Isoprene and Rubber. Part 32.The Constitution of Rubber

1931 ◽  
Vol 4 (3) ◽  
pp. 368-380
Author(s):  
H. Staudinger
Keyword(s):  
Molecular Weight ◽  
Colloidal Particles ◽  
Molecular Size ◽  
Group Method ◽  
Decomposition Products ◽  
True Solution ◽  
Rubber Part ◽  
Molecular Substances ◽  
Molecular Compounds ◽  
End Group

Abstract 1. The establishment of the molecular size of high molecular compounds which are composed of fiber molecules by the end-group method of determination is only possible if homologous polymeric series of similar type are concerned. 2. The end-group method assures reliable values with molecules up to a molecular weight of 1000 at the highest. With higher molecular products, like cellulose and rubber, the method is inexact. 3. The molecular weight of rubber and balata may be determined by viscosity determinations in the following two ways: (a) M=ηsp/cKm (b) M=Kc.Kcm. The constants Km and Kcm are determined with low molecular decomposition products. 4. Rubber and balata are composed of fiber molecules, which in one dimension have the magnitude of colloidal particles and in both the others, the dimensions of low molecular substances. 5. In highly viscous rubber solutions, there is the characteristic state of solution. As a result, the sphere of action of the dissolved molecule is greater than the volume at the disposal of the solution. This solution is midway between a true solution and a gel, and is therefore designated as a gel solution. It occurs only with high molecular substances, and is characteristic of them. 6. The readiness with which rubber solutions vary is explained by the fact that the rubber molecules are very sensitive to chemical influences and to changes in temperature as a result of the position of the double bonds. This sensitivity varies with the length of the molecules.

Isoprene and Rubber. Part 29. High Molecular Hydrorubbers

1932 ◽  
Vol 5 (2) ◽  
pp. 136-140
Author(s):  
H. Staudinger ◽  
W. Feisst
Keyword(s):  
Molecular Weight ◽  
Catalytic Reduction ◽  
Molecular Form ◽  
Average Molecular Weight ◽  
Molecular Size ◽  
Decomposition Products ◽  
Molecular Weights ◽  
Rubber Part ◽  
Derivatives Of ◽  
Suitable Process

Abstract The molecular concept in organic chemistry is based upon the fact that the molecules, whose existence is proved by vapor density determinations, enter into chemical reactions as the smallest particles. If now it is assumed that organic molecular colloids like rubber are dissolved in dilute solution in molecular form then it must be proved that in the chemical transposition of macromolecules as well no change in the size of the macromolecules occurs. In the case of hemicolloids, therefore for molecular colloids with an average molecular weight of 1000 to 10,000, this has been proved by the reduction of polyindenes, especially of polysterenes, to hydroproducts with the same average molecular weight, and also by the fact that cyclorubbers do not change their molecular weight upon autoöxidation. The molecular weights of hemi-colloidal hydrocarbons are therefore invariable. This is much more difficult to prove in the case of rubber, although there are many more ways in which unsaturated rubber can be transposed than the stable polysterenes, polyindenes, and poly cyclorubbers. In most of the reactions with rubber, as in its action with nitrosobenzene, oxidizing agents, hydrogen halides, and halogens, an extensive decomposition takes place as a result of the instability of the molecule, which is referred to in another work. Therefore derivatives of rubber are not formed, but derivatives of hemi-colloidal decomposition products. The catalytic reduction of rubber in the cold appears to be the most suitable process of making it react without changing its molecular size in order to prove that in a chemical transposition its molecular weight remains the same.

