Simulated autohydrolysis of aspen milled wood lignin in the presence of aromatic additives: Structural modifications

In a previous article the authors have described changes in molecular weight which occur when aspen milled wood lignin is subjecte to autocatalyzed hydrolysis (autohydrolysis) in the presence of three aromatic additives: 2-naphthol, resorcinol, and p-hydroxybenzoic acid. In the present work, the reactions of these additives have been studied from the viewpoint of their effect on the structure of the lignin. The use of milled wood lignin instead of aspen wood served to distinguish those reactions between the additives and the lignin, without involving the other wood components. The reaction products have been charactrized by elemental analysis and UV and IR spectroscopy. It was concluded that keto groups, generated on the lignin side-chain during autohydrolysis, condense with the additives, which become incorporated into the lignin. This occurs most probably through an aromatic eletrophilic substitution reaction. While 2-naphthol condensed primarily with the β-keto carbonyl groups, resorcinol attacked also the α-keto carbonyl groups. When p-hydroxybenzoic acid was the additive, its incorporation was accompanied by an increase in lignin carboxylic acid groups.     

Thermal degradation of poly(vinyl chloride) in presence of additives part III. Studies in molecular weight distribution

The changes in molecular weight and molecular weight distribution of PVC degraded in presence of maleic anhydride, benzoquinone and anthraquinone were studied by gel permeation chromatography. Chain scission and crosslinking reactions were indicated on the basis of M?_n and M?_w of degraded samples. Crosslinking was predominant when degradation was carried out in presence of anthraquinone.     

The effect of low molecular weight additives on the properties of aromatic polyamide membranes

Salts contained in aromatic polyamide solutions were found to have a considerable effect on the performance and structure of reverse osmosis membrannes cast from these solutions. As in cellulose acetate membranes, certain salts greatly increase membrane fluxes without a detrimental effect on rejection. Highly dissociated salts such as LiClO₄ or Mg(ClO₄)₂ exert a stronger influence than the commonly used LiCl. With mixtures of different salts, stronger effects may be obtained than with a single additive. Many experimental facts indicate that the “salt effect” in aromatic polyamide membranes is due to a general effect on solvent activity and thus on the kinetics and equilibria associated with evaporation and coagulation process.     

碱木素分子量及其分布的GPC表征

采用水溶性凝胶渗透色谱测定了碱水素的分子量特征,并对影响分子量分布测定的因素进行了探讨。结果发现,所用流动相的酸度对碱木素在凝胶色谱柱上可能发生的吸附影响比较显著。当流动相的碱性不够时,碱水素会发生吸附,并且大分子量木素优先被吸附,当pH升至12时可消除吸附现象。流动相的离子强度增大亦可以部分消除木京的吸附。     

Solution properties of lignin. Thermodynamic properties and molecular weight determinations

Number-average molecular weights and the thermodynamic parameters ΔF?₁, ΔH?₁, and ΔS?₁ have been obtained for lignin in the solvents dimethylsulfoxide, dimethyl-formamide, and dioxane. Widely different molecular weights were found in the different solvents and at the different temperatures as a consequences of molecular association. Analysis of the thermodynamic parameters revealed that these quantities are dominated by the change in solvent structure accompanying the solution process. A correlation between the “goodness” of a lignin solvent and the Hildebrand solubility parameter is consequently misleading in such systems.     

酶促木质素与酚聚合反应分子量及分布实验

在反相微乳液系统中 ,进行了过氧化物酶催化木质素与酚共聚反应实验 ,考察了酶浓度、WO(水 /表面活性剂 ,质量比 )、表面活性剂浓度、单体 (酚、木质素 )浓度及醇烃比对聚合物分子量的影响。结果表明 ,聚合物重均分子量可用表面活性剂浓度、酶浓度、单体浓度及油相中醇烃比来调控。用单纯形优化法关联了实验数据 ,得到了聚合物重均分子量的关联式 :M =6 2 7× 10 4 (Y1× 10 7) -0 .3 4Y0 .982 Y0 .83 Y2 .4 64 Y1.0 55。聚合物分子量分布出现双峰 ,是两种反应机理竞争的结果。     

