Synthesis and characterization of carboxymethyl cellulose powder and films from Mimosa pigra

Mimosa pigra peel was sun‐dried for 2 days and then ground before being boiled with 30%w/v sodium hydroxide (NaOH) at 100°C for 3 h, washed and then dried at 55°C to constant weight. The cellulose was then synthesized using different NaOH concentrations and monochloroacetic acid (MCA) in isopropyl alcohol (IPA). Effects of various NaOH concentrations on degree of substitution (DS), viscosity and thermal of carboxymethyl cellulose from Mimosa pigra peel (CMC_m) were investigated. The increasing of NaOH concentration resulted in increasing DS and viscosity. However, viscosity of CMC_m decreased as temperature increased. Thermal properties were studied using differential scanning calorimetry (DSC). The melting point of the samples decreased as %NaOH increased. The effects of various NaOH concentrations in CMC_m synthesis on the mechanical properties and water vapor permeability (WVP) of the CMC_m films were investigated as well. With increasing NaOH concentrations (30–50%) were also found to result in improved mechanical properties. However, when the level of NaOH concentration was 60%, the mechanical properties of the CMC films decreased. This result indicates that the highest mechanical properties were found for 50% NaOH‐synthesized CMC_m films. The WVP of the CMC_m films increased as %NaOH increased. In addition, the CMC_m films were tested to determine the effect of glycerol as a plasticizer on the mechanical properties. Increasing the amount of glycerol showed an increase in elongation at break but also led to a decrease in tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Carboxymethylation of cellulosic material (average degree of polymerization 2600) isolated from cotton (Gossypium) linters with respect to degree of substitution and rheological behavior

Carboxymethylation of cellulosic material (average degree of polymerization 2600) containing 76.5% cellulose and 23.6% xylose isolated from cotton (Gossypium) linters was studied under varying reaction conditions with respect to maximum degree of substitution (DS). The influence of reaction conditions on the apparent viscosity of the prepared derivatives was also studied. The conditions optimized were sodium hydroxide concentration 3.75M, monochloroacetic acid concentration 2.05 mol/AGU, carboxymethylation time 3.5 h, and temperature 55°C, to yield carboxymethyl cellulose of DS 0.77. Rheological studies of 1 and 2% solutions of the optimized product revealed their non‐Newtonian pseudoplastic behavior. Repeating units of the optimized product were also determined by HPLC after complete depolymerization of the polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1477–1482, 2005     

Starch derivatives with high degree of functionalization. III. Influence of reaction conditions and starting materials on molecular structure of carboxymethyl starch

Carboxymethyl starch (CMS) was prepared in a completely heterogeneous procedure in a methanol/water slurry activated with aqueous sodium hydroxide (45%, w/v) using monochloroacetic acid as the etherifying agent. The influence of the reaction conditions and the type of starting starch (amylose content and preactivation) was evaluated in regard to the formation of the main repeating units (i.e., unfunctionalized and mono‐, di‐, tri‐, and tetra‐O‐carboxymethylated) and the pattern of functionalization within the anhydroglucose units (AGU). The reproducible synthesis gave products with a maximal degree of substitution of CM groups (DS_CM) of 0.66, which was reached in a one‐step synthesis. Repeated carboxymethylation led to products with a DS_CM of 0.88. As revealed by means of HPLC analysis after complete acidic depolymerization, in any sample the mono‐O‐carboxymethylated glucose (mono‐O‐CMglc) was preferably present while the di‐O‐CMglc was formed to a very low extent only. The tri‐O‐CMglc was found in some samples while tetra‐O‐CMglc was not detected. The mole fractions determined did not follow the simple Spurlin statistic as shown for CM cellulose synthesized under comparable conditions. Within the carboxymethylated AGUs a preferred functionalization at position 2 was analyzed by means of ¹H‐NMR spectroscopy after hydrolytic chain degradation. Consequently, the CMS samples synthesized contained mainly 2‐mono‐O‐CM‐AGU. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2036–2044, 2001     

Synthesis and surface properties of chemodegradable anionic surfactants: Sodium (2-n-alkyl-1,3-dioxan-5-yl)sulfates

