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  • Polymer and Materials Science  (440)
  • Biochemistry and Biotechnology
  • LUNAR AND PLANETARY EXPLORATION
  • 1945-1949  (440)
Collection
Publisher
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 455-465 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the copolymerization of many monomer pairs induced by benzoyl peroxide has shown that an order of monomer reactivity with radicals exists. By utilizing the data available, it was possible to make a semiquantitative arrangement of many monomers according to their relative rates of reaction with radicals. A symmetrical selectivity factor is assumed to account for deviations from the order in copolymerization reactions. This selectivity may be attributed to (1) complex formation between monomers or to (2) dipole, steric, or other factors which are independent of concentration. Copolymerization equations have been derived for each case and application of them to styrene-methyl methacrylate mixtures has indicated that selectivity due to (2) is most important in this system. The equation for case (2) has been applied to other copolymer systems.
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  • 2
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 475-483 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationships which exist between the solvation and shape of colloid particles, as well as between solvation and viscosity, are discussed. From the most important experiments on these subjects the following conclusions may be drawn. Solvation is dependent on the size and shape of the particles and on the chemical relationship of the dispersion medium to the dispersed portion. True or chemical solvation is generally very small and there is no reason to speak of a thick and tightly bound solvent layer. The solvation of compactly formed particles of spherocolloids is greater, the smaller the particles (all other conditions being equal). Solvation is greater, the more loosely the particles are formed (for dispersion mediums having similar chemical properties and for similar dispersed or dissolved substances). Solvation increases when a corpuscular particle is transformed into a rodlike or threadlike particle; the viscosity also increases; if the threads are further broken down into smaller fragments, then the viscosity decreases, but a further increase in the chemical solvationis supposed to occur. The stability of many lyophilic sols, especially the proteins, depends very little on the solvation; it is mainly dependent on the chemical characteristics of the atomic groups which are found on the surfaces of the particles; the least stability is found for surfaces which contain heteropolar groups - that is, surfaces which have the same number of positive and negative ions.
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  • 3
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general theory is proposed to account quantitatively for the heat polymerization and gelation of the nonconjugated vegetable oils. This is based on a direct approach to polyfunctionality as developed from quantitative considerations of partial random distribution of the fatty acid components in the triglyceride molecules. The differing polymerization rates of linseed and soybean oils are accounted for on the basis of the assumed influence of certain cis-trans geometric isomers. The theory accounts for the anomalous extensive linear polymerization and nongelation of olive oil. Calculations from the theory agree substantially with experimental results on average molecular weight, iodine value, and the percentage of insoluble, infusible cross-linked polymers.
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  • 4
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 535-539 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the rolling of Plastic sheet the viscous work gives rise to heating of the plastic sheet. The maximum temperature reached in the interior of the sheet during shearing is of the interest, both in the theoretical calculation of roll pressure, and from the point of view of possible thermal decomposition effects. A calculation is given for a simple, some-what artificial, model, which leads to an upper value for this maximum temperature if a measurement of the average temperature of the emergent sheet is given. The model taken is that of an infinite sheet, of thickness 2δ, in which heat is continuously liberated at the rate of 4ηφ2 cal. cc. -1 sec. -1, where φ is the relevant value of the rate of compression (assumed constant across the sheet). The curve giving the temperature distribution across the sheet is calculated numerically for two cases; it is relatively flat, as would be expected on physical grounds, since the viscosity, η, decreases as the temperature rises. It is concluded that these thermal effects may be neglected in the calculation of roll pressure in Part 1.
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  • 5
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 581-581 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 7
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 549-580 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This and a previous article (p. 127) review the literature from 1910-1945 on polymerization of olefins and diolefins in suspension and emulsion, and present a number of new measurements not published to date. The subject is considered mainly from the point of view of scientific information on the mechanism of polymerization in aqueous suspensions and emulsions, but brief mention is also made of the more important disclosures in the patent literature. The new data presented in this article refer to (1) initial rates of polymerization of styrene, methyl methacrylate, vinyl acelate and acrylonitrile in aqueous suspensions and in soap emulsions as a function of catalyst concentration, temperature, and soap concentration; (2) influence of water-soluble activators, such as sodium bisulfite; (3) influence of initial size of monomer droplets on initial rates of monomer consumption; (4) study, with the aid of the electron microscope, of size of monomer droplets and polymer particles throughout polymerization; and (5) a few experiments on side reactions in the domain of higher conversions. No attempt is made in this paper to review and appraise the very large number of recent patents (from about 1930 on), which protect special procedures on the use of various promoting, regulating, or modifying ingredients. A complete digest of this practice does not exist at present, but reference may be made to the excellent chapter on emulsion polymerization in the book of Talalay and Magat, to the very valuable compilation of patents by Hoseh, and to the enumeration of a selected number of patents in the book of Scheiber.1
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  • 8
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductance in diphenyl ether at 35°C. and 60 cycles of the picrate of a 4-vinylpyridine-styrene copolymer (10:90) has been measured. The equivalent conductance, based on the nitrogen content, is of the same order as that of picoline picrate, and varies with concentration in accordance with the law of ion association.
