Homogenous synthesis of hydroxyethylcellulose in NaOH/urea aqueous solution

Hydroxyethylcellulose (HEC) was synthesized by a fully homogenous method from cellulose in 7.5 wt.-% NaOH/11 wt.-% urea aqueous solutions under mild conditions. HEC samples were characterized with NMR, SEC-LLS, solubility, and viscosity measurements. The MS and DS values of the obtained HEC samples are in the range from 0.54 to 1.44 and 0.45 to 1.14, respectively, and the relative DS values at C-2 and C-6 hydroxyl groups are slightly higher than those at C-3 hydroxyl groups. HEC samples are soluble in water starting from a MS of 0.57 and DS of 0.49, which display high viscosity in aqueous solutions. Moreover, a NaOH/urea aqueous solution is a stable system for cellulose etherification. In this way, we could provide a simple, pollution-free, and homogeneous aqueous solution system for synthesizing cellulose ethers.     

Analytische Charakterisierung von Verdickungsmitteln auf Polysaccharidbasis

Zusammenfassung Im vorliegenden zweiten Teil der dreiteiligen Übersicht zur Analytik der Polysaccharide wird am Beispiel einer Methylhydroxyethylcellulose (MHEC) die Erfassung der Celluloseether und -mischether mittels der Gas-Chromatographie vorgestellt. Dabei handelt es sich um die Beschreibung einer quantitativen Methode hoher Empfindlichkeit, die erforderlich ist, um Cellulosederivate mit geringer Mischsubstitution zu identifizieren und zu unterscheiden. Dazu werden die Celluloseether in einer speziell entwickelten Apparatur mit Iodwasserstoffsäure bei 140°C erhitzt. Von den sich bildenden Spaltprodukten werden die abdestillierten Alkyliodide in gekühltem Hexylbromid aufgefangen, gas-chromatographisch getrennt und identifiziert; gebildete Olefine werden durch Bromaddition erfaßt. Reproduzierbarkeit: 3% rel. Erfassungsgrenze: = 0,01% Hydroxyethylcellulose (HEC). Die Methode eignet sich auch zur Erfassung von Estern, S-Alkylgruppen, Methylimidverbindungen, Glykolanteilen oder bestimmten Tensiden.

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Analytical characterization of polysaccharide based thickenersPart II. Qualitative and quantitative determination by zeisel-cleavage

Summary In this second part of the three-part review on analysis of polysaccharides the characterization of cellulose ethers and cellulose mixed ethers by means of gaschromatography is described. The identification of the wide varying field of this cellulose ethers is presented using methylhydroxyethylcellulose (MHEC) as an example. To differentiate all cellulose mixed ethers, even those with little substitution of one of the two ether components, the method has to work qualitatively and quantitativly with a high sensitivity. The cellulose ethers are treated with hydriodic acid at 140°C in a special apparatus. The alkyliodides formed are distilled into cooled hexyl bromide. They are separated and identified by gaschromatography. Olefins also formed are determined by addition of bromine. Reproducibility: 3% rel. Limit of detection: = 0.01 % Hydroxyethylcellulose (HEC). This method can also be used for the determination of esters, S-alkyl groups, methylimides, glycols and some detergents.

Herrn Dr. Bruno W. Werdelmann zum 60. Geburtstag gewidmet     

Investigation of the cellulose ethers effect on the Portland cement hydration by thermal analysis

Cellulose ethers (CE) are introduced in almost all cement-based dry mortars in order to retain water in mortar mass avoiding losing it too quickly by substrate absorption or water evaporation. In this way the workability of the fresh material, the adherence to the substrate and internal-strength characteristics of mortar, render or tile adhesive are improved. One of the side effects of cellulose ethers is the Portland cement hydration delaying. The influence of six commercial cellulose ethers, hydroxyethylmethyl cellulose (HEMC) type, on the hydration of Portland cement CEM I 42.5 R, was followed by thermal analysis (TG and DTA curves). Three of these cellulose ethers are unmodified, and have different viscosities, while three of them have the same viscosity but differ in the degree of modification (unmodified, one with medium modification and one with high modification). The interest of dry mortars producers for the effects of these cellulose ethers, is generated by the wide offer available on the market and by the absence of systematic data on the effect of different viscosities and degrees of modification on dry mortars properties. In order to quantify the effect of the CE on the cement hydration, the surface area of the endothermic effect corresponding to the dehydration of portlandite (Ca(OH)₂), formed after 1, 3, and 7 days of hydration, was defined. It was noted that the proportion of Ca(OH)₂ in samples containing CE after 1 day was 30–40 % lower than in reference sample. After 3 and 7 days of hydration the proportion of Ca(OH)₂ in samples containing CE approaches that of reference sample (10–20 % less). For the same period of hydration, the different viscosity, and different degree of modification of cellulose ethers cause variations in narrow limits of the proportion of Ca(OH)₂, and the degree of cement hydration, respectively.     

