Preparation of Rh-containing cellulose acetate films and the chemistry of Rh in cellulose acetate

RhCl [P(C₆H₅)₃]₃ complexes have been incorporated in cellulose acetate as a dispersion medium using cosolvent (tetrahydrofuran). The interactions between Rh (I) complexes and cellulose acetate (CA) are examined by infrared spectroscopy and thermal analysis. The chemical reactivities of Rh–CA films have been investigated by reacting Rh sites with CO, H₂, O₂, and C₂H₄ in the temperature range 90–150°C and at a pressure of less than 1 atm. Three different Rh-carbonyls and a Rh-hydride species formed in CA are characterized by their infrared spectra. Treatment of 10 or 20 wt % Rh–CA films with hydrogen (600 torr) at 150°C produces small Rh metal particles of ca. 10 Å or less in diameter in CA, which show catalytic activities under mild conditions in various reactions such as hydrogenation of C₂H₄, oxidation of CO, and Fischer–Tropsch type reactions.     

The states of water in cellulose acetate membranes

Differential scanning calorimetric melting endotherms of wet and half-dried cellulose acetate membranes and salt distribution coefficients were studied to clarify the states of water in membranes. We have suggested that (a) there are four states of water in cellulose acetate membranes; (b) these states of water are those of completely free water, free water very weakly interacting with polymer, bound water which can contain salts, and bound water which rejects salts; (c) the semipermeability of membranes depends on the ratio of four states of water in membranes.     

纤维素乙酸酯的现状及发展前景

从生产工艺流程及应用方面,介绍了乙酯纤维和纤维素乙酯膜的现状及发展。对纤维素乙酸酯的发展提出了几点建议。指出目前是国内开发乙酯产品的较佳时机。     

纤维素化学研究进展

为了研究当前纤维素化学发展现状,综述了纤维素超分子结构及其成因,介绍了纤维素自组装的结构模型,讨论了纤维素的多种原材料（细菌纤维素、人工化学合成纤维素、棉花、木材、禾草植物、韧皮纤维以及农业废弃物）,着重介绍了细菌纤维素的制备与商业用途以及人工化学合成纤维素,综述了目前纤维素化学研究的热门课题：选择性取代、新纤维素溶剂、纤维素的预处理、纤维素衍生物以及纤维素功能材料的发展现状、再生纤维的研究发展现状、纳米纤维素的制备与表面化学改性.选择适宜的原材料,对天然纤维素进行可控物理、化学结构设计,从而可以制备特殊功能的精细化工产品.纤维素化学是21世纪可持续发展的化学工程研究的重要课题之一.     

Thermoplastic cellulose acetate and cellulose acetate compounds prepared by reactive processing

Novel families of thermoplastic polysaccharides such as cellulose-2,5-acetate were produced by means of reactive processing technology that grafted cyclic lactones simultaneously onto polysaccharide, hydroxyfunctional plasticizer, and optionally also onto hydroxyfunctional fillers. Organosolv lignin, cellulose, starch, and chitin were added to effect reinforcement of the polymer matrix. Mechanical and thermal properties depended upon molecular architecture of the components and process parameters such as temperature, feed ratios, and screw speed. Such blends and composites utilize renewable resources and are of interest in waste disposal via biodegradation. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 213–242, 1997     

The thermodynamic state of water in cellulose acetate membranes

Using experimental sorption data and corresponding experimental results from calorimetric investigations, the state of water in cellulose acetate (CA) membranes is discussed by applying a theoretical treatment of sorption reported previously (1–3). The sorption of water can be attributed to a gain in surface energy at the polymer/vapor interface. Using differential thermodynamic potentials of sorbed water together with experimentally determined heat capacities of sorbed water, the thermodynamic potentials G, H, and S of sorbed water are estimated for the temperature interval ?40 to + 40°C. At constant temperature, each thermodynamic potential depends on the water content. The resulting distribution function of G indicates that the sorbed water exists in different states. Comparing the Gibbs free energy of sorbed water with that of ice or liquid water at the same temperature leads to the conclusion that none of the sorbed water freezes to ice within the temperature interval used. Based on the Gibbs free energy of water in electrolyte solutions and the distribution function of G for sorbed water, partition coefficients of salts within CA membranes may be estimated. The results are in good agreement with experimentally determined partition coefficients which are available from the literature. As the partition coefficient of a salt is directly related to the salt rejection of the membrane, this provides a method of estimating the desalination performance of a membrane from its water sorption isotherm.     

