Homogeneous acylation of Cellulose diacetate: Towards bioplastics with tuneable thermal and water transport properties

Boulven, Manon; Quintard, Guilhem; Cottaz, Amandine; Joly, Catherine; Charlot, Aurélia; Fleury, Étienne

doi:10.1016/j.carbpol.2018.11.030

Cited by 32 publications

(18 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Although industrially available cellulosic derivatives (cellulose esters and, in particular, cellulose acetate) constitute an appealing bio-sourced alternative for the replacement of petroleum-based plastics, the presence of strong intermolecular and intramolecular hydrogen bonds is responsible of their high viscosity and elevated T g , requiring their previous plasticization to improve their processability as thermoplastics [42]. In this regard, besides the conventional use of plasticizing additives, grafting of molecules which act as “internal plasticizers”, by destroying the hydrogen bonds network and promoting the mobility of the macromolecular chains, has also been proved effective in lowering the T g of cellulosic derivatives [7,42,43]. For this reason, NaCMC, HCMC and the amidated CMC derivatives were analysed by differential scanning calorimetry, in order to assess the ability of the bound amine substituents to separate the polymer chains and increase their mobility (Figure 8).…”

Section: Resultsmentioning

confidence: 99%

“…Interestingly, a significantly low T g (115 °C, Figure 10B) is obtained for CMC-Thio (Table 1, Entry 12), bearing a thiophene group, spaced from the CMC chain by a C2 alkyl segment. Previous studies demonstrated that the presence of bulky groups can play a dual role on the thermoplastic properties of cellulosic polymers: if the increase in the free-volume caused by the presence of bulky groups can lead to a decrease in T g , an elevated steric hindrance could limit their plasticizing effect [7,42]. The presence of a longer alkyl spacer between the bulky terminal moiety and the cellulose chain is therefore responsible of the higher flexibility and higher mobility of the modified product, that is reflected by a substantial lowering of T g .…”

Section: Resultsmentioning

confidence: 99%

“…In this regard, cellulose, the most abundant polymer on earth [5], and its derivatives represent a promising source of raw materials, thanks to their high availability, low environmental impact, non-toxicity and presence of reactive groups. This last characteristic is particularly appealing, as their further chemical functionalization can be conveniently used to suitably modify their properties, potentially extending their applicability to new and unconventional uses [6,7]. Carboxymethyl cellulose (CMC), a cellulose ether in which some of the hydroxyl groups of the glucopyranose units are substituted by sodium carboxymethyl groups (–CH 2 COONa), is one of the most important cellulose ether derivatives, with 583.782 tons of annual global production and a wide range of applications (e.g., food industry, personal care, pharmaceuticals, textiles, paper, adhesives, ceramics) [8,9].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Solvent-Free Synthesis of Amidated Carboxymethyl Cellulose Derivatives: Effect on the Thermal Properties

2019

Self Cite

View full text Add to dashboard Cite

The present work explores the possibility of chemically modifying carboxymethyl cellulose (CMC), a widely diffused commercial cellulose ether, by grafting of hydrophobic moieties. Amidation of CMC, at high temperature and in heterogeneous conditions, was selected as synthetic tool for grafting on CMC a panel of commercially available amines (bearing long aliphatic chains, alkyl aromatic and heteroaromatic groups, more or less spaced from the cellulose backbone). The reaction was successfully carried out in absence of solvents, catalysts and coupling agents, providing a promising and more sustainable alternative to conventional amidation procedures. Relationships between the chemical structure of the obtained CMC derivatives and their thermal properties were carefully studied, with a particular attention to the thermal behavior. Grafting of aromatic and heteroaromatic alkyl amines, presenting a linear alkyl chain between CMC backbone and a terminal bulky moiety, allowed for efficiently separating the polysaccharide chains, improving their mobility and resulting in a consequent lowering of the glass transition temperature (Tg). The Tg values obtained (90–147 °C) were found to be closely dependent on both the size of the aliphatic spacer, the structure of the aromatic ring and the extent of amidation.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Solvent-Free Synthesis of Amidated Carboxymethyl Cellulose Derivatives: Effect on the Thermal Properties