红麻硫酸盐法蒸煮中溶出木素的分子量分布及变化

采用凝胶色谱法（GPC）对红麻皮和秆芯硫酸盐法蒸煮过程中溶出木素的分子量及其分布的变化进行了研究。结果表明，随着蒸煮的进行，红麻皮和秆芯溶出木素的平均分子量逐渐增大，多分散性和特性粘数也相应增大。此外，在同一蒸煮条件下，红麻秆芯溶出木素的平均分子量高于红麻皮，这也说明了红麻秆芯比红麻皮更难脱木素。研究还发现，红麻原料木素以及溶出木素的分子量分布曲线都呈单峰现象。     

MALDI-TOF study of oligomers distribution in spray-dried glyoxalated lignin for wood adhesives

Spray drying of glyoxalated lignin used in tannin/lignin adhesives for exterior- and interior-grade wood particleboard and other types of panels has been shown to be capable of maintaining its reactivity after spray drying with no decrease in performance of the adhesive once the spray-dried material is re-dissolved in water. This indicates that spray drying is a very suitable method for long-term storage of the adhesive without loss of performance. A clear variation in the distribution of oligomers in the material after spray drying has been observed by Matrix-Assisted Laser Desorption/Ionization Time of Flight analysis. One effect of the reaction that has been noticed with aging is the assembly of the monomers and lower molecular mass oligomers such as dimers into structures of higher molecular weight as a consequence of their condensation with glyoxal and the formation of glyoxylene bridges between them.     

凝胶色谱法在聚丙烯分子量及分子量分布测定中的应用

根据聚丙烯在凝胶色谱柱上的淋洗特点,确定了测定其分子量及分子量分布试验条件;采用示差和黏度双检测凝胶色谱系统,利用普适校正方法,不需要Mark常数K、α值,可直接测定聚丙烯分子量分布并给出分子量分布曲线;采用统计方法计算数均分子量、重均分子量、黏均分子量,可以为课题研究提供一定的依据和指导。     

Engineering plastics from lignin. XVII. Effect of molecular weight on polyurethane film properties

A series of five fractions with number average molecular weights (M?_n) between 1500 and 10,000 daltons were isolated from a Kraft hydroxypropyl lignin (HPL). From ¹H-NMR and UV analysis the chemical properties of the HPLs were found to vary slightly with molecular weight. The hydroxyl content decreased while the glass transition temperature (T_g) increased as the HPL molecular weight increased. The Fox-Flory equation adequately described the M?_n vs. T_g relationship. The HPL fractions were used as polyols for the preparation of solvent-cast polyurethane networks (PU) in film form. The T_g of the PUs increased from 40° to 120°C as the M?_n of the polyol rose from 1500 to 10,000 daltons. The molecular weight between crosslinks (M?_c) of the networks was determined by swelling. An observed decrease in M?_c with an increase in M?_n was related to the functionality of the system. The strength properties of films prepared from fractionated HPLs were superior to those prepared from nonfractionated HPLs.     

Determination of molecular weight averages and molecular weight distribution by g.p.c. of N-trifluoroacetylated polyamides

To determine their molecular weight averages and molecular weight distribution, N-trifluoroacetylated (TFA) polyamides are studied using gel permeation chromatography in tetrahydrofuran at 25°C. Several calibration methods (calibration with polydisperse standards, universal calibration) are tested; among these, direct calibration of M_w of polydisperse samples vs. peak maximum of the corresponding g.p.c. chromatogram leads to the best results. Calculated molecular weight averages of nylon 6-TFA and Trogamid^R-TFA are compared with data from light scattering, viscometry and osmometry.     