Isoprene and Rubber. XIX. The Molecular Size of Rubber and Balata

1930 ◽  
Vol 3 (3) ◽  
pp. 519-521 ◽  
Author(s):  
H. Staudinger ◽  
H. F. Bondy
Keyword(s):  
Molecular Weight ◽  
Organic Solvent ◽  
Average Molecular Weight ◽  
Molecular Size ◽  
Dilute Solution ◽  
Decomposition Products ◽  
Viscosity Measurements ◽  
Gutta Percha ◽  
Preceding Work

Abstract It was shown in the preceding work that a very dilute solution of balata in an organic solvent contains macromolecules in solution and not micelles. The same is true of rubber. On the basis of these findings it is possible to calculate the molecular weight of rubber and balata from viscosity measurements by means of the formula developed in a previous work: M=η8p/c. Km. The supposition is made that the molecules of rubber and balata have the form of threads and double threads, respectively. Also it is necessary to determine the constant KKm, and this may be calculated in the case of low molecular products, where the average molecular weight can be determined as well as the viscosity of the solutions. Such semi-colloidal decomposition products were obtained by heating rubber or gutta-percha in either tetralin or xylene. As shown by the following table the four samples thus obtained gave the constant: 0.3×10−3,5

Isoprene and Rubber. Part 41. The Hydrogenation of Rubber and Balata

1934 ◽  
Vol 7 (3) ◽  
pp. 496-502
Author(s):  
H. Staudinger ◽  
E. O. Leupold
Keyword(s):  
Molecular Weight ◽  
Particle Sizes ◽  
Colloidal Solutions ◽  
Uniform Size ◽  
Micellar Structure ◽  
Molecular Weights ◽  
Rubber Particles ◽  
Rubber Part ◽  
Points Of View ◽  
Molecular Substances

Abstract Viscosity measurements of dilute solutions of rubber and of balata led to the following values for the size and form of the molecules of these hydrocarbons. It is therefore not a question of definition whether the particle sizes shown above are to be regarded as the molecular or the micellar weights of these substances, for here the concept of molecular weight has the same significance as in the case of lower molecular substances, i. e., the molecule comprises the sum of all atoms combined by normal, i. e., homopolar atoms. The only difference between low and high molecular substances is that low molecular substances are composed of molecules of uniform size, whereas high molecular substances are a mixture of homologous polymers, so that the values above refer to average molecular weights. These results, which explain the nature of colloidal solutions of rubber, are at variance with the views of most investigators of colloids, who ascribe a micellar structure to the rubber particles, and in this way explain the property which rubber has of forming colloidal solutions. This makes clear why until very recently explanations of the constitution of rubber have been open to question among these particular investigators themselves. In order to lend further support to our opinion, the reduction of rubber and balata and low molecular homologous polymeric hydrocarbons was undertaken from certain points of view, as shown in the work which follows.

End-Group Method for Molecular Weight Determination of PET Depolymerization under Microwave Irradiation

2012 ◽  
Vol 554-556 ◽  
pp. 1933-1937 ◽  
Author(s):  
Qing Hua Feng ◽  
Qing Hua Tang ◽  
Wei Lu Zhang ◽  
Yan Hua Jia ◽  
Dong Zhang
Keyword(s):  
Molecular Weight ◽  
Microwave Irradiation ◽  
Average Molecular Weight ◽  
Relative Number ◽  
Group Method ◽  
Molecular Weight Determination ◽  
Stannous Oxide ◽  
Hydrolytic Depolymerization ◽  
End Group

A series of catalysis hydrolytic depolymerization of PET catalyzed by zinc acetate, zinc sulfate, stannous oxide respectively under microwave irradiation at different temperature with time was studied, in which the microwave power was 260W, the ratio of water to PET was 10:1 and the dosage of the catalysts was 0.5% of PET. The relative number average molecular weight of the undepolymerized PET was determined by end-group method. The results show that the molecular weight of the undepolymerized PET decreases with the reaction time increasing, and tends to be stable at the end of the depolymerization reaction. Under the same time, the temperature is higher, the molecular weight is smaller. The molecular weight of the undepolymerized PET reduces most quickly with stannous oxide among the three catalysts.

