Cyanoethylated cellulose prepared by homogeneous reaction in paraformaldehyde-DMSO system

A series of cyanoethylated celluloses with various degrees of substitution was prepared by homogeneous reaction of cellulose in PF/DMSO system. Their thermal deformation properties changed regularly with the degree of cyanoethylation. By comparing highly cyanoethylated cellulose in the series with that prepared by a traditional cyanoethylation method, it was seen that they were quite different in physical properties such as thermal deformation or tensile properties. Based on the results of dynamic mechanical measurements and infrared spectroscopy, cyanoethylated cellulose prepared in PF/DMSO system was found to be a new cellulose derivative, which includes oligo-oxymethylene groups at the position between the glucopyraneose ring and the cyanoethyl group in the side chain. The maximum DS value of this cyanoethylated cellulose was estimated to be ca. 2.5.     

Studies in chemically modified celluloses. VII. Periodate oxidation of cellulose dyed with reactive dyes

Periodate oxidation of cellulose and cellulose dyed with reactive dyes at 32°C in the presence and absence of various concentrations of alkali metal chlorides and sulfates has been studied. The extent of oxidative degradation undergone by cellulose and assessed in terms of copper number and cuprammonium fluidity of the oxidized dyeing, the oxygen consumption during the oxidation, and the rate constant were shown to be markedly increased by the presence of the salts in the oxidizing solution. Borohydride and chlorous acid treatment were used to further modify the periodate oxycelluloses, and the effect of these treatments on the properties was studied.     

Chemically modified celluloses. XIII. Periodate oxidation of cellulose dyed with reactive and direct dyes in the presence of electrolytes

Periodate oxidation of cellulose dyed with vinyl sulfone-type reactive dyes at 32°C in the presence of various concentrations of alkaline earth metal chlorides and a cationic dye-fixing agent has been studied. The extent of the oxidation has been assessed in terms of rate constant, time of half reaction, and percent accessibility to periodate ions. Remazol Black B was used in the study. This dye on reduction with sodium hydrosulfite after reaction with the fiber removes the sulfonic acid group containing a portion of the dye, leaving behind a portion reacted with the fiber and not containing a sulfonate group. The study has also been extended to a few direct dyes which, unlike reactive dyes, have been shown not to inhibit the rate of periodate oxidation of cellulose.     

甘蔗渣纤维素均相接枝制备阴离子吸附剂

在离子液体均相体系下,在甘蔗渣纤维素表面上接枝功能单体甲基丙烯酸二甲氨基乙酯(DMAEMA)制备一种阴离子吸附材料,研究了引发剂浓度、温度、单体用量、交联剂浓度和时间对产物接枝率的影响。结果表明,甘蔗渣纤维素与单体DMAEMA质量比为1:5,引发剂浓度为2%,交联剂浓度为3%,温度为50℃和反应时间为4 h,产物的接枝率最大为330%,在含有较低浓度的氟离子溶液中,其吸附能力为2.6 mg/g,为高效阴离子吸附剂的制备提供了理论依据。     

Rapid homogeneous esterification of cellulose extracted from Posidonia induced by microwave irradiation

In this article, we report on the synthesis of cellulose esters by the reaction of cellulose and some cyclic anhydrides, such as succinic, maleic, and phthalic anhydrides. For this, an esterification method was finalized. Indeed, cellulose extracted from Posidonia biomass was first solubilized in the solvent system lithium chloride (LiCl)/N,N‐dimethylacetamide and then esterified by cyclic anhydride in the presence of catalysts such as N,N‐dimethyl‐4‐aminopyridine, tripropylamine, tributylamine, and calcium carbonate. This method was fast and reproducible with the LiCl system as a solvent and with an efficient activation by controlled microwave power. In this way, the reaction time was reduced from several hours to just a few minutes. The reaction products were characterized by IR and solid‐state cross‐polarization/magic angle spinning ¹³C‐NMR spectroscopy. The degree of substitution (DS) and the grafted ester group content of the different products were obtained by alkali saponification followed by titration of the excess alkali. Two activation methods were compared, and the results show that the application of classical heating gave less successful results than those obtained by microwave activation. Indeed, with microwave activation, a higher DS (2.25) was obtained after 10 min. However, with classical heating, a value of DS equal to 1.2 was obtained after 12 h. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Methane partial oxidation to methanol-solid initiated homogeneous methane oxidation

The initiation temperature of methane partial oxidation was markedly lowered by platinum wire placed upstream of a high pressure reactor. Added hydrogen in the reactant gas promoted the methanol selectivity. The radicals formed on the platinum surface were desorbed from it and initiated the reaction.     

高碘酸钠氧化纤维素的研究

研究了用高碘酸钠(NaIO4)溶液氧化纤维素的过程与性能,用红外光谱验证了氧化纤维素的结构.考察了溶液pH值、氧化时间、氧化温度和氧化剂浓度等因素对氧化纤维素醛基含量和回收率的影响.结果表明,随IO4-浓度的增大、氧化时间的延长、氧化温度和pH值的升高,纤维素降解程度愈深,其回收率愈低;随IO4-浓度和氧化温度的升高,醛基含量愈高,而pH值和氧化时间存在一个使醛基含量相对较高的值.     

