Acetylation of DMSO:PF solutions of cellulose

Three different techniques for esterifying solutions of cellulose dissolved in mixtures of dimethyl sulfoxide (DMSO) and paraformaldehyde (PF) were evaluated and are herein described. The evaluation and development of suitable synthetic procedures and the characteristics of the resulting acetylated cellulose are reported. Glacial acetic acid (glacial HOAc), acetyl chloride (AcCl), and acetic anhydride (Ac₂O) were compared as acetylating agents for solutions of cellulose in DMSO:PF, and it was demonstrated that mixtures of pyridine (Py) and Ac₂O rapidly acetylated the cellulose to yield beige to amber acetone-soluble cellulose acetates which were partially oxidized. These thermoplastic resins exhibited softening points between 80 and 110°C and thermal stabilities (in nitrogen atmospheres) similar to those of native celluloses (350 to 375°C). Degree of acetyl substitution (DS) values ranged from 0 to 2.0 as a function of acetylation time.     

Characterization of cellulose acetates by nuclear magnetic resonance

An NMR method for determining the distribution of acetyl groups in cellulose acetates was developed. Treatment of cellulose acetates with acetyl-d₃ chloride gave products having simple spectra which could be analyzed quantitatively to give the distribution of acetyl groups in the original sample. The method was applied to studying (1) the hydrolysis of cellulose triacetate with ammonia, (2) the acetylation of cellulose acetate with acetyl chloride, and (3) the acetylation of cellulose acetate with acetic anhydride.     

FT Raman spectroscopic investigation of cellulose acetate

This study reports on a new method characterizing cellulose acetates and determining the contents of acetyl groups within cellulose acetates based on FT Raman spectroscopy. Cellulose acetates exhibiting diverse degrees of substitution ascribed to acetyl groups (DS_Ac) were obtained after the deacetylation of highly acetylated cellulose, i.e. cellulose diacetate and cellulose triacetate (CTA), with aqueous sodium hydroxide solution or 1,6-hexamethylenediamine (HMDA). After plotting the Raman intensity ratios between the bands at 1,740 and 1,380 cm⁻¹ against the DS_Ac, a calibration curve with high correlation coefficient of more than 0.99 was obtained. During the deacetylation of highly acetylated cellulose, a by-product—sodium acetate (NaOAc)—forms as the most possible salt among others. In order to determine the content of NaOAc, the mixtures of cellulose acetates and NaOAc were measured with FT Raman spectroscopy. Based on the relationship between the Raman intensity ratios as I₉₂₉/I₁₃₈₀ and the contents of NaOAc in the mixtures, a calibration curve exhibiting high correlation coefficient of more than 0.99 was generated.     

Nanofiber cellulose di- and tri-acetate using ferric chloride as a catalyst promoting highly efficient synthesis under microwave irradiation

An efficient method for the generation of cellulose di- and tri-acetate nano-structures is obtained through testing ferric chloride hydrate (FeCl₃·6H₂O) as a valuable Lewis acid catalyst with acetic anhydride under microwave irradiation. Our target was to evaluate the effects of the reaction conditions on the products' properties such as surface area and particle size distribution. It was found that changes in the degree of substitution (DS), the surface area, the degree of polymerization and the particle size distribution of the products correlated with reaction conditions. Cellulose tri-acetate nanofibers with DS of 2.94 with 98.03% yield was prepared using 200 mg of FeCl₃·6H₂O, 25 ml of Ac₂O and 4 minutes of microwave irradiation. Also, cellulose di-acetate nanofibers were prepared with DS values ranged between 2.37 and 2.72 with yield ranged between 78.92 and 90.58%. The percentage of acetyl groups (Ac%) as well as the BET specific surface area, total pore volume, mean pore diameter, mono layer volume and the mean particle size of the products were determined. The maximum specific surface area obtained for the acetylated cellulose was about ten times larger than that measured for the commercial cotton cellulose and about six times larger than that of the commercial cellulose acetate. The lowest mean particle size (34.90 nm) was about eleven times smaller than the mean particle size of the commercial cellulose acetate (394 nm). The present work has proved that FeCl₃·6H₂O was a highly active catalyst for the esterification of cellulose with unexpected yields and for the formation of nanofibers with low molecular weight.     