Iodine-initiated,solid-state copolymerization of tetraoxane with 1,3-dioxolane in the presence of methylal. V. Studies on molecular weight distribution of copolymer

The iodine-initiated, solid-state copolymerization of the tetraoxane–1,3–dioxolane-methylal system has been studied by measuring the molecular weight distribution of the copolymer. The molecular weight distribution of the copolymer is found to be strongly dependent on the addition method of the 1,3-dioxolane–methylal solution to tetraoxane. The copolymer obtained by the one-addition copolymerization has a molecular weight distribution curve that shows a very broad distribution, with a discernible shoulder; and the copolymer obtained by the continuous-addition copolymerization has a very sharp curve. Particle size of the copolymer also influences the molecular weight distribution. For the one-addition copolymerization, the larger the particle size of the copolymer, the broader the molecular weight distribution. For the continuous-addition copolymerization, however, the molecular weight distribution is nearly constant regardless of particle size. The dependence of the molecular weight distribution on the polymerization time and the concentrations of iodine, 1,3-dioxolane, and methylal is discussed in detail. These results suggest that this copolymerization system is characterized by a reaction that proceeds from the surface to the center of the tetraoxane crystals.     

Influence of molecular weight and molecular weight distribution on the tensile properties of amorphous polymers

Tensile property data for polystyrene samples of varying polydispersity are correlated with various parametric measures of molecular weight. Traditional measures of molecular weight, such as M?_n, M?_w, and M?_z, are shown to be unable to account for the variation of tensile properties with molecular weight. However, a new molecular weight parameter, termed the failure property parameter, is able to provide a single relationship between tensile strength and the parameter for both the broad and narrow distribution polymers. The form of this parameter is consistent with its having origins in the view that it is the entanglement network in an amorphous polymer that provides the observed strength properties. Specifically for polystyrene, the failure property parameter results indicate that material below 60,000 molecular weight does not contribute to polymer strength. Although the results of this investigation are specifically for polystyrene, the arguments used to develop the failure property parameter are not dependent on polymer chemical structure. Consequently, we believe that both the concepts and definition of this new parameter are applicable to all amorphous polymers.     

Change in molecular weight characteristics of an aromatic copolyamide during the polycondensation process

Conclusions The change in molecular weight characteristics and in viscosimetric data during the synthesis process of an aromatic copolyamide has been analyzed. It has been found that, with rise in the degree of completion of the reaction, at definite molecular weight values the dynamic viscosity rises sharply, which indicates the presence of a significant structural component of this system.The effect of polymer molecular weight on fibre physicomechanical properties has been shown. An increase in fibre strength has been noted on increase in molecular weight from 5400 to 7300. The impairment in physicomechanical properties on further increase in polymer molecular weight is connected with difficulties in processing the strongly structured spinning solutions. Processing polymer with a high molecular weight, and, as a consequence, with an elevated dynamic viscosity requires new approaches both to spinning conditions and, possibly, also to synthesis conditions.Translated from Khimicheskie Volokna, No. 2, pp. 29–30, March–April, 1989.     

宽分子量分布聚合物的制备

分别对采用物理共混法、自由基聚合、配位聚合和离子聚合法制备宽分子量分布聚合物进行了综述。指出目前应用较为广泛的是物理共混法，配位聚合容易实现分子量和分子量分布宽度可控，近几年已成为研究热点。     

Application of the weibull distribution function to the molecular weight distribution of cellulose

The molecular weight distribution of a linear homologous polymer is usually obtained empirically for any particular sample. Sample-to-sample comparisons are made in terms of the weight- or number-average molecular weights and graphic displays of the distribution curves. Such treatment generally precludes data interpretations in which a distribution can be described in terms of differing proportions of mixed populations. However, a statistical continuous univariate distribution function such as the Weibull can be applied to the molecular weight distributions measured for cellulose nitrate samples. The size distributions of samples degraded under some gentle stress may then be indentified as consisting of differing proportions of populations with similar characteristic distributions. Analyzing data in this way should permit interpretation of the results as for breakdown of oligomers in a small-molecule system.