ATRP法均相制备纤维素/甲基丙烯酸丁酯接枝聚合物

在纤维素LiCl/DMAc均相溶液中,通过氯乙酰氯（ClC₂OCl）与纤维素的均相酰化反应制得纤维素氯乙酸酯（Cellulose-ClAc）后,将其溶解在DMAc中,在FeCl₂/4-二甲氨基吡啶（DMAP）的催化作用下,引发甲基丙烯酸丁酯（BMA）的均相ATRP 聚合反应,制备了纤维素/BMA接枝共聚物（Cellulose-g-PBMA）,考察了反应时间、反应温度、反应物配比等对酰化及接枝聚合反应的影响,并通过测试Cellulose-g-PBMA薄膜的接触角,对最终产物的疏水性能进行了研究;采用FTIR、NMR、SEM、TEM、AFM等分析手段对Cellulose-ClAc及Cellulose-g-PBMA的结构进行了表征;利用GPC分析了接枝聚合反应的活性特征。     

Solution studies of cellulose tricarbanilates obtained in homogeneous phase

A number of cellulose samples was submitted to homogeneous phase carbanilation in dimethylacetamide/LiCl. The process is quantitative and leads to a completely substituted product, as verified by elemental analysis and UV spectroscopy. Tricarbanilated samples were characterized by viscometric and light-scattering measurements in tetrahydrofuran. Our results are in good agreement with those reported in the literature, concerning products obtained in the heterogeneous phase. Gel permeation chromatography was performed for evaluating the molecular weight distribution of the parent cellulose, using both universal and linear calibration. The chromatographic technique is not adequate for samples exhibiting a high degree of polymerization. © 1995 John Wiley & Sons, Inc.     

Effect of ethylamine pretreatment on the oxidation of cellulose by periodate

The effect of ethylamine pretreatment on the rate and uniformity of the periodate oxidation of cotton has been studied. Although water is essential to the oxidation its presence has been kept to a minimum by using 40% aqueous dimethylformamide as the oxidation medium. This both retarded the rate of oxidation sufficiently to eliminate its dependence on diffusion and reduced the extent to which the swollen structure produced by ethylamine collapsed when the amine was replaced by periodate solution. The best way that has been found of maintaining the open structure consists in partial acetylation of the ethylamine-treated material. This resulted in a much more nearly random attack on the 1,2-diol groups by periodate than occurred with untreated cotton.     

氢氧化钠/尿素水溶液中纤维素均相接枝制备高吸水材料

以氢氧化钠／尿素(NaOH／Urea)水溶液为纤维素溶剂，进行了纤维素均相接枝丙烯酸制备高吸水材料的研究。该吸水材料吸去离子水达400多倍、自来水达近200倍。讨论了纤维素在NaOH／Urea水溶液体系中的溶解，考察了反应温度、交联剂用量、引发剂用量对接枝产物吸水性能的影响。     

Chain reaction mechanism of cellulose pyrolysis

Chatterjee and Conrad¹ studied the kinetics of pyrolysis of cotton cellulose in the temperature range 270–310°C and proposed a chain reaction mechanism. Lipska and Parker⁸ studied the pyrolysis of the α-cellulose in the temperature range 250–300°C and interpreted the kinetic data differently. Both articles were published almost simultaneously. In this paper Lipska and Parker's complete data have been again analyzed and reinterpreted in light of the chain reaction mechanism. The energies of activation for initiation and propagation steps of the cellulose decomposition reaction are discussed.     

活性炭表面模拟烟气与元素汞间均/异相氧化反应特性

通过固定床吸附实验,在130℃温度下模拟研究燃煤烟气组分在椰壳活性炭(CS-AC)表面吸附气态元素汞(Hg⁰)过程中的作用与影响,揭示模拟烟气组分、Hg⁰以及活性炭表面三者间的均相、异相氧化反应特性。实验研究了CS-AC在N₂和模拟烟气气氛下对Hg⁰的吸附,模拟烟气组分与Hg⁰间的均相氧化反应,以及吸附模拟烟气组分后CS-AC在N₂气氛下对Hg⁰的吸附。研究表明在N₂气氛下CS-AC对Hg⁰不具备物理吸附的能力,而在模拟烟气组分下CS-AC对Hg⁰具有较强的吸附能力,初始吸附效率达80%。仅在模拟烟气均相反应作用下,大约只有14%的Hg⁰被氧化为Hg²⁺。经过预先跟常规模拟烟气吸附反应,CS-AC表面具备一定氧化性化学元素基团（如NO_x）后,能够在N₂气氛下对Hg⁰进行化学吸附,初始吸附效率达67%左右。可以认为模拟烟气和Hg⁰两者间的均相作用不是促进CS-AC在模拟烟气组分下对Hg⁰具有较强的吸附能力的主因。活性炭吸附Hg⁰的过程中,活性炭表面在烟气组分氧化Hg⁰的过程中起到了积极的促进作用。无论在N₂气氛下,还是在模拟烟气下,CS-AC吸附Hg⁰是气氛中氧化性组分、Hg⁰和活性炭表面三者间的异相化学氧化吸附反应过程。     