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  • 9
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 21-35 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A polyvinyl acetate polymer of medium viscosity was fractionated into sixteen fractions (first series) and three of the larger of these further separated into twenty subfractions (second series). The intrinsic viscosities and the osmotic pressure molecular weights were determined at 25°C. and the relation between them was found to be expressed by the equations: first series: [η] = (1.88 × 10-4) M0.69; second series: [η] = (1.76 × 10-4) M0.68. The data indicate that little, if any, increase in homogeneity is to be expected by further successive fractionations and that the equations applicable to the second fractionation series are representative of essentially homogeneous polyvinyl acetates in acetone. An equation applicable to fractionated and unfractionated vinyl acetate polymers is described that is useful in obtaining the intrinsic viscosity from a single viscosity measurement. Several unfractionated materials from different sources were also studied and the calculated ratios of the viscosity-average to the number-average molecular weight indicate that the degree of heterogeneity of chain-length distribution increases with increasing average molecular weight.
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  • 10
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of emulsion copolymerization of butadiene and styrene, with soap as emulsifier and potassium persulfate as catalyst, is extremely small at 50°C. The presence of very small amounts of high-molecular mercaptans promotes the copolymerization reaction. The promoting effect is at a maximum for primary, secondary, and tertiary dodecyl mercaptans and decreases for mercaptans of either higher or lower molecular weight. The promoting effect is independent within wide limits of the amount of mercaptan added after the minimum quantity has been exceeded. Mercaptans which are poor promoters may be so because they fail to bring about chain initiation or because they aid in chain termination. The low-molecular mercaptans which are poor promoters prevent the high-molecular mercaptans from exerting their good promoting effect when a mixture of both types of mercaptans is used. The mechanism of the promoting effect of mercaptans upon the emulsion copolymerization of butadiene (75 parts) and styrene (25 parts) or upon the polymerization of butadiene alone is not yet clear.
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  • 11
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An empirical equation is described which predicts the intrinsic viscosities of 75:25 butadiene-styrene emulsion copolymers from data on mercaptan consumption. The form of the equation is as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$\left[ \eta \right] = \left[ {\frac{{aP}}{{R_0 R}} + \frac{b}{{R_0 }}\int_0^P {\frac{{dP}}{{dR}}dP} } \right]^c $$\end{document} where [η] is the intrinsic viscosity, P is the conversion, R is the fraction of mercaptan consumed, R0 is the mercaptan charged, and a, b, and c are constants equal to 0.22, 1.12, and 0.66, respectively. Evidence is given that the intrinsic viscosity of mutual-recipe polymers can be described satisfactorily in terms of mercaptan consumption.
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  • 12
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 107-109 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 13
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The calculation of the “theoretical” minimum modifier requirement, TMMR, for butadiene-styrene (75:25) copolymers of given intrinsic viscosities at various conversions is described. The TMMR of 75% conversion polymer of intrinsic viscosity 2.0 is R0 = 0.28, which is only about 60% of the value of R0 for commercial primary dodecyl mercaptan (C.M.) in large-size reactors. The efficiency, E, of a modifier for 75:25 butadiene-styrene copolymerization using soap as emulsifier and persulfate as catalyst has been defined by and calculated from the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$E = \frac{{P\left( {0.2 + P} \right)}}{{R_0 \left( {M_v \times 10^{ - 5} } \right)}}$$\end{document} where Mv is the intrinsic viscosity molecular weight of the polymer at conversion, P, with an amount of mercaptan, R0, charged with the monomers. For all modifiers the efficiency is low at low conversions and gradually increases to a maximum with increasing conversion. For different modifiers this maximum may be as at low as 10% conversion or at higher than 80% conversion. After the maximum the efficiency decreases with further increase of conversion. The most efficient modifier for the production of polymers of intrinsic viscosity, [η], at conversion, P, will meet the following conditions, R = 1 at conversion, P, and dP/dR is constant. Inefficient modifiers may be made more efficient by changing the conditions or procedure of polymerization in such a way that the modifier more nearly complies with the above conditions.