In the reaction of cis- and trans-2-n-alky-5-hydroxyl-1,3-dioxane mixtures with SO₃ · pyridine complex, followed by neutralization with sodium hydroxide or sodium carbonate, a new group of anionic surfactants, i.e., sodium cis- and trans-(2-n-alkyl-1,3-dioxan-5-yl)sulfates were obtained. The hydrophobic intermediates used in the sulfation reaction were obtained in high yields from four-component glycerol acetals by the process of transacetalization and selective crystallization of 1,3-dioxane derivatives. The physical data of the new compounds and some of their surface properties, such as critical micelle concentration (CMC), effectiveness of water surface tension reduction π_CMC, standard free energies of adsorption and micellization, ΔG _ads ^o and ΔG _CMC ^o , surface excess concentration, Γ_CMC, and the surface area demand per molecule, A_CMC, were determined. It was shown that the surface activity of the standard anionic surfactant sodium dodecyl sulfate should be similar to the surface activity of sodium (2-n-decyl-1,3-dioxan-5-yl)sulfate. Part XXX in the series: Chemical Structure and Surface Activity. Part XXIX: Sokołowski, A., B. Burczyk, and H.-R. Holzbauer, Adsorption of n-butyloligooxypropylene-pentaoxyethylene block copolymers at the aqueous solution-air interface, Collid Surfaces, in press.     

Synthesis and characterization of amphiphilic graft copolymers with poly(ethylene glycol) and cholesterol side chains

Amphiphilic graft copolymers comprising monomeric units of methoxy poly(ethylene glycol) (mPEG)-acrylate, 2-hydroxyethyl methacrylate (HEMA)–cholesterol conjugates and HEMA were synthesized and their properties characterized. The value of the critical micelle concentration (CMC) for these copolymers is linearly proportional to the ratio of the number of mPEG–acrylates to that of the HEMA–cholesterol conjugates per macromolecule (N_PEG/N_c), which is the most important parameter which influences the formation of polymeric micelles. The latter show excellent colloidal stability and their sizes decrease with increasing CMC. Based on the quenching of pyrene fluorescence, the relatively high levels of the loading capacity of pyrene are attributed to the elevated hydrophobicity of the micelle core. The loading capacity of pyrene decreases with increasing CMC. The weight-average partition coefficient for pyrene in polymeric micelles increases with increasing polymer concentration because more micelles are available for accommodating pyrene. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of the new cellulose derivative films based on the hydroxyethyl cellulose prepared from esparto “stipa tenacissima” cellulose of Eastern Morocco. II. Esterification with acyl chlorides in a homogeneous medium

Esparto “Stipa tenacissima” cellulose esters derivatives: HECA‐COO? C₄H₈? COOC₂H₅, HECA‐COO? C₈H₁₆? COOC₂H₅, and HECA‐COO? C₆H₄? COOC₂H₅ were successfully prepared in Tetrahydrofuran (THF)/triethylamine system with a degree of substitution (DS), respectively, DS_AD‐Et=0.32, DS_SB‐Et=0.22, and DS_TRP‐Et=0.50 using hydroxyethyl cellulose acetate (HECA; DS_AC=0.50) as intermediate product, and we avoided the drawbacks of cellulose solubility. The structural modifications were investigated using Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance (¹H‐NMR), Carbon‐13 nuclear magnetic resonance (¹³C‐NMR), and Distortionless Enhancement by Polarization Transfer 135° (DEPT‐135). The results from these analyses revealed the presence of the characteristic groups indicating that the grafting reaction was successful. The crystallinity and the structure order changes during the esterification reactions were recorded by X‐ray diffraction (XRD), it is found that the crystallinity degree decrease from 63.1% for Esparto “Stipa tenacissima” cellulose to 27.74% for HECA. The thermal stability of the esterified and unmodified cellulose samples was studied by thermogravimetric analysis (TGA)‐differential thermal analysis (DTA); the modified HECA exhibits a decrease in thermal stability relatively to the unmodified HECA, and this may be related to the groups grafted. The resulted cellulose esters HECA‐P_x (x = 1, 2, or 3) were soluble in THF and present an amorphous structure justified by XRD spectra. It was noted by TGA‐DTA analysis that the cellulose esters with low melting range were proved as thermoplastic polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Starch derivatives of a high degree of functionalization. VI. Multistep carboxymethylation

