Alkoxylation of cellulose nitrates

Reactions of high nitrogen-containing cellulose nitrate with a series of aliphatic alcohols are studied. In the course of physicochemical studies most probable pathways of chemical reaction were established. They include substitution of nitrate groups by alkoxy group, opening of glucopyranose ring with the addition of the fragment of alcohol by the free bonds formed and formation of the carbonyl group, and also saponification of nitrate groups while studying the process in alkaline medium.     

硝酸酯类分子力学参数的确定和应用

运用MM2(85年版)分子力学程序, 以硝酸甲酯、硝酸乙酯的实验结构为参比, 调试确定了硝酸酯类化合物的伸缩力常数(K~s)、弯曲力常数(K~b)和旋转力常数(V~1、V~2、和V~3)。用这套力场参数计算了硝酸甲酯、硝酸乙酯和硝化甘油的平衡几何构型、生成热和偶极矩, 计算结果与实验值和从头计算结果相一致。还用这套参数计算了结构未见报道的异基硝酸酯、丙烯基硝酸酯和苯基硝酸酯, 所得结果与MNDO全优化几何构型相符。     

Synthesis of bacterial cellulose nitrates

Russian Chemical Bulletin - The conceptual possibility to synthesize bacterial cellulose nitrates with the use of commercial mixed acid was demonstrated. The initial bacterial cellulose was...     

Molecular structure and properties of cellulose acetate chemically modified with caprolactone

Cellulose acetate (CA) with a degree of substitution of 1.7 was modified with caprolactone (CL) under various reaction conditions in an internal mixer. Processing temperature changed from 120 to 220 °C, while reaction time varied between 5 and 45 min. The composition and structure of the polymer was analyzed by various methods including FTIR, MALDI-TOF and NMR spectroscopy and its mechanical characteristics were determined by dynamic mechanical analysis and tensile testing. The results indicate that homopolymerization occurs under relatively mild conditions, while grafting requires higher temperatures and longer times. Grafted polycaprolactone (gPCL) chains are attached mainly to positions 2 and 6 of the glucose ring and their length increases with increasing reaction time and temperature, but the chains are always much shorter than those obtained in solution polymerization. Changes in the degree of substitution during grafting are small indicating that homopolymerization proceeds easier than grafting. Grafting seems to be easier in cellulose acetate with a larger degree of substitution in spite of the smaller number of active -OH groups present. Internal plasticization is more efficient than the external plasticizing effect of monomeric caprolactone. Plasticization results in a decrease of stiffness and strength, but deformability increases only slightly.     

Degradation of cellulose nitrates in low-water media

The kinetics of degradation of cellulose nitrates in low-water organic solvents in the presence of various catalysts was examined.     

Molecular parameters of sodium cellulose xanthate in dilute solution

Molecular parameters of sodium cellulose xanthate in NaOH solution have been determined by means of light scattering and viscometry. The effect of the degree of substitution on the molecular configuration of sodium cellulose xanthate has been studied for three series of samples of varying degree of substitution. The expansion factor has been determined from the expression due to Orofino and Flory. The effective bond length b and the ratio of the unperturbed dimension to the dimension assuming free rotation of the chain units (R?_o²/R?_f²)^1/2, have also been determined. It is concluded that sodium cellulose xanthate in dilute solution is a loosely coiled molecule, comparable to other cellulose derivatives in chain stiffness.     

Molecular weight distribution of cellulose by fractionation in cadoxen solutions

The fractionation of cellulose in cadoxen solutions has been carried out by precipitation with aqueous propanol. The reproducibility of the method has been tested by means of parallel fractionations, and shown to be good, for both research and routine work. The fractionation data have been analysed using Beall and Schulz methods, and the results compared.     

High-resolution solid-state 13C-NMR spectroscopy of cellulose nitrates

Solid-state ¹³C-NMR spectroscopy has been used to investigate the structure of cellulose nitrates prepared from cotton linters. The solid-state technique has the advantage that the entire range of substitution can be studied, which is not possible at present by solution methods. The spectra change progressively with increasing degree of substitution (DOS = 3 for cellulose trinitrate), and can be used to quantify the extent of substitution at C6, C2, and C3. Progressive nitration leads to elimination of the original C6 resonances of native cellulose by DOS = 1.39. The first nitration of C6 occurs in the amorphous regions, and this is complete by DOS = 0.50. Substitution at C6 is accompanied by decrystallization, as indicated by the decrease in the resonance assigned to crystalline C4, which also disappears at DOS = 1.39. A new resonance assigned to C1 appears at DOS = 0.28 at 101 ppm; the original C1 resonance for cellulose declines steadily and disappears by DOS = 2.65. This change is assigned to nitration of C2, based on the published solution spectra. Finally, development of intensity at 82 ppm at DOS = 1.83 is assigned to the effect of nitration at C3. There is no indication of any rearrangement of the unsubstituted regions analogous to those that occur on Mercerization of native cellulose.     