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  • 14
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A comparison has been made of the ultraviolet spectrophotometric and chlorine analysis methods for the composition of copolymers of butadiene and p-chlorostyrene. The results of the two methods are in good agreement.
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  • 15
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 249-258 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The density-gradient tube is a special glass vessel in which a vertical linear density gradient of almost any desired magnitude can be maintained in a stable condition for prolonged periods by using liquids or solutions of the proper density. This article describes the application of such a device to three typical problems appearing in the field of high polymers: crystallization-rate data, inhomogeneities in composition of copolymers, and rates of polymerization. Possible application to still other problems is indicated.
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  • 16
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 565-582 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the results of initial acid-catalyzed hydrolysis of cellulose, and from certain data in the literature it is concluded that (1) native cellulose possesses an indefinitely high molecular weight; (2) as a consequence of common procedure adhered to by most investigators, native cellulose is unintentionally degraded to about DP 3000; (3) mild, initial acidic degradation, intentional or accidental, causes further decrease in the DP values down to the probable limiting value of 128 or 256, with complete loss of the tensile strength of the cellulose fiber; and (4) the few covalent bonds (about 0.3%) which become cleaved during these mild reactions are equally spaced, acid-sensitive, and entirely different from the regular 1,4-glycosidic bonds which are responsible for the random hydrolysis of cellulose in strongly acidic media. It is suggested that these acid-sensitive linkages represent hemiacetal or acetal bonds which originate from openchain glucose anhydride residues of “limit hydrocellulose” units and connect the latter along the a and b axes of the fiber. The length of the “limit hydrocellulose” is supposed to correspond to that of 27 = 128 glucose anhydride residues - that is, 660 Å., or twice these figures. Extension of this concept to starch leads to the postulate of a three-dimensional network of glucose anhydride units of indefinite number. The latter are held together by regular 1,4-α-glucopyranosidic bonds and, at short intervals, probably by acetal bonds of open-chain glucose anhydride residues. On mild, acid-catalyzed hy-drolysis these acid-sensitive linkages rupture rapidly and completely, giving rise to a material which consists of linear molecules only, containing 1,4-, 1,6-, and possibly 1,3-, glycosidic bonds between two adjacent glucose anhydride residues.
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  • 17
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Butadiene and styrene have been copolymerized by the use of sodium sand as a catalyst. The copolymers containing 75 parts of butadiene and 25 parts of styrene and made at 30° and 50° are soluble in benzene and have intrinsic viscosities ranging from 2.5 to 7.5. The copolymers has a very nearly constant composition throughout the course of the polymerization. The amount of butadiene which has entered the chain by 1,2 addition is greater than in the case of the emulsion copolymer.
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  • 18
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 289-292 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixed cellulose acetate-ethers were prepared which contain basic-type nitrogen groups whose films were dyed by xylene brilliant blue. β-Aminoethoxylcellulose acetate was prepared from cellulose diacetate and yarn-type cellulose acetate-propionate using ethyleneimine. β-Cyanoethoxylcellulose acetate was prepared from β-cyanoethoxylcellulose and from cellulose acetate using acrylonitrile with an organic base as catalyst. The solubilities of the mixed ether-esters containing basic type nitrogen groups were less than those of cellulose esters and ethers of comparable degrees of substitution.
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  • 19
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Whatever additional factors may be concerned in the production of good vulcanizates from natural rubber by the action of sulfur, there is no doubt that the action of sulfur on olefinic materials in general at the ordinary vulcanization temperature is a chemical one, the primary course of which is determined largely by the constitution of the olefin, and hence may be profitably studied by experimentation with olefins of different unsaturation patterns. Unaccelerated reaction between sulfur and simple monoolefins leads almost exclusively to cross linking of the separate olefin molecules, mostly in pairs, by groups of sulfur atoms. When, however, two or more olefinic units occur in the same molecule, as in the disoprenic hydrocarbons, intramolecular cross linking, i.e., cyclization, at once becomes possible, and the result of sulfur action consists partly in the cross linking of separate molecules as with the monoolefins, but largely in cyclization of the individual olefinic chains, thereby forming sulfur-containing rings. These changes entail a certain loss of unsaturation, from which deductions can be made as to the mechanism of the reaction.