For the first time, carboxymethyl starch (CMS) samples with a very high degree of substitution (DS_CM = 2.1) were synthesized by multistep carboxymethylation under heterogeneous reaction conditions in methanol/water with sodium hydroxide and monochloroacetic acid as an etherifying agent. The stepwise increase in the total DS_CM value gradually decreased with an increasing DS_CM value of the starting polymer. The determination of the functionalization pattern of CMS by ¹H‐NMR spectroscopy after chain degradation indicated a high preference for 2‐O‐substitution. The distribution of the carboxymethyl functions was in the order O‐2 ? O‐6 > O‐3. A detailed analysis of the depolymerized sample by means of high‐performance liquid chromatography and capillary electrophoresis revealed a monomer composition that was in very good agreement with the statistical model of Spurlin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 743–752, 2002     

Effect of Substituents on Dielectric β-Relaxation in Cellulose

The dielectric characteristics for some cellulose derivatives, namely chlorodeoxycellulose (Cell-Cl; degree of substitution of chlorine, DS_Cl=0·87), bromodeoxycellulose (Cell-Br; DS_Br=0·92) and thiocyanatodeoxycellulose (Cell-SCN; DS_SCN=0·88), all substituted only at C-6, together with those of regenerated cellulose, have been investigated in the temperature range -60 to 120°C, and in the frequency range 0·2–100kHz. Only one relaxation process, designated as β, was identified within the frequency and temperature ranges studied. The activation energy of this relaxation increases in the order Cell-Cl<Cell-Br<Cell-SCN, suggesting that the bulkiness of the substituent was the determining factor of the activation energy. The characteristic dielectric parameters, namely polarization magnitude (Δε) and shape parameter (α or β-), were obtained by the analysis of absorption bands and are discussed in relation to the substituent effect. © of SCI.     

Morphological and structural formation of the regenerated cellulose membranes recovered from its cuprammonium solution using aqueous sulfuric acid

Morphological and structural formation of the regenerated cellulose membranes from its cuprammonium hydroxide solution by acid coagulation was investigated. Scanning electron microscopic observation revealed that the morphology of the membranes changed drastically as functions of both the cellulose concentration in the original cellulose solution C_Cell and the concentration of sulfuric acid as a coagulant C_H2SO4. It was found that at a constant polymer concentration (8 wt %) the membrane prepared by using 5 wt % aqueous sulfuric acid exhibits higher water flux, far smaller swelling anisotropy parameter L_t, and larger porosity P_r with a thinner skin structure, and these parameters were proven to be associated with lower (11 0) crystal plane orientation coefficient f_{∥(11 0)} compared with those for the membranes obtained by aqueous sulfuric acid with more than 10 wt %. On the other hand, at constant coagulant concentration (10 wt %) the membrane prepared by using the polymer solution with 5 wt % shows far greater P_r with practically no distinct skin structure; hence, a higher flux. The drastic changes in the morphology and structural parameters as functions of C_Cell and C_H2SO4 were found to be well correlated with abrupt changes in material transportation (copper ion, ammonium ion, and water) from the polymer solution to aqueous coagulants as a function of C_Cell and C_H2SO4. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1669–1678, 1999     

Nucleophilic displacement reactions on tosyl cellulose by chiral amines

Summary New 6-deoxy-6-amino cellulose derivatives with a degree of substitution (DS) in the range from 0.4 to 0.6 were synthesized by nucleophilic displacement (S_N) reactions of cellulose tosylates (DS_Tos 0.74 and 1.29) with R(+)-, S(−)- and racemic 1-phenylethylamine under homogeneous conditions in N,N-dimethylformamide and water. The structure of the polymers was characterized by elemental analysis, FTIR and ¹³C NMR spectroscopy. The DS values obtained as well as the optical rotation and circular dichroism measurements in dimethyl sulfoxide reveal that the initial chirality of the cellulose backbone does not have any significant influence on its reactivity with either of the two enantiomeric amines. Received: 21 September 2000/Accepted: 5 January 2001     