The electret effect in cellulose acetate reverse osmosis membranes

The electret potentials developed by reverse osmosis electret membranes help control the undesirable deposition of charged colloidal particles on the membrane surfaces during membrane desalination. These antifouling electret membranes should help prevent the costly flux declines normally associated with deposition of colloidal iron oxides on the reverse osmosis membrane surfaces. Homocharge and heterocharge behavior of cellulose acetate membrane electrets have been studied. Asymmetric reverse osmosis membranes and dense membrane films were studied. The homocharge and heterocharge of cellulose acetate reverse osmosis electret membranes have been explained.     

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.     

Compostability of cellulose acetate films

Composting is an accelerated biological decay process viewed by many to be a potential solution to the solid-waste management crisis existing in many parts of the world. As part of a program to develop environmentally nonpersistent polymers that are compatible with a composting environment, we have developed a bench-scale compost methodology that emulates a high efficiency municipal windrow composting operation. A series of cellulose acetate films, differing in degree of substitution, were evaluated in this bench-scale system. In addition, commercially available biodegradable polymers such as poly(hydroxybutyrate-co-valerate) (PHBV) and polycaprolactone (PCL) were included as points of reference. Based on film disintegration and on film weight loss, cellulose acetates, having degrees of substitution less than approximately 2.20, compost at rates comparable to that of PHBV. NMR and GPC analyses of composted films indicate that low molecular weight fractions are removed preferentially from the more highly substituted and slower degrading cellulose acetates. © 1994 John Wiley & Sons, Inc.     

纤维素化学的现状与发展趋势

本文综述了纤维素化学的研究现状和发展趋势，包括近10年来纤维素结构、纤维素衍生物如纤维素磷酸酯、纤维素醋酸酯、纤维素硝酸酯、羧甲基纤维素、羟丙基纤维素和乙基纤维素等，以及纤维素的裂解与能源、纤维素液晶及其复合材料、新型纤维素衍生物及其功能材料的合成、生物技术在纤维素化学中的应用等主要研究领域。探讨了未来20年的研究课题：（1）纤维素制品的高质和高值化；（2）食用纤维素及纤维素保健食品；（3）新型纤维素功能材料的制备及应用；（4）生物技术应用的工业化。     

Phenol transport in cellulose acetate membranes

Past detailed studies of solute transport through reverse-osmosis membranes have been conducted only with simple salts. The present work with phenol was undertaken largely because of the practical observation that the transport of low molecular weight organics is much more rapid than that of the salts. Studies of phenol sorption from dilute aqueous solution indicate that the diffusion coefficient for phenol in water-saturated 39.8 wt.-% acetyl cellulose acetate is 9.6 × 10^-10 cm.²/sec., and the equilibrium distribution coefficient between the acetate phase and water is 42. Thus, the diffusion coefficient is quite close to that measured for sodium chloride, and the higher permeability of the membranes to phenol can be attributed entirely to their greater sorption of this solute. In direct osmosis experiments performed with significant water flow a measurable interaction or positive coupling between water and phenol flows has been observed. Further evidence of flow coupling is derived from reverse osmosis experiments in which significant negative solute rejection is observed; i.e., the permeate is enriched in phenol by as much as 20%. It is shown that a solution-diffusion transport model is not adequate to rationalize the results, and a more complex transport model is apparently required.     