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  • 20
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogen sulfide has often been thought to play an important role in the sulfur vulcanization of natural rubber. A study has therefore been made of the reaction of hydrogen sulfide with olefins, including polyisoprenes, with special reference to the capacity of the reagent to react with olefins in the presence of free sulfur. Comparison of the products so obtained with those derived (a) by light-catalyzed reaction of hydrogen sulfide and (b) by reaction of free sulfur with polyisoprenes has greatly assisted the understanding of the course of sulfur reaction in vulcanization processes.
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  • 21
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 329-339 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of experiments on the elastic behavior of various textile materials was carried out. All results are described with the aid of a mechanical model. For this purpose it is necessary to introduce the possibility of a blockade of a part of the model. The elastic properties are characterized by the values of seven independent fundamental constants of the model. The value of one of these constants associated with the blockade can be determined experimentally in a direct way; it is found to be independent of the moisture content. The most important properties of the model correspond with the molecular image of Hermans.
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  • 22
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental data are presented on the monomer composition of copolymers of butadiene and styrene prepared by emulsion polymerization at 50°C. The composition of the copolymers is shown to be unaffected by variations in the amount of emulsifier, of mercaptan, and of the nature of the water-soluble polymerization catalyst. The composition of the copolymers formed from a charge containing 25% styrene (by wt.) can be represented accurately over the entire conversion range by the approximate theory according to which each monomer disappears by a first order reaction with the growing chain of the polymer, without taking into account the fact that the end of the growing chain to which the monomer adds may be a radical derived from either of the two monomer molecules. If the ratio of monomers in the charge is varied within wide limits, however, it is found that the simple theory is not adequate and it is necessary to consider that the chain may end with different radicals. The analysis of the experimental data shows that a butadiene molecule adds more rapidly than a styrene molecule to a radical derived either from a butadience or a styrene molecule.
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  • 23
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Squalene containing six isoprene units is more free of end-group effects and less limited in the range of space-distributional contortions of its carbon chain than mono- and diolefins. Hence it is more comparable with rubber than the latter group where matters of chemical reactivity are concerned. Nevertheless, in its reaction with sulfur, squalene pursues a course very similar to that followed by the diisoprene, dihydromyrcene, in that intramolecular sulfide linkages as well as intermolecular polysulfide linkages are formed. Taking into consideration the amount of sulfur which would suffice for the establishment of some given number of the simplest possible intermolecular linkages (i.e., monosulfide linkages), the efficiency of sulfur as a cross-linking reagent during the vulcanization of squalene is seen to be of a rather low order; this condition might be expected to hold for rubber in the absence of auxiliary mechanisms. So far as can be determined by direct experiment the action of sulfur in forming cross links is not essentially different from that encountered with squalene, since there are indications that both intra- and intermolecular sulfide linkages are formed - the latter being of both dialkenyl and dialkyl sulfide type, and, possibly also of alkenyl alkyl type. Under the influence of small amounts of zinc oxide or of various nitrogen-containing organic accelerators, sulfur reacts with the thiol groups of organic mercaptans forming di- and polysulfides, together with hydrogen sulfide. In the presence of rubber the same reaction occurs without actual liberation of hydrogen sulfide and it thus appears that if any thiol groups are formed as intermediates in vulcanization reactions, they will undergo ready conversion into intermolecular di- and polysulfide linkages. This may well represent an important auxiliary mechanism of cross linking.
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  • 24
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the emulsion polymerization of butadiene, styrene, or both, potassium persulfate is often used as the catalyst. A convenient concentration of potassium persulfate in the aqueous layer of the charge is 0.10-0.2%; the method of analysis should therefore be suitable for very small persulfate concentrations. Three methods have been investigated. In the volumetric method the persulfate is allowed to react in an acid medium with an excess of standard ferrous iron, the excess being back-titrated after a given period of time with standard ceric cerium solution. The recommended procedure was found accurate and precise within 0.5%, even at such small concentrations as 5 mg. of potassium persulfate per 100 ml. When latex is analyzed by this method, the polymer is first removed by coagulation with sulfuric acid and the persulfate determined in the filtrate. In order to obtain reliable results the reaction between the persulfate and ferrous iron in the filtrate must be carried out in the absence of oxygen, although this is not necessary in solutions of pure persulfate. The interference by oxygen is attributed to substances of peroxidic character in the fatty acid soaps used as emulsifiers in the emulsion polymerization. The colorimetric method (“Becco” method) is based upon the oxidation of the leuco base of commercial wool green BSMA to a green dye by the persulfate and (colorimetric) measurement of the dye formed. The various factors affecting the accuracy and precision of this method have been investigated and a procedure is given for the analysis of latex. For several reasons, the volumetric and polarographic methods are superior to the colorimetric method. Persulfate in a latex can be determined accurately by polarographic analysis of the latex filtrate after removal of the polymer with sulfuric acid. The polarographic determination can be carried out, in the presence of oxygen, with simple equipment. The method is rapid and precise.