Kinetic Model of Two‐Phase Epoxidation with Ionic Liquids as Micellar Catalysts

The biphasic catalytic epoxidation of cyclooctene using the ionic liquid (IL) 1,2‐dimethyl‐3‐octyl‐imidazolium perrhenate ([OMMIM]ReO₄) as micellar catalyst and H₂O₂ as oxidant was investigated. Kinetic experiments were carried out in the intrinsic kinetic regime as proved by variation of stirring rate and temperature. Variation of catalyst concentration allowed for determination of the critical micellar concentration (CMC) of the catalytic IL. The effect of substrate concentrations on the reaction rate was also assessed. Based on the experiments, a kinetic model adapted from enzyme catalysis was proposed to account for the micellar reaction environment. The model takes into account the onset of micelle formation at the CMC. The application of the kinetic model illustrated the good agreement with the experimental data. The model will be applied to other micellar epoxidation reactions and for the design of an appropriate reaction setup in the future.     

Specific hydroxide ion catalysis of the endwise depolymerization of cellulose

The endwise depolymerization (unzipping reaction) of hydrolyzed cotton cellulose (x = 200) in water under a nitrogen atmosphere was followed at 98°C at several alkalinities in the pH range of 8.0–10.5. The observed apparent first-order rate constant k₁ was invariable at low alkalinity (k₁ = k₀), while above pH 8.5, k₁ increased with pH. The data conform with the expression where [SH] denotes substrate concentration. The specific hydroxide ion catalysis is considered to involve ionization of the anomeric hydroxyl group at the reducing chain end that leads to elimination of the glucosidic oxygen atom bearing the polymer chain from C4 of the terminal D-glucose residue. In this initiation process, the glucosidic oxygen is eliminated as an anion so that rapid propagation of the unzipping along the polymer chain may occur. Thus, entire chains will depolymerize. The kinetic chain length v is defined as the ratio k₁:k_t, where k_t is the pseudofirst-order rate constant for chain terminations, and a value of v ～ 100 D-glucose residues was found at all the alkalinities investigated.     

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.     

Synthesis and surface properties of chemodegradable anionic surfactants: Diastereomeric (2-n-alkyl-1,3-dioxan-5-yl) sulfates with monovalent counter-ions

Sodium, potassium and ammonium cis- and trans-(2-n-alkyl-1,3-dioxan-5-yl) sulfates 6–8 (alkyl: n-C₉H₁₉, 6a–8a, and n-C₁₁H₂₃, 6b–8b) were synthesized in a reaction of aliphatic aldehydes 1a,b with glycerol 2 followed by separation in high yields of individual geometric isomers of cis-and trans-2-n-alkyl-5-hydroxy-1,3-dioxanes, cis-3a,b and trans-3a,b, followed by sulfation with sulfur trioxide-pyridine complex, and finally neutralization with NaOH, KOH, and NH₄OH, respectively. Physical data of the compounds and some surface properties of 2-n-nonyl derivatives, such as critical micelle concentration (CMC), effectiveness of aqueous surface tension reduction (Π_CMC), surface excess concentration Γ_CMC, and the surface area demand per molecule (A_CMC), were determined. It was shown that the surface activity of these compounds is influenced both by their geometric structure and by the monovalent counter-ion.     

Surface and Aggregation Properties of Synthesized Cetyl Alcohol Based Bis-Sulfosuccinate Gemini Surfactants in Aqueous Solution

A series of cetyl alcohol based anionic bis‐sulfosuccinate gemini surfactants (BSGSCA1,4; BSGSCA1,6 and BSGSCA1,8) with different spacer lengths was prepared using dibromoalkanes. The surfactant structure was elucidated using elemental analysis, Fourier transform infrared spectroscopy (FT‐IR) and nuclear magnetic resonance spectroscopy (NMR). Surface tension measurements were used to determine the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), surface pressure at the CMC (π_CMC) and efficiency of adsorption (pC20). On the basis of surface studies, the CMC and γ_CMC decreases with increasing length of the spacer group. The micelle aggregation number, determined by fluorescence quenching studies, increases with increasing surfactant concentration above the CMC. The micropolarity in the micelle increases with increasing length of the spacer and decreases with increasing surfactant concentration.     