Isoprene and Rubber. Part 20. The Colloidal Nature of Rubber, Gutta-Percha, and Balata

1930 ◽  
Vol 3 (4) ◽  
pp. 586-595
Author(s):  
H. Staudinger
Keyword(s):  
Molecular Weight ◽  
Characteristic Viscosity ◽  
Specific Viscosity ◽  
Decomposition Products ◽  
Molecular Weights ◽  
Gutta Percha ◽  
Viscosity Increase ◽  
Preceding Work ◽  
Rubber Part

Abstract I. The Molecular Weight of Rubber, Gutta-Percha, and Balata In the preceding work the molecular weight of rubber and balata was calculated on the basis of relations between specific viscosity ηsp and molecular weight which are shown by semi-colloidal decomposition products, on the assumption that this relation is also true for eucolloids. The value ηr−1 was taken as the specific viscosity, i. e., the characteristic viscosity increase of a substance of definite concentration and known solvent. The expression “specific viscosity” has already been used by J. Duclaux. In viscosity investigations of nitrocellulose solutions he represents this by a constant K which is calculated from the relations of the change of viscosity at various concentrations derived by Arrhenius: Based on these constants, nitrocelluloses show different average molecular weights for the increase in viscosity, that is, this constant K is greater with high molecular products than with low. In the following, this constant represents not the specific viscosity, but the viscosity-concentration constant Kc; the earlier constant Km which, on the basis of the formula: expressed the relation between the specific viscosity and the molecular weight, is called the viscosity-molecular weight constant.

Rate of Adsorption of High Polymers on Carbon Black in Relation to Their Molecular Weight

1956 ◽  
Vol 29 (4) ◽  
pp. 1300-1302 ◽  
Author(s):  
A. I. Yurzhenko ◽  
I. I. Maleev
Keyword(s):  
Molecular Weight ◽  
Carbon Black ◽  
Butyl Acetate ◽  
Benzene Solution ◽  
Plant Sample ◽  
Fractional Precipitation ◽  
Characteristic Viscosity ◽  
Molecular Substances ◽  
Work Samples ◽  
Molecular Compounds

Abstract The nature and rate of adsorption of high-molecular substances on carbon black is of interest in a number of instances, particularly in the development of adsorption methods of fractionation of high-molecular substances, but also in the use of carbon black as a filler for rubber ; the number of papers on the adsorption of high-molecular compounds is small. The effect of the molecular weight of different polymers on the rate of adsorption of high-molecular substances from their dilute solutions at C=0.1–0.25 per cent was studied in this work. Samples of polyisoprene, polystyrene, emulsion polymerization at a temperature of +5° and +50°, and also a plant sample of SKS-30 rubber, were the objects of the investigation. Moreover, a series of polystyrene fractions was obtained by the method of fractional precipitation from methyl ethyl ketone and butyl acetate, using methanol as the precipitant. For all the polymers and their fractions the characteristic viscosity was determined, from which the molecular weight value of the polymer was determined. Carbon black of the Ukhtinsky and Dashavsky factories was used as the adsorbent, the specific surface of which was determined by the adsorption of acetic acid from a benzene solution.

Suppressive Effect of Dextran on Platelet Adhesiveness

1966 ◽  
Vol 16 (03/04) ◽  
pp. 384-394 ◽  
Author(s):  
S Cronberg ◽  
B Robertson ◽  
Inga Marie Nilsson ◽  
J.-E Niléhn
Keyword(s):  
Molecular Weight ◽  
Bleeding Time ◽  
Slight Modification ◽  
Molecular Size ◽  
Suppressive Effect ◽  
Factor Ix ◽  
Factor V ◽  
Platelet Adhesiveness ◽  
History Of ◽  
Mean Molecular Weight

Summary43 normal volunteers, 3 patients with thrombophlebitis, and 1 patient with a high platelet adhesiveness and a history of thrombophlebitis have received dextran and its action on the mechanism of haemostasis has been studied. Platelet adhesiveness has been investigated by a slight modification of Hellem’s methods for whole blood and plasma. Dextran with a mean molecular weight of 70,000 produced a markedly lowered platelet adhesiveness together with a moderate prolongation of the Ivy bleeding time. Factor VIII was decreased by about 50% and factor V, factor IX and fibrinogen were decreased slightly more than could be expected from haemodilution alone. No fibrinolysis occurred. Dextran of lower molecular size was less potent. The possible use of dextrans as a thrombosis prophylactic agent is discussed.