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  • 25
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    Journal of Polymer Science 1 (1946), S. 353-363 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixtures of butadiene and dimethylbutadiene with varying quantities of styrene and acrylonitrile have been copolymerized under various catalytic conditions at 100°C. The formation of cyclic dimers from dienes and vinyl compounds is, in some cases, much more pronounced than the dimerization of the dienes alone. Since the latter is also a kind of Diels-Alder reaction, a series with increasing dienophilic properties can be established from a comparison of the yields of cyclic dimers. From solubility and swelling experiments it is evident that the polymers prepared from butadiene and the vinyl compounds and those from dimethylbutadiene and acrylonitrile are true copolymers. The mechanical properties of the copolymers from butadiene and increasing amounts of a vinyl compound change gradually from those of a rubber to those of the polyvinyl compound. The copolymers from a mixture containing 30% styrene or acrylonitrile are very similar, respectively, to Buna S and Perbunan. Copolymers of the same composition from dimethylbutadiene and acrylonitrile, on the other hand, form a new class of thermoplastics with a much higher temperature of elasticity.
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  • 26
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    Journal of Polymer Science 1 (1946), S. 364-379 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymerization in emulsion of butadiene with varying amounts of styrene and acrylonitrile and of dimethylbutadiene with the latter vinyl compound has been studied on a laboratory scale. An essential difference between polymeric vinyl compounds and polydienes is the olefinic character of the latter, which leads to typical secondary changes in the polymers originally formed during the completion of the reaction. Such changes are of fundamental importance for the ultimate mechanical properties of polymers and copolymers based on dienes. After a brief discussion of the general theoretical line of thought serving as a base for our experiments, the influence of various factors on the rate of polymerization is pointed out and demonstrated by experiments. The changes in the nitrogen content of copolymers from acrylonitrile and the yields as a function of the reaction time have also been studied. From an investigation of some physical properties, such as solubility and swelling, the existence of true copolymers (of unknown irregularity) has been established. Copolymers from dimethylbutadiene and acrylonitrile represent a new class of olefinic thermoplastics resembling gutta-percha. Abbreviations used are BP (benzoyl peroxide) and DAB (diazoaminobenzene).
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  • 27
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    Journal of Polymer Science 2 (1947), S. 583-592 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various problems related to the determination with x-rays of the atomic configuration of organic fibers are discussed. Because of the approximate nature of the underlying theory, too far-reaching conclusions should be avoided, especially since, in the case of organic fibers, the situation is much less simple than in the case of sodium chloride powder or metallic wires, for example. Because of these facts, and because of the relative poorness of fiber patterns, the atomic coordinates as well as the space group of the structure can be found only within certain limits. Though the use of macroscopic models is very helpful in visualizing the spatial arrangement, no conclusions of a quantitative nature can be reached with their aid because the assumptions embodied in these models are too numerous and too inexact to justify speculations on details of the structure. In the case of cellulose fibers, it is shown that the problem cannot yet be solved completely; the outlook for a really unique solution is not hopeful. The structure proposed by Meyer and Misch is still the best approximation available. More recent propositions are shown to be less well founded; the atomic configuration introduced by Peirce, being at variance with chemical, crystallographic and x-ray evidence, is to be discarded.
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  • 28
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    Journal of Polymer Science 2 (1947), S. 612-622 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intrinsic viscosity, calculated in accordance with the empirical relation established by Schulz and Huggins, deviates considerably from its true value in the case of increasing viscosities. The introduction of a simple corrective, second degree term η2sp/150, applicable to most of the polymers, permits the direct computation of intrinsic viscosity based upon polymer solutions of various concentrations. Specific viscosities may vary to a great extent and reach a value as high as 15; the use of high concentrations permits the reduction of experimental errors and the determination, to within an average of one per cent, of the intrinsic viscosity of the polymer sample, and thus of its molecular weight.