Ion movements in cellulose acetate membranes

The behavior of ions in a cellulose acetate membrane was discussed from the standpoint of mobilities obtained from the membrane potentials. The mobilities of univalent ions larger in radius or divalent ions relative to Na⁺ ion mobility in the membrane are much different from those in aqueous solutions. The order of the mobilities of ions in the membrane is shown quantitatively. The mobilities of the ions with radii larger than a certain value in the membrane decrease with increase in their size. This could be explained by the physical friction between the ion and the membrane wall. This friction is of importance as the ionic radius comes close to the intermolecular gaps between polymer chains. The mobilities of Na⁺ anyd 1^? ions in the membrane are (2–3) × 10^?7 cm²/sec-V and are about three to four orders of magnitude less than those in aqueous solutions.     

The bulk-dyeing of cellulose acetate with disperse aldehyde dyes

Conclusions 1. The possibility of obtaining dyed cellulose acetate by the addition to an acetonic solution of cellulose acetate of acetone-soluble aldehyde dyes which form strong chemical bonds with it has been studied.2. The optimum conditions for bulk-dyeing with aldehyde dyes have been worked out.3. It has been shown that the reaction of an aldehyde dye with cellulose diacetate leads to partial saponification of the acetyl groups. The hypothesis has been put forward of the subsequent acetylation of the hydroxy groups liberated by the aldehyde dyes.Institute of Chemistry, Academy of Sciences of the Tadzhik SSR. Novosibirsk Institute of Organic Chemistry, Siberian Division of the Academy of Sciences of the USSR. Translated from Khimicheskie Volokna, No. 3, pp. 39–41, May–June, 1969.     

醋酸纤维素的降解性研究进展

介绍了醋酸纤维素的生物降解、水解、光解的降解机理与研究现状,并对影响醋酸纤维素降解速率的因素进行了探究。从现有研究中可知,影响醋酸纤维素降解速率的主要因素为醋酸纤维素自身的分子结构（如取代度、取代度分布及结晶性等）,物理改性、化学改性及增塑改性会通过改变醋酸纤维素的分子结构,进而影响醋酸纤维素的降解性能。最后,总结了醋酸纤维的应用领域,并做出了展望。     

A new perspective and comparative study on demixing and gelation behavior of cellulose acetate,cellulose acetate propionate and cellulose acetate butyrate ternary solutions

Cellulose acetate (CA), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB) were fabricated as membrane via nonsolvent induced phase separation process. N,N‐Dimethylformamide (DMF) and N,N‐Dimethylacetamide (DMAc) as solvents and water as nonsolvent were employed. Ternary phase diagrams for all six ternary systems were constructed using Flory‐Huggins theory. In this way, cloud points as well as Berghman's points were determined. Modulus of polymers steepened in various concentration of solvent/nonsolvent mixtures were measured to find the weight fraction of polymer (w_p) in which vitrification takes place. W_P values for CA, CAP, and CAB were obtained 0.59, 0.67, and 0.74 in presence of DMF while those were 0.69, 0.74, and 0.84 in presence of DMAc; whereas glass transition temperatures (T_g) for three polymers were determined 180°C, 142°C, and 101°C correspondingly. Pure water flux for CA, CAP, and CAB membrane increased from 75.7 to 83.4 and 290.3 and from 109.6 to 116.1 and 400.3 L/m² h bar when DMF and DMAc were used as solvents, respectively. Results revealed that as T_g of polymer decreases, the membrane structure vitrifies at higher polymer concentration with more porous structure, bigger pores, higher permeate flux followed by decrease in mechanical strength. POLYM. ENG. SCI., 58:1135–1145, 2018. © 2017 Society of Plastics Engineers     

Formation of asymmetric cellulose acetate membranes

Cellulose acetate membranes were prepared from casting solutions containing dioxane as a solvent and varying concentrations (up to 6%) of maleic acid as an additive. Coagulation took place in water at different temperatures. The effect of these variables on membrane structure and membrane properties is related to two phenomena of phase separation in the system cellulose acetate/dioxane/water, viz. gelation in the toplayer and liquid-liquid phase separation in the sublayer of the membrane. We adopted a solution transport model which correlates membrane flux with the skin thickness and membrane salt rejection with the compactness (microstructure) in the skin. Effects of variables such as maleic acid concentration and coagulation temperature on the position of curves in the phase diagram and on membrane properties are discussed. It is concluded that more work should follow on the kinetics of the phase changes mentioned.