Oxidation of alcohols by metal nitrates supported on silica gel

Many metal nitrates, especially zinc(II) and copper(II) nitrates, supported on silica gel, oxidized secondary and benzylic alcohols to the corresponding ketones and aldehydes efficiently.     

Molecular weight dependence of positron lifetime parameters in PEEK samples

Positron lifetime measurements have been performed on differently manufactured PEEK samples of different molecular weights. Our measurements confirmed an old assumption: the o-Ps lifetime changes linearly with the molecular weight of the polymer. We have found that both the size of the free volumes and their number increase with increasing molecular weight of the investigated polymers.     

Molecular weight distribution of cellulose esters by gel permeation chromatography and fractional precipitation

Fractional precipitation and gel permeation chromatography yield comparable information on the molecular weight distribution of various cellulose esters. The GPC technique applied to samples obtained by fractional precipitation gives a much more definitive analytical tool than either method used independently. One practical application of this work showed the same molecular weight distribution of two cellulose acetates prepared by different methods.     

Zirconium dioxide xerogel modified with powdered cellulose

Zirconium dioxide xerogel was synthesized in the presence of powdered cellulose. The samples obtained were studied in a model liquid-phase catalytic process of oxidative dehydrogenation of trimethylhydroquinone with atmospheric oxygen and in decomposition of hydrogen peroxide.     

New polyurethane foams modified with cellulose derivatives

New polyurethane foams were elaborated with different cellulose derivatives as raw material, by the one-shot process. The foams were submitted to soxhlet extraction in order to quantify the amount of cellulose derivative incorporated in the foam by chemical bonding. The foams were characterized by means of FTIR, solid state ¹³C NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy and dynamic mechanical analysis (DMA). The FTIR- and solid state ¹³C NMR showed characteristic peaks for cellulose derivatives and polyurethane. DMA measurements indicated that storage modulus increased with increasing content of cellulose derivatives. The highest value was obtained for foams prepared with cellulose sulphate.     

Equilibrium constants of nitration of alcohols and thermal stability of their nitrates

The data on equilibrium constants of the nitration of polyhydric alcohols and cellulose were examined and generalized. Changes in values of the equilibrium constants and Gibbs's energy of nitration related to the position of the nitrated hydroxyl group in the molecule and the existence of the adjacent hydroxyl and nitrate groups were established. An empirical method for calculating rates of thermal decomposition of different nitrate groups using experimental equilibrium constants of nitration was suggested. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1802–1804, October, 1997.     

Thermal analysis of cellulose acetate modified with caprolactone

Cellulose acetate (CA) was modified with caprolactone (CL) under various reaction conditions in an internal mixer. The thermal behavior and relaxation transitions of the samples were determined by dynamic mechanical analysis and differential scanning calorimetry. Various relaxation transitions were detected in externally and internally modified cellulose acetate by DMTA. These were assigned to the glass transition of the main chain, to the movement of single glucose units and to hydroxymethyl groups. The β′ transition must belong to structural units larger than a single glucose ring and their formation must depend on sample preparation conditions. No transition could be assigned to grafted polycaprolactone (PCL) chains by DMTA. Contrary to other groups, we could not detect even the transitions of modified CA by DSC. Only the crystallization of oligomeric PCL homopolymer was observed mostly when it diffused to the surface of the sample.     

Molecular iodine-catalyzed benzylation of arenes with benzyl alcohols

A novel molecular iodine-catalyzed benzylation of arenes with benzyl alcohols has been developed. The reaction can be carried out under mild conditions to afford a series of diarymethane derivatives in high yields and good regioselectivities.     

Molecular structure of liquid alcohols

A new thermodynamic treatment of continuous association is presented, where the various equilibria between i-mers are replaced by a single equilibrium between an OH groups in the bonded and the non-bonded states, linked in both cases to an indefinite ensemble of molecules. The treatment leads to an association constant K which differs from those considered in the theories of Kretschmer and Wiebe and of Wiehe and Bagley. For pure alcohols the association constant can be estimated from the vapor pressure of the alcohol and that of the homomorphous hydrocarbon. The fraction γ of free OH groups determined in this way is markedly smaller than those calculated from the other theories. For the normal alcohols the product $\text{K}\text{V}{}_{\mathrm{<mtext>A</mtext>}}$ is approximately constant at a given temperature, $\text{V}{}_{\mathrm{<mtext>A</mtext>}}$ being the molar volume. This can be expected from the increasing of the standard entropy of the non-bonded molecules when the molecular volume increases. For secondary and tertiary alcohols the product K$\text{V}{}_{\mathrm{<mtext>A</mtext>}}$ is significantly lower due to steric hindrances. However for all the alcohols considered here the enthalpy of the hydrogen bond remains nearly constant — δH being equal to 24.8 ± 2 kJ mol^?1.