Characteristics of fouling due to clay-organic substances in potable water treatment by ultrafiltration

1996 ◽  
Vol 34 (9) ◽  
pp. 157-164 ◽  
Author(s):  
Kim C.-H. ◽  
M. Hosomi ◽  
A. Murakami ◽  
M. Okada
Keyword(s):  
Molecular Weight ◽  
Organic Matter ◽  
Humic Acid ◽  
Fulvic Acid ◽  
Size Distribution ◽  
Ultrafiltration Membrane ◽  
Organic Substances ◽  
Decomposition Products ◽  
Microbial Decomposition ◽  
Fouling Materials

Effects of clay on fouling due to organic substances and clay were evaluated by model fouling materials and kaolin. Model fouling materials selected were protein, polysaccharide, fulvic acid, humic acid and algogenic matter (EOM:ectracellular organic matter, microbial decomposition products) and kaolin was selected as the clay material. Polysulfone membrane (MWCO(Molecular Weight Cut-Off) 10,000, 50,000 and 200,000) was used as an ultrafiltration membrane. In particular, the flux measurement of solutions containing algogenic matter used an ultrafiltration membrane of MWCO 50,000. The flux of protein and polysaccharide with coexistence of kaolin increased in the case of the ratio of MW/MWCO being greater than one, but did not increase in the case of the MW/MWCO ratio being below one. In contrast, the flux of fulvic acid and humic acid with coextence of kaolin decreased regardless of the ratio of MW/MWCO. The addition of dispersion agent and coagulant in the organic substances and kaolin mixture solution changed the size distribution of kaolin, and resulted in a change of the flux. EOM and microbial decomposition products decreased with the increase of the fraction of organic matter having molecular weight more than MWCO of membrane. The flux of the algogenic organic matter with coexistence of kaolin decreased with the increase of the amount of kaolin. It was suggested that the decline of the flux with coexistence of kaolin was due to the change of the resistance of the kaolin cake layer corresponding to the change in kaolin size distribution with charge.

Effect of extractant and molecular size on the optical and chemical properties of soil humic acids

Soil Research ◽  
1969 ◽  
Vol 7 (3) ◽  
pp. 229 ◽  
Author(s):  
JHA Butler ◽  
JN Ladd
Keyword(s):  
Molecular Weight ◽  
Amino Acid ◽  
Humic Acids ◽  
Gel Filtration ◽  
Chemical Properties ◽  
Molecular Size ◽  
Carboxyl Content ◽  
Peptide Bonds ◽  
Molecular Weights ◽  
Amino Acid Contents

Humic acids extracted from soil with sodium pyrophosphate have greater proportions of lower molecular weight material, less acid-hydrolysable amino acid nitrogen contents, but greater carboxyl contents and extinction values (260 and 450 nm) than humic acids extracted subsequently from the same sample with alkali. Humic acids extracted with alkali from fresh soil samples have intermediate values. Extinction values at 260 nm are directly correlated with carboxyl contents for a given soil. Different crop histories have no significant effect on the measured properties of the extracted humic acids. An alkali-extracted humic acid has been fractionated by gel filtration into seven fractions of different nominal molecular weight ranges. As the molecular weights of the fractions increase, both aliphatic C-H (based on infrared absorption at 2900 cm-1) and acid-hydrolysable amino acid contents increase, whereas extinction values at 260 nm and carboxyl contents decrease. The infrared spectra of the high molecular weight fractions have peaks at 1650 and 1510 cm-1 which correlate with acid-hydrolysable amino acid contents and which correspond to amide I and II bands of peptide bonds. Alkaline hydrolysis to split peptide bonds eliminates both these peaks. The spectra also have peaks at 1720 and 1210 cm-1 which correlate with the carboxyl content.

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