Deterioration behavior of cellulose acetate films in acidic or basic aqueous solutions

The deterioration behavior of cellulose acetate (CA) films (degree of substitution = 2.5) was examined in hydrochloric acid (HCl) and sodium hydroxide (NaOH) solutions of various concentrations to determine acid and base catalytic effects in heterogeneous systems at room temperature. With concentrations of 0.5N HCl and 0.01N NaOH and higher, the physical properties of the films changed. The films, recovered after 1–10 days of immersion, were slightly opaque and rubbery from swelling in the solutions before drying. They became brittle and shrank when they dried. For HCl immersion, the weight change of a film depended on the HCl concentration and the immersion time. With 6.0N HCl, the film shape was broken, and a fine powder was deposited in the solution with a recovery of 53.8 wt %. The infrared spectrum of this deposit indicated that it was completely deacetylated cellulose. For NaOH immersion, although the weight change depended on the NaOH concentration, the weight loss reached 40–50% within the first 24 h, and it was constant with respect to the immersion time and base concentration in 0.5N NaOH or NaOH of a higher concentration. The infrared and gel permeation chromatography analyses showed that this deterioration mainly depended on the deacetylation of CA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3354–3361, 2004     

二醋酸纤维素的碱降解性能

研究了室温下醋酸纤维素在各种浓度的氢氧化钠溶液中的降解行为。红外光谱分析显示,醋酸纤维素在碱溶液中的重量损失主要是由于脱乙酰化作用。扫描电子显微镜照片显示,在碱处理后的醋酸纤维素表面光滑,没有出现溶解和脱落,可能是由于生成了碱纤维素。5 mol/L的氢氧化钠处理后,可观察到微纤化结构。纤维强力的测试结果表明,随着碱液浓度的增加,纤维的强力和模量降低,断裂伸长增加,可能是由于降解后微纤非纵向排列的结果。     

预处理结合纤维素酶处理对醋酯纤维降解的研究

采用纤维素酶降解经氢氧化钠预处理过的醋酯纤维,考察了pH值、温度、酶用量、处理时间以及助剂对酶解效果的影响,并初步探索了超声波对氢氧化钠预处理效果的影响。结果表明,氢氧化钠预处理后,使用纤维素酶降解醋酯纤维的工艺条件为:pH值4.5,温度55℃,酶用量3 mL/L,反应时间4 h;使用超声波辅助氢氧化钠预处理后,醋酯纤维的取代度较单一碱处理略有降低,酶解活性提高;在纤维素酶催化水解反应中,加入非离子表面活性剂可以提高醋酯纤维的酶解效果。     

Aerobic biodegradation of cellulose acetate

Two separate assay systems were used to evaluate the biodegradation potential of cellulose acetate: an in vitro enrichment cultivation technique (closed batch system), and a system in which cellulose diacetate (CDA) films were suspended in a wastewater treatment system (open continuous feed system). The in vitro assay employed a stable enrichment culture, which was initiated by inoculating a basal salts medium containing cellulose acetate with 5% (v/v) activated sludge. Microscopic examination revealed extensive degradation of CDA (DS = 2.5) fibers after 2–3 weeks of incubation. Characterization of the CA fibers recovered from inoculated flasks demonstrated a lower average degree of substitution and a change in the mol wt profiles. In vitro enrichments with CDA (DS = 1.7) films were able to degrade > 80% of the films in 4–5 days. Cellulose acetate (DS = 2.5) films required 10–12 days for extensive degradation. Films prepared from cellulose triacetate remained essentially unchanged after 28 days in the in vitro assay. The wastewater treatment assay was less active than the in vitro enrichment system. For example, approximately 27 days were required for 70% degradation of CDA (DS = 1.7) films to occur while CDA (DS = 2.5) films required approximately 10 weeks before significant degradation was obtained. Supporting evidence for the biodegradation potential of cellulose acetate was obtained through the conversion of cellulose [1-¹⁴C]-acetate to ¹⁴CO₂ in the in vitro assay. The results of this work demonstrate that cellulose acetate fibers and films are potentially biodegradable and that the rate of biodegradation is highly dependent on the degree of substitution. © 1993 John Wiley & Sons, Inc.     