Green Synthesis and Characterization of Hybrid Collagen–Cellulose–Albumin Biofibers from Skin Waste

Collagen (C) and cellulose are prominent biopolymers from the animal and plant kingdom and widely used in bioengineering. Albumin, on the other hand, is the most abundant plasma protein present in mammalian blood. In this work, collagen extracted from animal skin waste was blended with hydroxyethyl cellulose (HEC) and bovine serum albumin (A) and wet-spun to form hybrid biodegradable C/HEC/A fibers. They were further cross-linked with glutaraldehyde vapors and analyzed. X-ray diffraction and infra-red spectroscopic studies of the hybrid fibers display peaks corresponding to collagen, cellulose, and albumin. Incorporation of cellulose into the biopolymeric matrix leads to a reasonable improvement in mechanical, swelling, and thermal properties of hybrid fibers. Addition of albumin improves the regularity of fiber surface without altering the porosity as observed under a microscope. Hence, the formed hybrid biofibers can be potentially used as a suture material as well as for different biomedical applications due to their improved properties.     

Cooperativity in the adsorption of cellulose ethers and fibrinogen at liquid-solid interfaces

The possibility of reducing fibrinogen adsorption to solid surfaces by competitive adsorption of cellulose ethers (EHEC, HEC) was investigated. The surface concentration of fibrinogen adsorbed onto hydrophilic and hydrophobic (methylized) glass was measured with an enzyme-linked immunosorbent assay. The immunoassay was calibrated by ellipsometry, using the initial mass transport limitation of adsorption for calculations of the maximum amount of adsorbed protein.At a hydrophobic surface, the presence of cellulose polymers caused a decrease of the adsorption of fibrinogen. The hydrophobic EHEC (cloud point 35°C) was most efficient and abolished surface-adsorption of the protein.At a hydrophilic surface, positive cooperativity was seen between fibrinogen and cellulose polymers. The hydrophilic HEC (cloud point >100°C) gave the most prominent effect.The results indicate that the affinity between a water soluble polymer or protein and a solid surface is not the only factor determining surface adsorption. The finding that there may be both positive and negative cooperativity in the adsorption of polymers shows the importance of polymer compatibility in layers of adsorbed polymers.     

PVP/HEC分子间缔合作用机理探讨

通过粘度、紫外光谱、红外光谱和DSC谱的测定,探讨了PVP/HEC分子间的缔合机理.结果表明,PvP/HEC复合体系相对于单一体系产生了粘度的负协同效应,NaCl的加入使单一体系和复合体系的粘度均下降;在紫外可见吸收光谱中,PVP/HEC复合体系的最大吸收波长λmax相对于PVP、HEC各自的λmax都发生红移;PVP/HEC复合物的红外光谱在2370 cm-1出现新的吸收峰;DSC谱中复合物的峰温高于简单混合物,而其焓变低于简单混合物,这一切均证明HEC与PVP之间未发生疏水缔合,而是HEC的羟基与PVP的羰基之间通过氢键缔合成复合物,复合物的分子链排列较为紧密.     