Bi-acylation of cellulose: determining the relative reactivities of the acetyl and fatty-acyl moieties

The global reaction between acetic anhydride and a fatty acid yields, at equilibrium, an asymmetric acetic-aliphatic anhydride in a medium containing finally: acetic-fatty anhydride, acetic anhydride, fatty acid, acetic acid and fatty anhydride. No solvent or catalyst was used to evaluate the impact of the actual reactivity of the anhydrides. The competition between the formation of acetyl and fatty acyl ester functions was evaluated by determining the ratio of acetyl/fatty acyl groups grafted on solid cellulose. The influence of temperature, reaction time, and length of fatty chain on the total degree of substitution and on the ratio of acetyl/fatty acyl ester functions was investigated. For the first time, a correlation has been established between esterification and the length of the aliphatic chain of the fatty acid. Reactivity of the medium decreased with the number of carbons in the fatty acid, raised to the power 2.37.     

Reversible hydrophobization and lipophobization of cellulose fibers via trifluoroacetylation

The surface modification of cellulose fibers with trifluoroacetic anhydride (TFAA) was studied using the heterogeneous cellulose/TFAA/pyridine/toluene system. The degree of substitution (DS) of the ensuing trifluoroacetylated fibers ranged from 0.04 to 0.30. This treatment conferred a high degree of both hydrophobicity and lipophobicity on the fibers' surface, even at low DS values. Both the dispersive and the polar contributions to the surface energy were drastically reduced. However, the original cellulose hydrophilicity could be readily restored through hydrolysis, by treating the modified fibers with neutral water.     

Stannoboroxanes : II. Synthesis and reactions of tris(trialkyltin) borates

Tris(trialkyltin) borates B(OSnR₃)₃ (R = Me, Et, Pr, Bu, i-Bu and Ph) have been prepared by esterification of boric acid with trialkyltin hydroxide or bis(trialkyltin) oxide. These reacted with boric anhydride to give the corresponding trialkyltin metaborates (R₃SnOBO)₃. Reactions of tris(tributyltin) borate with hydrogen chloride, acetyl chloride, acetic acid, acetic anhydride, phenol, butanethiol, thiophenol and isopropyl acetate have been studied. The infrared spectra of these compounds are discussed.     

Acetylation of cellulose I and II studied by limiting viscosity and X-ray diffraction

When cellulose triacetates and some hydrolyzed acetates are boiled in 2.5N hydrochloric acid there is no residue. Under the same conditions cellulose is hydrolyzed, and a residue is obtained with a limiting viscosity that is related to the average length of the cellulose crystallites. These findings are combined to develop a method for studying the progress of acetylation through the amorphous portion of cellulose and into the crystallites, and to investigate the relative reactivities of cellulose I and cellulose II. Acetates were made from cotton and wood cellulose by a “fibrous” (heterogeneous) esterification involving sulfoacetic acid or perchloric acid catalyst in acetic acid-acetic anhydride; the final acetyl contents (10–41%) were attained by stopping the reaction at various points short of the triester (rather than by hydrolyzing a triester). When these acetates were boiled in 2.5N HCI they did not disappear completely, and the residues were cellulose I, indicating that cellulose acetate had been removed. With increasing acetyl the yield of residue decreased, and beyond about 33% acetyl the viscosity and x-ray measurements showed that the length and width of the crystallites decreased. However, when a nonsolvent such as toluene was added to the acetylation medium, the limiting viscosity did not change over the same acetyl range (up to 40%). Samples of varying acetyl values were taken during a regular acetylation of cotton linters in a mixer with sulfuric acid catalyst. X-ray studies of the residues obtained by boiling the acetates in 2.5N HCI revealed the presence of unreacted cellulose I even after 40% acetyl had been reached. This explains why the manufacture of cellulose esters from cellulose I requires complete esterification before they are hydrolyzed to the desired acetyl level. It was shown that there is a distinct difference between the acetylation reactivity of cellulose I and cellulose II. This indicates the importance of avoiding cellulose II formation during the refinement of cellulose for the manufacture of cellulose acetate in a process involving activation with acetic acid.     

Surface only modification of bacterial cellulose nanofibres with organic acids

Bacterial cellulose (BC) nanofibres were modified only on their surface using an esterification reaction with acetic acid, hexanoic acid or dodecanoic acid. This reaction rendered the extremely hydrophilic surfaces of BC nanofibres hydrophobic. The hydrophobicity of BC increased with increasing carbon chain length of the organic acids used for the esterification reaction. Streaming (zeta-) potential measurements showed a slight shift in the isoelectric point and a decrease in ζ_plateau was also observed after the esterification reactions. This was attributed to the loss of acidic functional groups and increase in hydrophobicity due to esterification of BC with organic acids. A method based on hydrogen/deuterium exchange was developed to evaluate the availability of surface hydroxyl groups of neat and modified BC. The thermal degradation temperature of modified BC sheets decreased with increasing carbon chain length of the organic acids used. This is thought to be a direct result of the esterification reaction, which significantly reduces the packing efficiency of the nanofibres because of a reduction in the number of effective hydrogen bonds between them.     