Further studies on the action of alkali metal hydroxides on cotton

X-Ray diagrams revealed that the conversion of the lattice structure from cellulose I to cellulose II is substantially complete in cotton treated at 0°C with LiOH, NaOH, or KOH of approximately 5N concentration. With concentrations less than 5N, there were marked differences in the ability of these reagents to cause lattice conversions in cotton. Below a minimum concentration which is dependent on both the alkali and the treatment temperature, conversion from cellulose I to cellulose II cannot take place in cotton irrespective of the swelling caused by the reagent. We suggest that extensive swelling by one of these alkalis is not sufficient by itself to cause conversion from cellulose 1 to cellulose II and that the concentration of the alkali is of prime importance. There was no direct relation between the swelling induced in cotton by treatment with LiCH, NaOH, or KOH at 0°C and the sorption ratio of the resulting product. Also, although treatment with 5N KOH caused less swelling than that obtained with either 5N NaOH or LiOH, KOH reduced the level-off degree of polymerization (LODP) of cotton most, indicating the importance of the size of alkali cation in reducing crystallite length. In additional experiments, cotton was treated at 21°C with a solution of 4.7N NaOH to which boric acid had been added. Although the swelling of the cotton was little affected, the addition of the boric acid caused the sorption ratio of the product to decrease, whereas the LODP increased. Also conversion of the lattice structure from cellulose I to cellulose II was inhibited.     

Preparation of polyacrylonitrile and cellulose acetate blend fibers through wet‐spinning

Fibers containing both polyacrylonitrile (PAN) and cellulose acetate (CA) were prepared through wet‐spinning by using N,N‐dimethylformamide (DMF) as a solvent. Compatibility of PAN and cellulose acetate blend (PCB) fibers was investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared (IR) spectrophotometry. The absorptive capacity and mechanical properties of the fibers were measured. It was observed that the surface and the cross section of PAN fibers were quite smooth and free from voids and microcracks, whereas cracks and voids were present on the surface and cross section of blend fibers, which increased with the incorporation of CA in the blend. Moisture regains of blend fibers were quite high while their tensile properties showed a partial decrease. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2000–2005, 2007     

New detergent mechanism using cellulase revealed by change in physicochemical properties of cellulose

Sebum in naturally soiled cotton undershirt and oleic acid in artificially soiled cotton cloth, which entered interfiber space in the interior of cotton fibers were easily removed by alkaline cellulase fromBacillus sp., but only with difficulty by commonly used detergent ingredients such as surfactant and protease. Adsorption isotherms and the rate of hydrolysis of alkaline cellulase against insoluble cellulose powders revealed that the lower the relative crystallinity of cellulose powder, the more adsorptive alkaline cellulase became and the more hydrolysis was promoted. With alkaline cellulase, cotton having the highest relative crystallinity was adsorbed at pH 9 and 5°C, liberated a negligible small amount of reducing sugar at pH 9 and 40°C, and produced no changes in the degree of polymerization of cotton cellulose and in the tensile strength of cotton fabric at pH 9 and 30°C. On the other hand, differential scanning calorimetric studies revealed that under similar conditions even a small quantity of alkaline cellulase drastically reduced the amount of water bound to cellulose in cotton. Because water was bound only with hydroxy groups of cellulose molecules in the amorphous region of cotton fibers, it can be understood that soil entering the interfiber space of amorphous interlamellae in the interior of cotton fibers, was easily removed as the hydrated cellulose in the interlamellae was slightly hydrolyzed by alkaline cellulase. A new detergent mechanism is proposed.     

Influence of alkali treatment on the fine structure and morphology of bamboo fibers

Bamboo fibers in the form of strips and dust were treated with NaOH solution of varying concentration (10, 15, and 20%). These treated and untreated samples were then subjected to FTIR and morphological studies. Again XRD study was carried out on those treated and untreated bamboo samples in both strip and dust form. It was found that during alkali treatment a lattice transformation from cellulose‐I to cellulose‐II took place. It is observed from IR index value that the conversion is maximum in between 15 and 20% of alkali treatment. Swelling in NaOH introduces considerable changes in crystallinity, orientation angle, etc. Degree of crystallinity and crystallinity index for bamboo strips increases with increasing treatment concentration of alkali and falls off after 15% alkali concentration. This is also supported by d‐spacing value. Orientation factor f_x was calculated from the FWHM and it was found that f_x value has been increased from 0.9879 to 0.9915 for 15% alkali treated and again lowered to 0.8522 for 50% alkali treated samples. Same observation of X‐ray study was obtained for dust samples but at an earlier concentration. Morphological study of bamboo dust with scanning electron microscope indicates fibrillation at higher alkali concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5050–5056, 2006     

Dissolving states of cellulose and chitosan in trifluoroacetic acid

Chemical structures of cellulose and chitosan dissolved in trifluoroacetic acid (TFA) and those of cellulose and chitosan films cast from their TFA solutions were studied by ¹³C-NMR and infrared (IR) spectroscopy. Cellulose is trifluoroacetylated selectively at the C6–hydroxyl groups in the TFA solution, and chitosan is dissolved in TFA by forming amine salts with TFA at the C2–amine groups. IR analyses of cellulose films cast from its TFA–acetic acid solutions showed that partly trifluoroacetylated cellulose in the solution state turns to partly acetylated cellulose in the solid state during evaporation of the solvents in air by the ester interchange. Chitosan films cast from its TFA–acetic acid solutions still have the amine salts with TFA. These acetyl groups in cellulose films and TFA in chitosan films are removable by soaking the films in 1N NaOH at room temperature for 1 day.     