Interactions between sodium dodecyl sulphate and non-ionic cellulose derivatives studied by size exclusion chromatography with online multi-angle light scattering and refractometric detection

The novel approach described allows to characterise the surfactant-polymer interaction under several sodium dodecyl sulphate (SDS) concentrations (0-20 mM) using size exclusion chromatography (SEC) with online multi-angle light scattering (MALS) and refractometric (RI) detection. Three different cellulose derivatives, hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC) and hydroxyethyl cellulose (HEC), have been studied in solution containing 10 mM NaCl and various concentrations of sodium dodecyl sulphate. It is shown that this approach is well suited for successful application of both Hummel-Dreyer and multi-component light scattering principles and yields reliable molecular masses of both the polymer complex and the polymer itself within the complex, the amount of surfactant bound into the complex as well as appropriate values of the refractive index increment (dn/dc)micro, of both the complex and the polymer in question. The more hydrophobic derivatives HPC and HPMC adsorbed significantly more SDS than HEC. The inter-chain interactions close to critical aggregation concentration (cac) were clearly seen for HPC and HPMC as an almost two-fold average increase in polymer molecular mass contained in the complex.     

羟乙基纤维素和聚氧化乙烯在超声波辐照下的降解与嵌段共聚的研究

本文分别研究了在超声波辐照下羟乙基纤维素(HEC)和聚氧化乙烯(PEO)在水溶液中的降解规律,HEC与PEO在水溶液中的超声波辐照共聚反应。用DTA、IR、MS、X射线衍射和偏光显微镜初步研究了共聚物的结构,证明所得产物主要是嵌段共聚物。将浓度为0.5％的HEC/PEO水溶液在25±1℃,频率为18.2kHz,超声波强度(以逆变器主迴路输入电流表示)为2.5A下辐照10分钟,共聚物产率为55.07％。     

均相体系中纤维素化学改性研究概述

本文概述了近十年来纤维素在均相体系中化学改性的研究成果,重点介绍了纤维素在氯化锂/N,N-二甲基乙酰胺（LiCl/DMAc）、二甲基亚砜/三水合四丁基氟化铵（DMSO/TBAF3H2O）、离子液体、碱/尿素体系中的均相酯化、醚化以及接枝共聚合反应.同时,总结了纤维素在这些溶剂中的反应特性及其衍生化产物的结构、性质和应用.     

Water‐dispersive PLA‐based materials: from reactive melt processing to properties

Melt blending of poly(l ‐lactide) (PLLA) and water‐soluble polymers was carried out through reactive melt processing with the objective to prepare water‐dispersible PLLA‐based materials. For this purpose, both polyvinyl alcohol (PVOH) and hydroxyethyl cellulose (HEC) were considered. Prior to melt blending, the preparation of plasticized PVOH and plasticized HEC was performed. The so‐obtained blends have been characterized in terms of morphology and thermomechanical properties. The morphological analysis evidenced the possibility to prepare co‐continuous PLLA/plasticized HEC blends. Nevertheless, their low melt strength did not allow producing monofilaments by melt spinning. Thus, PVOH was considered as an alternative to HEC. The results showed that using maleic anhydride‐grafted polylactide as a compatibilizer for PLLA/plasticized PVOH 40/60 (w/w) blends allowed preparing co‐continuous blends leading to tough monofilaments with high ultimate elongation. Moreover, the assessment of the water dispersiveness revealed that the monofilaments readily swelled in water and started to break up after 30 min. A full fragmentation of the monofilaments was observed within 1 hr. Copyright © 2015 John Wiley & Sons, Ltd.     

Application of NIR reflectance spectroscopy for the identification of pharmaceutical excipients

For manufacturing of medicaments, all ingredients must be reliably identified. Wet chemistry methods for identification of cellulose ethers, used by the Pharmacopoea Europea, is time consuming and expensive. To distinguish microcristalline and powdered cellulose, only unspecific sedimentation properties are used. However, applications as well as technological and pharmacokinetic properties of cellulose and various cellulose ethers are different.

NIR reflectance spectroscopy speeds up the identification of excipients. So this technique causes fewer delay in manufacturing processes. The discrimination of powdered and microcristalline celluloses as well as cellulose and cellulose ethers is made possible by factor analysis and soft independent modelling of class analogies (SIMCA). The classification was improved by spectral pretreatment multiplicative scatter correction (MSC), derivation and wavelength selection. The discrimination of powdered and microcristalline celluloses is statistically highly significant, so the identification can be done reliably. Cellulose ethers can be quickly identified by NIR spectroscopy, although a large number of samples of different manufacturers and physical properties, for example viscosity, were used. The only exception is the discrimination of methylcellulose and cellulose ethers containing methyl and hydroxyalkyl substituents, which show identical spectra. But even for those excipients, the wet chemistry expenses can be reduced to one test. The developed strategy for data evaluation is quite general in nature, hence it can be applied to other pharmaceutical powders, excipients and active components as well.     