Novel bis(acetylacetonate)palladium/boron trifluoride etherate catalyst system for the polymerization of norbornene

The boron trifluoride etherate, BF₃OEt₂, was used as an activator towards bis(acetylacetonate)palladium precursor in the polymerization of norbornene. The catalyst system Pd(Acac)₂/BF₃OEt₂ was highly active in the polymerization of norbornene. Catalytic activity up to 20,220 kg/(mol Pd · h) and intrinsic viscosities up to 2.64 dL/g were observed, respectively. Catalytic activity, polymer yield and polymer molecular weight could be controlled by varying the reaction parameters. The molar mass distribution indicates a single-site, highly homogeneous character of the active catalyst species. NMR spectroscopy study of the polymer showed exclusively 2,7-enchained repeating units of polymer backbone.     

Hydrothermal synthesis of potassium–sodium niobate powders

Potassium–sodium niobates (K_xNa_1−xNbO₃, 0 < x < 1, KNN) were hydrothermally synthesized under varying alkaline ratios (K⁺/Na⁺), total hydroxide concentration, reaction temperature, and time. Compositional surveys were developed by using Rietveld analyses derived quantitative volume fractions. The data demonstrated that phase pure KNN synthesis can be achieved by reacting the niobium source with the hydroxide solution having 6 M total hydroxide concentration, cation ratio (K⁺/Na⁺) of above 6 at temperatures ≥200°C for 24 h. Dissolution–precipitation events through intermediate products including hexaniobates were postulated as a plausible formation mechanism. It was shown also that the single-phase KNN approaching the morphotropic phase boundary (MPB) could be obtained by further incorporation of sodium ions into the crystal via post-annealing at 800°C/2 h, following the hydrothermal synthesis.     

Synthesis and lyotropic behavior of mesogen‐linked cellulose acetates

Three aromatic (p‐carboxyl phenyl) esters, 4‐(benzoyloxy) benzoic acid, 4‐(4′‐methylbenzoyloxy) benzoic acid, and 4‐(4′‐chlorobenzoyloxy) benzoic acid, were synthesized and they showed nematic monotropic or thermotropic behavior. The mesogen‐linked cellulose acetates were first prepared by the reaction of aromatic (p‐carboxyl phenyl) esters with cellulose acetate through esterification in the presence of N,N‐dicyclohexylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Their degrees of mesogenic unit substitution (DS_‐meso) were between 0.27 and 0.41. It was found that they can form cholesteric lyotropic phases in dichloroacetic acid and their critical concentration was about 25 wt %. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2693–2697, 2004     

Polymeric surfactants for enhanced oil recovery. Part V: Prediction models for the effect of temperature and length of polyoxyethylene chain or hlb on surface and thermodynamic properties of some ethoxylated polymeric nonionics

Several equation models were investigated to find the relationship between temperature (T). number of ethylene oxide (EO) units (n) or the hydrophile-lipophile balance (HLB) and the surface and thermodynamic properties of some ethoxylated alkylphenol-formaldehyde polymeric nonionic surfactants. These properties include critical micelle concentration (CMC), free energy of micellization (ΔG_mic), surface tension at CMC (7_CMC), effectiveness (γ_CMC) and efficiency (pC₂₀) of surfactant to reduce the surface tension of water. The values of the ratio CMC/C_{2(π = 20)} were also considered. The linear multiple regression technique was employed to determine the parameters of the equations and to choose the best forms with the highest values of R² and F-ratio which reflect the goodness and the reliability of the fit.     

Preparation,structural characterization,and flocculation ability of amphoteric cellulose

A series of amphoteric celluloses (QACMCs) were prepared from sodium carboxymethyl cellulose (CMC) and 2,3-epoxypropyltrimethylammonium chloride (EPTMAC) with a cationic degree of substitution (DS_cat) of 0.24–1.06 and a carboxymethyl degree of substitution (DS_ani) of 0.60. The structures of the samples were characterized by FTIR and NMR spectroscopy, which revealed that DS_cat depended on the ratio of EPTMAC to CMC in the reaction mixture and that the substituent distribution of the cationic group at the C2, C3, and C6 positions of the QACMCs ranked as follows: C2 > C6 > C3. The QACMCs dissolved over a wide range of pH levels and exhibited flocculation ability against kaolin suspensions. In particular, the samples with high DS_cat exhibited excellent flocculation performance. In addition, the flocculation characteristics of the QACMCs depended on the pH of the kaolin suspension.