Physicochemical characterization of celluloses extracted from Esparto “Stipa tenacissima” of Eastern Morocco

Increasing ecological concerns have given rise to renewed interest in the use of natural materials, considering their renewability and possibility of disposal at the end of their life cycle without damage to the environment. In this study, we examined the isolation of cellulose from Esparto “Stipa tenacissima” of Eastern Morocco by two different ways; the first one using an acetic acid solution catalyzed by nitric acid. The objective is to determine the optimum amount of this catalyst needed to the extraction. The second way consists to study the cellulose extraction with change of the alkaline solution concentration in order to choose the required value. The cellulosic samples were characterized by FT‐IR spectroscopy and X‐ray diffraction, the morphology of the isolated fibers was investigated by optical microscopy. Thermal analysis (DT‐TGA) were carried out to study the thermal behavior of the cellulose isolated compared with the control sample. The degree of polymerization (DP) of the samples extracted is estimated from the intrinsic viscosity value using the Mark‐Houwink equation in two different solutions (DMAc/9%LiCl) and (6%NaOH/4%urea/90%H₂O). We have demonstrated that the extraction using an acetic acid solution has been very successful by adding 2% in volume of nitric acid (HNO₃). However, the extraction process using an alkaline solution (NaOH; 1M) is preferable because of the absence of acetylating reaction and the high purity and the nondegradation of the resulted fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Methods for reducing the tendency of lyocell fibers to fibrillate

A study has been made of the influence of various process parameters on the fibrillation characteristics of Lyocell fibers, which are spun from a solution of cellulose in N-methylmorpholine-N-oxide (NMMO). The parameters were air gap length, temperature, and humidity; line speed; draw ratio; polymer solution cellulose and water contents; and coagulation bath concentration and temperature. Fibrillation was induced in the fibers by an ultrasonic treatment and compared by defining a fibrillation index from optical micrographs. By selecting combinations of the parameters described above, fibrillation can either be increased or decreased without significantly affecting the tensile properties of the fibers. A method for spinning nonfibrillable filaments on a laboratory scale is presented. © 1996 John Wiley & Sons, Inc.     

Homogeneous synthesis and characterization of polyacrylamide‐grafted cationic cellulose flocculants

In this work, cationic cellulose (CC) with different degrees of substitution (DS) was successfully synthesized by the reaction between cellulose and 3‐chloro‐2‐hydroxypropyl‐trimethylammonium chloride (CHPTAC) in a 7 wt % NaOH and 12 wt % urea aqueous solution. The structure of the CC was characterized by using elemental analysis, ¹H‐NMR, and FTIR. The DS values of CC ranged between 0.18 and 0.50, which could be obtained by adjusting the reaction temperature, reaction time, and molar ratio of CHPTAC to anhydroglucose unit of cellulose. The cationic cellulose–graft–polyacrylamide flocculant (CC‐g‐PAM) based on CC and polyacrylamide (PAM) was also synthesized in a homogeneous aqueous solution. The flocculation characteristics of CC and CC‐g‐PAM were evaluated in a kaolin suspension. The results showed that CC‐g‐PAM was an effective flocculant for the kaolin suspension under acidic or neutral conditions, and the flocculation efficiency was over 90%, while the CC showed better flocculation performance under alkaline conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43106.     

Experimental study on carboxymethylation of cellulose extracted from Posidonia oceanica

The production of carboxymethylcellulose (CMC) from bleached cellulose pulps obtained from Posidonia oceanica was explored. The optimal reaction conditions were studied for the carboxymethylation of cellulose in organic liquids. The carboxymethylation reaction was carried out with NaOH and monochloroacetic acid (MAC) as the reagent. Different alcohols were compared in terms of the degree of substitution (DS). The highest DS was obtained with n‐butanol. For this alcohol, the effects of the temperature, alkali concentration, and MAC concentration were studied. The reaction was also carried out in three consecutive steps. The resulting CMC had a DS of about 2.75. The functionalization of cellulose was checked using FTIR spectroscopy and ¹³C‐NMR. The X‐ray analysis showed that the crystalline structure of cellulose decreased when the DS increased and the structure was totally amorphous in high DS material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1808–1816, 2006     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

Controlled heterogeneous modification of cellulose fibers with fatty acids: Effect of reaction conditions on the extent of esterification and fiber properties