X-ray and neutron reflectometry investigation of Langmuir-Blodgett films of cellulose ethers

Langmuir-Blodgett films of a series of cellulose ethers are investigated by X-ray and neutron reflectometry. Two types of samples are considered: simple alkyl ethers of cellulose and derivatives obtained by the alkylation of (2-hydroxypropyl)cellulose (HPC). All of the cellulose ethers form stable monolayers at the air-water interface. Significant differences are, however, found in the surface pressure-area compression isotherms. Ethers prepared from HPC typically exhibit larger limiting molecular areas and higher surface pressures than the corresponding simple cellulose ethers. The ease of monolayer transfer to hydrophobic silicon substrates differs greatly from one type of molecule to another. Successful transfer conditions are found only for ethers that form stable monolayers at sufficiently high surface pressures. Surprisingly, deuterated HPC ethers, prepared for neutron reflectivity measurements, exhibit monolayer properties significantly different from those of their hydrogenated analogues. Although essentially identical limiting molecular areas are found, the surface pressure corresponding to a characteristic plateau transition in the compression isotherm is found to decrease by about 8-10 mN m(-1) upon side chain deuteration. X-ray reflectivity results show a linear increase of film thickness with the number of deposited layers, indicating a regular and reproducible transfer. Observed average layer spacings are, however, significantly smaller than the calculated length of fully extended side chains. Neutron reflectivity curves recorded for composite LB films composed of both deuterated and hydrogenated polymers exhibit regular Keissig fringes, but no Bragg peak. This result indicates that these LB films do not possess an internal periodic structure and the initial layer-by-layer organization is lost by large interlayer diffusion.     

Clouding and phase behavior of nonionic surfactants in hydrophobically modified hydroxyethyl cellulose solutions

Clouding phenomena and phase behaviors of two nonionic surfactants, Triton X-114 and Triton X-100, in the presence of either hydroxyethyl cellulose (HEC) or its hydrophobically modified counterpart (HMHEC) were experimentally studied. Compared with HEC, HMHEC was found to have a stronger effect on lowering the cloud point temperature of a nonionic surfactant at low concentrations. The difference in clouding behavior can be attributed to different kinds of molecular interactions. Depletion flocculation is the underlying mechanism in the case of HEC, while the chain-bridging effect is responsible for the large decrease of cloud point for HMHEC. Composition analyses for the formed macroscopic phases were carried out to provide support for associative phase separation for the case of HMHEC, in contrast to segregative phase separation for HEC. An interesting three-phase-separation phenomenon was reported in some HMHEC/Triton X-100 mixtures at high surfactant concentrations.     

Construction of conductive hydroxyethyl cellulose/soy protein isolate/polypyrrole composite sponges and their performances

Cellulose - In the present study, we have in situ synthesized polypyrrole (PPy) on the hydroxyethyl cellulose/soy protein isolate (HEC/SPI) sponges to construct electro-conductive HEC/SPI/PPy...     

Crosslinking Parameter on the Preparation of Cellulose Based Hydrogel with Divynilsulfone

Polymeric hydrogels are crosslinked polymers which display high sorption capacity in water and water solution. In this work, cellulose based hydrogel was prepared with divinylsulfone as crosslinking agent. Cellulose based hydrogel was synthesized as a mixture of sodium salt of carboxymethylcellulose (CMCNa) and hydroxyethylcellulose (HEC). The effect of chemical composition, temperature and reaction time during crosslinking processes was investigated both the value of equilibrium water uptake and swelling ratio. Infrared spectra of the synthesized polymeric networks were studied to investigate the chemical structure of crosslinking reaction qualitatively. The thermal properties and morphology of the obtained cellulose based hydrogels were observed by means of TGA (thermo-gravimetry analysis) and SEM (scanning electron microscopy), respectively. Crosslinking of CMCNa/HEC polymeric network results in a decrease in thermal stability. Hydrogel with weight ratio of CMCNa/HEC 5 to 1 at reaction temperature of 60 °C gave the highest absorption capacity in distilled water.     