2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although many hydroxyl groups on cellulose have been esteri ed by acetic acid to improve its compatibility with PLA, the remaining hydroxyl groups cause the CA to agglomerate easily and prevent the uniform dispersion of CA in PLA. At present, the compatibilization modi cation of PLA / CA blends includes grafting maleic anhydride on PLA [11], grafting long aliphatic chain on cellulose acetate [12], introducing the third component poly(hydroxyalkanoate) [13], PLA-g-CA graft copolymer [14], comb copolymer [15], transesteri cation agent to form PLA-co-CA copolymer [16], organic clay [17], etc.…”

Section: Introductionmentioning

confidence: 99%

Compatibilization and Toughening of Biodegradable Polylactic Acid/Cellulose Acetate Films by Polyamide Amine Dendrimers

et al. 2021

View full text Add to dashboard Cite

Due to the poor compatibility caused by the large difference in hydrophilicity and interface between polylactic acid (PLA) and cellulose acetate (CA), the blending of the two materials is di cult and the application is limited. To solve this problem, a type of polyamide amine (PAMAM) dendrimer was introduced to modify PLA / CA blends in this work. The results showed that PAMAM could improve the compatibility of PLA / CA blends, promote the distribution of CA and crystallization of PLA. At the same time, adding PAMAM could enhance the mechanical properties of the blend material, and the toughness and tear strength were increased by 551% and 141%, respectively. In addition, the incorporation of PAMAM increased hydrophobicity and oxygen permeability of PLA/ CA blends, and the oxygen permeability could be increased by up to 3 orders of magnitude. Degradation test results showed that the blend exhibited good biodegradability. The overall performance of the PLA/ CA blend lm was optimal when the content of PAMAM was 3 phr. The biodegradable blend lms with excellent performance provided wide application prospect in the food green packaging elds.

show abstract

“…Cellulose diacetate (CDA) as an important cellulose ester is available at industrial scale (Rustemeyer 2004;Simon et al 1998;Wang et al 2018), and usually applied for manufacturing CDA fiber through wet spinning process from its acetone solution (Cho et al 2013;Edgar et al 2001). CDA is not easily meltprocessable by conventional extrusion or injection processes (Boulven et al 2019), because it has a high glass transition temperature (Tg) and a narrow window between flowing temperature (Tf) and decomposition temperature (Td) (Benazzouz et al 2017;Iji et al 2013). From this perspective, plasticizers are necessarily introduced to disrupt strong dipolar interaction network, improving the CDA chain activity.…”

Section: Introductionmentioning

confidence: 99%

Interfacial Effects of Plasticizers On The Properties of Cellulose Diacetate Materials

Hu¹,

Zhang²,

Wei³

et al. 2021

Preprint

View full text Add to dashboard Cite

Cellulose diacetate (CDA) is a biodegradable biobased polymer, which is not easily melt-processable with a narrow window between flowing and decomposition temperature. Selecting the appropriate plasticizer and evaluating its effect on the properties are important for the application developments of CDA materials. In this paper, eco-friendly plasticizers, such as glycerin (GL), diacetin (DA), triacetin (TA) and polyethylene glycol (PEG) are necessarily introduced. The plasticizing effect is evaluated by harmonic interface energy between CDA and plasticizer from contact angle test. Compared with solubility parameter method, the interfacial method is more effective to estimate PEG with different molecular weight in CDA. Thermal behaviors verify the interfacial method works. Lower interface energy of CDA-DA shows lower glass transition temperature (Tg) determined by differential scanning calorimetry (DSC). Meanwhile, mechanical property, transparency and moisture permeability are all related to the interfacial effects of plasticizers. For instance, the elongation at break of CDA-DA and CDA-TA, which have lower interfacial energy, increase from 14% to 26% and 29%. The CDA-DA and CDA-TA films also have high visible light transmittance about 90%. The moisture permeability of plasticized CDA film increases with the decreased interface energy between water and plasticizer. Interfacial method provides a new route for preparing high-performance CDA materials.

show abstract

Homogeneous acylation of Cellulose diacetate: Towards bioplastics with tuneable thermal and water transport properties

Cited by 32 publications

References 39 publications

Solvent-Free Synthesis of Amidated Carboxymethyl Cellulose Derivatives: Effect on the Thermal Properties

Solvent-Free Synthesis of Amidated Carboxymethyl Cellulose Derivatives: Effect on the Thermal Properties

Compatibilization and Toughening of Biodegradable Polylactic Acid/Cellulose Acetate Films by Polyamide Amine Dendrimers

Interfacial Effects of Plasticizers On The Properties of Cellulose Diacetate Materials

Contact Info

Product

Resources

About