HPLC法监控辅酶Q_0生产的氧化反应

利用反相HPLC法监控氧化反应中辅酶Q0的含量,从而确定氧化反应终点。色谱条件采用C18反相柱,甲醇-水(8∶2)为流动相,检测波长237 nm,流速0.8 mL/min,柱温35℃,外标法定量。通过跟踪监测,发现3,4,5-三甲氧基甲苯氧化反应1 h即达反应终点。本法快速、准确、选择性好,可实现对生产的监控。     

The syngas production by partial oxidation using a homogeneous charge compression ignition engine

It is essential to develop the environment-friendly alternative energies urgently considering the limited fossil fuel and the global warming caused by environmental destruction. In this research, the new technology was studied to produce syngas from methane or simulated biogas with a HCCI reforming engine. The purpose is to provide the basics for the research on biogas treatment mainly comprising of methane and carbon dioxide, the cause of global warming.     

Decolorisation of textile effluent using homogeneous photochemical oxidation processes

In this paper, the results of COD and colour removal from textile effluent using homogeneous photochemical oxidation processes in a batch mode are presented. The results show that the best result was obtained using a combined O₃/H₂O₂/UV process, with 97% removal for COD and 99% removal for colour. Optimum conditions for pH and hydrogen peroxide dosage for this process was determined as 3 and 25 mg/l, respectively. Both H₂O₂/UV and O₃/UV combinations were found to result in similar levels of COD and colour removal efficiencies (over 91% removal for COD and 96% for colour). In addition, the associated operating costs of the various advanced oxidation processes were determined in this study. Received: 21 February 2005; Accepted: 14 June 2005.     

Catalytic wet oxidation of phenol with homogeneous iron salts

The catalytic wet oxidation of phenol has been investigated in a 1 L semi‐batch reactor in the presence of both ferrous and ferric salts. Oxidation reactions follow first‐order kinetics with respect to phenol and half‐order kinetics with respect to dissolved oxygen. The activation energy for the reaction was 44.5 and 48.3 kJ mol^?1 for runs employing Fe³⁺ and Fe²⁺, respectively. Rate constants and induction periods were also similar for both catalysts. This result could be explained by analysing the evolution of iron during the oxidation process. For pH > 2, Fe²⁺ was rapidly oxidized under reaction conditions to Fe³⁺, resulting in a unique catalytic redox system Fe²⁺/Fe³⁺. It was also shown that if pH < 2 the dissolved oxygen was unable to oxidize ferrous ion, resulting in a much slower oxidation rate of phenol. The absence of a redox pair resulted in a complete lack of catalytic activity of the dissolved iron salt. Copyright © 2005 Society of Chemical Industry     

Strategies for oxidation catalyzed by polyoxometalates at the interface of homogeneous and heterogeneous catalysis

A basic premise behind the use of polyoxometalates in oxidation chemistry is the fact that polyoxometalates are oxidatively stable. This, a priori, leads to the conclusion that for practical purposes polyoxometalates would have distinct advantages over widely investigated organometallic compounds that are vulnerable to decomposition due to oxidation of the ligand bound to the metal center. Since polyoxometalate synthesis is normally carried out in water by mixing the stoichiometrically required amounts of monomeric metal salts and adjusting the pH to a specific acidic value many structure types are accessible by variation of the reaction stoichiometry, replacement of one or more addenda atoms with other transition or main group metals, and pH control. The structural variety available has enabled the use of polyoxometalates as catalysts for oxidation of hydrocarbons and functionalized organic substrates (alcohols, amines, sulfides, etc.) with a wide range of oxygen donors ranging from molecular oxygen, hydrogen peroxide, nitrous oxide, ozone, alkyl hydroperoxides, periodate, sulfoxide and others. The wide purview of oxidation reactions is enabled because the structural variety leads to oxidation through a number of different mechanistic motifs.From a synthetic organic point of view, the most applicable uses of polyoxometalates as catalysts involve the green oxygen donors – hydrogen peroxide and molecular oxygen. Since practical applications are in hand in this area, practical considerations concerned with catalyst recycle and/or recovery and the elimination of environmentally problematic solvents are also coming to the forefront. In this paper, we will present some of our activities in the area of catalyst engineering for catalytic synthetic applications by polyoxometalates including: (a) catalytic mesoporous solids from organic-polyoxometalate hybrid materials, (b) fluorous phase polyoxometalates with and without fluorous solvents and (c) the use of aqueous biphasic media for oxidation with hydrogen peroxide.