Gas-phase esterification of microfibrillated cellulose (MFC) films

The barrier properties of microfibrillated cellulose (MFC) films were improved by heterogeneous gas-phase esterification using various combinations of trifluoroacetic acid anhydride, acetic acid and acetic anhydride. The temperature, reagent ratio and reaction time were varied in the experimental design. The effects of two different purification procedures on the barrier properties of esterified MFC films were investigated. Washing with water did not affect the barrier properties compared to those of the films that were not washed, while the use of diethyl ether led to improved barrier properties as measured by the contact angle (CA) of water. The chemical composition of the modified films was studied by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Alterations in hydrophobicity and oxygen permeability were evaluated using dynamic CA and oxygen transmission rate measurements, respectively.     

Effects of acyl donor type, catalyst type, and reaction conditions on the activity and selectivity of Friedel-Crafts acylation

Acylation of anisole and 3-methylanisole was performed with several acylating reagents (acetylation by AcCl and Ac₂O and bromoacetylation by BrAcCl and (BrAc)₂O) over different solid acid catalysts. The reaction conditions were optimized with respect to the acylation reagent, overall yield, solid acid catalyst, and the products selectivities. While acylation of anisole with acetyl chloride or acetic anhydride resulted in its full conversion to para-substituted acetophenone, the use of bromoacetyl bromide or bromoacetic anhydride yielded also the ortho-substituted product. Acylation of 3-methylanisole also yielded both para- and ortho-substitutions, and the products distribution was affected by the reaction conditions and catalyst type. It was found that while more acidic catalysts (caesium salt of heteropolyacid and zeolites) were the most active towards anisole acylation, the most active catalysts for the acylation of 3-methylanisole were ion-exchange catalysts. Employing HY-740 zeolite resulted in the highest ortho-selectivity in the acylation of anisole with bromoacetyl bromide and bromoacetic anhydride and in the acylation of 3-methylanisole with acetic anhydride.     

Fast and highly efficient acetylation of xylans in ionic liquid systems

In this study high molecular weight pure rye arabinoxylan and spruce arabinoglucuronoxylan were acetylated in ionic liquid (IL) systems. Two different ILs were used in our study. In both IL, using optimized procedures, it was possible to achieve acetylation within 5 min. The first system involved direct dissolution into 1-ethyl-3-methylimidazolium dimethylphosphate ([emim][Me₂PO₄]), followed by addition of acetyl chloride/pyridine (AcCl/Pyr) and additional chloroform (CHCl₃), as co-solvent. The other system involved direct dissolution into the novel protic IL 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]), followed by acetic anhydride/1,5-diazabicyclo[4.3.0]non-5-ene (Ac₂O/DBN) and no co-solvent added. The full acetyl substitution of the xylans was confirmed by FT IR and ¹H NMR. The acetylated xylans maintained a high molecular weight, which was confirmed by gel permeation chromatography. The products were soluble in CHCl₃ and dimethyl carbonate, which is considered as a ‘green’ reagent or solvent. This allowed for the casting of the materials into clear transparent films, opening opportunity for further processing and evaluation of these materials.     

Coulometric generation of acetylions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride mixture

Coulometric generation of acetyl (CH₃CO⁺) ions by oxidation of mercury in acetic anhydride and in acetic acid/acetic anhydride (5:95, v/v) is described. Current/potential curves for solvents, titrated bases, indicator and mercury showed that in both these solvents mercury is oxidized at potentials which are much more negative than those for the titrated bases and other components present in the solution. Quinoline, triethanolamine, triethylamine, pyridine and quinolin-8-ol in acetic anhydride, as well as triethylamine, 2,2′-bipyridine, 2,4,6-collidine, pyridine and sodium acetate in acetic acid/acetic anhydride were titrated with acetyl ions generated by the oxidation of mercury. In this way, it was established that the oxidation of mercury to mercury (I) ions proceeds quantitatively with 100% current efficiency.     

Acetylation of cellulose in LiCl-<Emphasis Type="Italic">N,N</Emphasis>-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

The acylation of three cellulose samples by acetic anhydride, Ac₂O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 °C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac₂O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac₂O/AGU = 3. For all celluloses, the dependence of DS on Ac₂O/AGU is described by an exponential decay equation: DS = DS_o − Ae^{−[(Ac2O/AGU)/B]}; (A) and (B) are regression coefficients, and DS_o is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B_(M-cotton) > B_(M-sisal) > B_(MCC); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, N_agg, of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 N_agg. To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac₂O/AGU, time, temperature.     