The controlled heterogeneous partial modification of cellulose fibers with fatty acids, partially preserving the fiber structure, was investigated. The effect of reaction conditions, such as reaction time, fatty acid chain length, and solvent types (swelling and non swelling), on the extent of esterification and fiber properties was evaluated by elemental analysis, IR‐ATR, X‐ray diffraction, ¹³C CPMAS NMR, contact angle measurement, thermogravimetry, and scanning electron microscopy. The degree of substitution (DS) increased with reaction time and with the swelling effect of the reaction medium and decreased with the fatty acids chain length. Higher the DS, higher is the decrystallization of cellulose as a result of the heterogeneous esterification reaction. The esterification with fatty acids enhanced the hydrophobic character of the fibers, but decreased their thermal stability. These properties are not strongly affected by the DS in the range investigated, viz. up to 1.4. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1093–1102, 2006     

FTIR spectroscopic study of the effect of microwave heating on the transformation of cellulose I into cellulose II during mercerization

Fourier transform infrared (FTIR) spectroscopy techniques were used in the study of the effect of microwave (MW) heating on the structural properties of cotton fibers and on the mercerization mechanism of these fibers. Samples of the fibers were microwave heated for different times and different microwave powers. Also, mixtures of cotton fibers and aqueous solution of NaOH with different concentrations were exposed to microwave radiation for different times and different powers. It was found that microwave heating of cotton fibers under these experimental conditions causes no observable changes in their spectral features apart from slight changes in the intensities of the absorption bands. The determined values of the absorbances ratio A1375 cm^?1/A2900 cm^?1 revealed that microwave heating for short periods and at low powers decreases the crystallinity of cotton as the result of the drying effect of microwave heating, while microwave heating for longer periods and at higher power results in recristallyzation of the fibers. The analysis of the experimentally obtained data revealed that microwave heating that causes molecular motions by migration of ions and rotations of the dipoles produces no considerable effects on the mechanism of mercerization but only reduces the concentration of NaOH in the solution and the time of treatment which are needed for the complete transformation of cellulose lattice type I into cellulose lattice type II without any heating. Also it was found that the magnitude of reductions depends on the applied power. Moreover the results proved that the deconvolution and the second derivatives of the FTIR spectra of cotton fibers can be used as a useful tool for distinguishing cellulose lattice type II from cellulose lattice type I. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution

In this work, the carboxymethylation of cellulose in the alkaline cellulose solvent, 7 wt% NaOH/12 wt% urea aqueous solution, was investigated. Carboxymethyl cellulose (CMC) samples were characterized with FT-IR, NMR, HPLC, and viscosity measurements. Water-soluble CMC with DS = 0.20–0.62 was prepared from both Avicel cellulose and cotton linters. Thus, carboxymethylation of cellulose in NaOH/urea leads to a polymer with the lowest DS value for water solubility (0.20) of CMC known. The total DS of CMC could be controlled by varying the molar ratio of reagents and NaOH to AGU and the reaction temperature. Structure analysis by means of HPLC after complete depolymerization showed that the mole fractions of the different carboxymethylated repeating units as well as those of unmodified glucose follow the simple statistic pattern. A distribution of the carboxymethyl groups at the level of the AGU in the order O-6 > O-2 > O-3 was determined. The results were similar with findings for CMC obtained by totally homogeneous reaction of cellulose in aqueous solvents such as Ni[tris(2-aminoethyl)amine](OH)₂.     

Alkaline hydrolysis of methyl acrylate grafted cellulose fibers

In this work, methyl acrylate grafted cellulose fibers were hydrolyzed in an aqueous NaOH solution to obtain a superabsorbent hydrogel. The effect of process variables, such as the hydrolysis reaction time, temperature, and NaOH concentration, during alkaline hydrolysis were carefully determined and optimized. The degree of hydrolysis was estimated on the basis of the determination of the carboxylate group contents. The material loss during hydrolysis followed a first‐order reaction mechanism. The differences in the behavior of the grafted fibers during hydrolysis could be explained by their structural differences. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

Selective aminolysis of mixed esters of cellulose

Aminolysis of cellulose esters was investigated. Of the amines tested (pyrrolidine, n-butylamine, sec-butylamine, 2,2-dimethylpropylamine, piperidine, cyclohexylamine, morpholine), pyrrolidine was the most reactive. The rate of aminolysis by pyrrolidine was approximately the same in dioxane as in dimethyl sulfoxide (DMSO). Using pyrrolidine in DMSO, the relative order of reactivity of the cellulose esters studied was acetate > butyrate ? phenylpropionate. With two mixed esters, cellulose acetate 2-phenylpropionate and cellulose acetate polystyrene carboxylate, deacetylation could be achieved with high specificity. Pyrrolidine in DMSO may also be used to perform a controlled deacetylation of cellulose triacetate in a homogeneous solution down to a degree of substitution of about 0.05. The aminolysis conditions did not cause any degradation of the cellulose chains.