Methane hydrate stability in the presence of water-soluble hydroxyalkyl cellulose

The effect of low-dosage water-soluble hydroxyethyl cellulose (approximate MW～90,000 and 250,000) as a member of hydroxyalkyl cellulosic polymer group on methane hydrate stability was investigated by monitoring hydrate dissociation at pressures greater than atmospheric pressure in a closed vessel. In particular, the influence of molecular weight and mass concentration of hydroxyethyl cellulose (HEC) was studied with respect to hydrate formation and dissociation. Methane hydrate formation was performed at 2℃ and at a pressure greater than 100 bar. Afterwards, hydrate dissociation was initiated by step heating from -10℃ at a mild pressure of 13 bar to 3℃, 0℃ and 2℃. With respect to the results obtained for methane hydrate formation/dissociation and the amount of gas uptake, we concluded that HEC 90,000 at 5000 ppm is suitable for long-term gas storage and transportation under a mild pressure of 13 bar and at temperatures below the freezing point.     

不同相对分子质量羟乙基纤维素对甲维盐微胶囊制备的影响

采用原位聚合法以三聚氰胺-甲醛树脂为壁材制备了甲维盐微胶囊。 探讨了不同黏均相对分子质量羟乙基纤维素作为乳化剂对微胶囊表面形貌、粒径及其分布、包覆率与载药量的影响,对使用不同黏均相对分子质量羟乙基纤维素作为乳化剂制备的微胶囊的释放性能进行了表征。 结果表明,以相对分子质量较小的羟乙基纤维素制备的微胶囊外形规则、致密且无黏连现象。 随羟乙基纤维素黏均相对分子质量的增加所得微胶囊的平均粒径及粒径分布逐渐增大,包覆率与载药量逐渐减小。 释放性能的研究表明,采用相对分子质量较小的羟乙基纤维素制备的微胶囊的释放性能较好。     

Superabsorbent materials derived from hydroxyethyl cellulose and bentonite: Preparation,characterization and swelling capacities

Superabsorbent polymers (SAPs) and composites (SAPCs) were prepared entirely by graft copolymerization of polyacrylamide (PAM) onto hydroxyethyl cellulose (HEC), using potassium persulfate (KPS) as an initiator, and N,N′-methylenebisacrylamide (MBA) as a crosslinker, in an aqueous solution. The extent of grafting was evaluated from % grafting efficiency (%GE) for various HEC/AM ratios, and a near optimal ratio was determined. Influences of various preparation parameters, i.e., the ratio of HEC/AM, amount of initiator and crosslinker, reaction temperature and time, and amount of filler on water swelling capacity of SAPs and SAPCs were studied. An FT-IR determination confirmed that the PAM was successfully grafted onto the HEC backbone, by showing absorption bands of the HEC backbone and new absorption bands from the grafted copolymer. The swelling capacity of SAPs and SAPCs depended strongly on different parameters, and the maximum swelling capacity was over 426 g/g and 538 g/g for the SAPs and SAPCs, respectively.     

Laser flash photolysis and time-resolved fluorescence measurements of the aggregation number of SDS-biopolymer complexes

Aqueous solutions of 0.5% sodium carboxymethyl cellulose, NaCMC, and 2-hydroxyethyl cellulose, HEC, and variable concentration of sodium dodecyl sulfate, SDS, were studied by the intensities ratio of pyrene fluorescence bands (I/III and monomer/excimer) and conductance measurements to determine the critical aggregation concentration, cac, and the degree of micellar dissociation, alpha, respectively. The cac of these systems is close to 2-4 x 10(-3)M and values of alpha are consistent with the formation of SDS micelles adsorbed cooperatively to the polymer backbone. Laser flash photolysis (LFP) and time-resolved fluorescence (TRF) techniques were employed to determine the micellar aggregation number, N, using the probes flavone and pyrene, respectively. The obtained N for HEC/SDS and NaCMC/SDS were 48 and 68, respectively. The presence of the counterions at the NaCMC backbone is the main factor responsible for this number. Besides, the transient spectra of flavone and present in 0.5% HEC or NaCMC with and in absence of SDS are discussed. Flavone triplet state exit rate constant from the biopolymer/SDS complexes showed that these systems are completely different from a pure SDS micelle.