Synthesis of carboxyl cellulose sulfates with regioselective sulfation and regiospecific oxidation using cellulose trifluoroacetate as intermediates

Synthesis of cellulose sulfates (CSs) and carboxyl cellulose sulfates (COCSs) with regioselectively or regiospecifically distributed functional groups within anhydroglucose units was reported. CS with regioselectively distributed sulfate groups at 2,3-O- or 2,6-O-position were homogeneously synthesized and cellulose trifluoroacetate (CTFA) was used as intermediates. The trifluoroacetyl groups were detected primarily at 6-O-position and their distributions could be altered by changing the amount of trifluoroacetyl anhydride (TFAA). Various sulfating agents were used for further homogeneous sulfation of CTFA. The total degree of sulfation (DS_S) and the distribution of sulfate groups within the repeating units were affected by the amount of TFAA, the type and amount of sulfating agents. Subsequent homogenous 4-acetamide-TEMPO or TEMPO-mediated oxidation of CS led to COCS with carboxyl groups regiospecifically distributed at C6 position, which may be interesting structural mimics for natural occurring heparin.     

Property Comparison of Cellulose Acetate Prepared Homogenously in Different Ionic Liquids

Cellulose acetates were synthesized homogeneously in four types of ionic liquids without any catalyst using cotton linter as the raw material and acetic anhydride as the esterification agent. FTIR, XRD and DSC were used to characterize the obtained products. It was shown that the homogeneously prepared cellulose acetates became completely amorphous. Degree of substitution of cellulose acetate synthesized in [C₄C₁Im][OAc] was found the highest; whereas T_g of this ester was the lowest. It was also found that the film made of cellulose acetate prepared in [C₄C₁Im][OAc] had lower toughness.     

有机溶剂作用下木粉的酯化

由前文,经有机溶剂处理后木粉中纤维素结晶大部分被破坏,达到一定的热塑性;溶剂处理后酯化是在纤维素分子链上嵌入酞基从而使消晶永久化,提高了木粉的塑性.本文讨论溶剂处理后木粉的酯化反应特性.     

Synthesis and Characterization of Cellulose Triacetate Obtained from Date Palm (Phoenix dactylifera L.) Trunk Mesh-Derived Cellulose

Cellulosic polysaccharides have increasingly been recognized as a viable substitute for the depleting petro-based feedstock due to numerous modification options for obtaining a plethora of bio-based materials. In this study, cellulose triacetate was synthesized from pure cellulose obtained from the waste lignocellulosic part of date palm (Phoenix dactylifera L.). To achieve a degree of substitution (DS) of the hydroxyl group of 2.9, a heterogeneous acetylation reaction was carried out with acetic anhydride as an acetyl donor. The obtained cellulose ester was compared with a commercially available derivative and characterized using various analytical methods. This cellulose triacetate contains approximately 43.9% acetyl and has a molecular weight of 205,102 g·mol⁻¹. The maximum thermal decomposition temperature of acetate was found to be 380 °C, similar to that of a reference sample. Thus, the synthesized ester derivate can be suitable for fabricating biodegradable and “all cellulose” biocomposite systems.     

Highly ordered three dimensional macroporous carbon spheres and their acid catalytic properties

Highly ordered three dimensional macroporous carbon spheres bearing sulfonic acid groups (MPCS-SO₃H) were prepared by incomplete carbonization of glucose in silica crystal bead template, followed by sulfonation and removal of the template. The composition and porous structure of the obtained carbon spheres were investigated by physical adsorption of nitrogen, scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy techniques. While the Fourier-transform infrared spectroscopy was used to characterize the functional groups on the surface of carbon spheres. The catalytic properties of the MPCS-SO₃H were evaluated by esterification of ethanol with acetic acid, indicating that MPCS-SO₃H possess remarkable catalytic performance (high stability and acid catalytic ability) for the esterification.     

纤维素在离子液体中的均相乙酰化及其选择性

在1-烯丙基-3-甲基咪唑氯盐(AMIMCl)离子液体中进行了纤维素的均相乙酰化. 酯化剂为乙酸酐和乙酰氯以及加入或不加入催化剂吡啶. 用滴定法确定了产物的取代度(DS), 根据¹³C NMR考察了产物的取代度分布. 结果表明: 酰氯酰化的反应速度比酸酐快; 吡啶能加快乙酸酐的酯化反应, 但减慢酰氯的反应; 使用乙酸酐/吡啶酯化时所得产物具有特殊的取代度分布, 即DS_C-2>> DS _C-3.