Polymerization of N-Boc-1,4-oxazepan-7-one: Synthesis, Characterization, and Self-Assembly

Wang

Hadjichristidis

2019

Macromolecules

View full text Add to dashboard Cite

Binary organocatalytic ring-opening polymerization (ROP) of N-Boc-1,4-oxazepan-7-one (OxP Boc ) is proposed as a versatile method to generate metal-free poly(amine-co-ester)s and the corresponding biodegradable polycationic homo/ block (co)polymers. Optimization experiments with different organocatalysts, including 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), DBU/1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea (TU1), and phosphazene/thiourea, revealed that t-Bu-P 4 /TU1 leads to a fast and controlled/living ROP with benzyl alcohol (BnOH) as an initiator and thus allows the formation of well-defined poly(amine-co-ester)s with high molecular mass (M n,SEC up to 38.8 kg mol −1 ) and narrow dispersity. Well-defined poly(N-Boc-1,4-oxazepan-7-one)-based diblock copolymers were also synthesized successfully via the controlled/living ROP, regardless of whether hydrophilic poly(ethylene glycol) (PEG) or hydrophobic polycaprolactone (PCL) was used as a macroinitiator. After treatment with trifluoroacetic acid, the corresponding water-soluble polycationic homopolymer, as well as the hydrophilic (PEG-based copolymer) and amphiphilic (PCL-based copolymer) polycationic diblock copolymers, was obtained. Dynamic light scattering in water and transmission electron microscopy analyses revealed that both polycationic copolymers self-assembled spontaneously to nanostructures; the hydrophilic block copolymer formed spherical nanoparticles, while the amphiphilic one formed rod-shaped nanoparticles.

show abstract

Synthesis of levulinic acid based poly(amine-co-ester)s

Abstract: Bio-based polyesters containing tertiary amines in the backbone have been synthetized from renewable chemical building blocks.

Cited by 19 publications

References 66 publications

Biobased Ketal–Diester Additives Derived from Levulinic Acid: Synthesis and Effect on the Thermal Stability and Thermo-Mechanical Properties of Poly(vinyl chloride)

Biobased Ketal–Diester Additives Derived from Levulinic Acid: Synthesis and Effect on the Thermal Stability and Thermo-Mechanical Properties of Poly(vinyl chloride)

One-Step Conversion of Crab Shells to Levulinic Acid Catalyzed by Ionic Liquids: Self-Healing of Chitin Fraction

Poly(amine-co-ester)s by Binary Organocatalytic Ring-Opening Polymerization of N-Boc-1,4-oxazepan-7-one: Synthesis, Characterization, and Self-Assembly

Contact Info

Product

Resources

About