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  • 29
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A solvent prepared by mixing 70 parts by volume of ethanol, 30 parts of toluene, and 10 parts of water is found to be a suitable solvent for the extraction of organic nonrubber material from GR-S. The presence of the water has no effect on the rate of extraction of the nonrubber, while it reduces the extractibility of low molecular polymer to one-tenth of that found in the absence of water in the solvent. A procedure is described for the determination of small amounts of GR-S in the extracts. This procedure is based on the quantitative precipitation of the ICl addition product of the rubber from a chloroform solution by addition of ethanol. A routine procedure for the determination of the amount of rubber in GR-S is given.
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  • 30
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    Journal of Polymer Science 3 (1948), S. 22-31 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A turbidimetric method has been developed for determining the styrene content in water and soap solution. The solubility of styrene in distilled water was 0.022% while in 2.0% potassium oleate solution it was 0.65 to 0.88%. The course of the polymerization of a saturated solution of styrene in 2% potassium oleate was followed by a colorimetric analysis based on reaction with dilute potassium permanganate. The rate of polymerization decreased rapidly after 50% conversion. The activation energy was estimated to be 17,000 kcal., somewhat less than in solution. The molecular weight of the polymer produced was 200,000. Occasional erratic results were ascribed to possible influence of various amounts of air sealed in the polymerization mixtures.
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  • 31
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been demonstrated that the homogeneity in respect to molecular weight of emulsion copolymers of butadiene and styrene can be increased by the use of certain derivatives of n-dodecyl mercaptan rather than the mercaptan itself. These derivatives decompose and relase n-dodecyl mercaptan at an even rate during the polymerization reaction. Several new derivatives of n-dodecyl mercaptan are described.
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  • 32
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Precise analytical methods are developed using iodine monochloride for the determination of unsaturation in polybutadiene and polyisoprene and their copolymers with styrene. The complicating side reactions, splitting out and substitution, as well as the influence of the solvent employed are investigated in detail. It is concluded that GR-S at various conversions has the theoretical unsaturation. Emulsion polybutadiene exhibits 97 to 98% of the theoretical unsaturation, emulsion polyisoprene 97% sodium polybutadiene 92%, and sodium polyisoprene 85%. The amount of unsaturation in these last two polymers as well as in the sodium copolymer of butadiene and styrene (75:25) is considerable less than theoretically expected.
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  • 33
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline soybean trypsin inhibitor has been inactivated by ultraviolet light (λ2537 Å.) with a quantum yield of 0.0088 based upton loss of ability to inhibit the action of trypsin on casein. Inactivation involves a “one-hit” process.
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  • 34
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The German redox system of emulsion polymerization of butadiene and styrene has been found to be very sensitive to exact details of experimental procedure. Soap may be substituted for the alkanesulfonate used by the Germans; it is then unnecessary to add ferric laurate to the system.Careful investigation of the soap-emulsified mixture leads to the conclusion that 0.25 parts of benzoyl peroxide, 0.50 parts of ferrous sulfate heptahydrate, and 3.0 parts of sodium pyrophosphate decahydrate were the optimum concentrations of the essential ingredients for polymerization of an emulsion of 75 parts of butadiene and 25 parts of styrene in 200 parts of water and 5 parts of Procter and Gamble soap Flakes (S.F.) at 30°. At very low iron concentration the addition of a reducing agent as “booster” was beneficial; for this purpose sorbose can be replaced by fructose or, less satisfactorily, by a number of other reducing agents.
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  • 35
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    Journal of Polymer Science 3 (1948), S. 325-326 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The rate constants for thermal polymerization of indene at 150° and 175° in the absence of oxygen have been found to be 6.0 × 10-6 and 3.16 × 10-5 min.-1, respectively. The average degree of polymerization at each temperature was slightly less than four.
    Notes: Die Geschwindigkeitskonstante der thermischen Polymerisation von Inden bei 150° und 175° in Abwesenheit von Sauerstoff wird zu 6.0 × 10-6 und 3.16 × 10-5 min.-1 resp., bestimmt. Der durchschnittliche mittlere Polymerisationsgrad war etwas geringer als 4 bei beiden Versuchstemperaturen.
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  • 36
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    Journal of Polymer Science 3 (1948), S. 216-222 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion polymerization of allyl acetate yields a polymer of the same average molecular weight as is obtained in bulk polymerization. The decomposition of potassimn persulfate is of the first order but is greatly accelerated by the presence of allyl acetate or of ethyl acetate. Three independent methods of analysis agree in indicating the presence of sulfate groups in 75% of the polymer molecules. It is concluded that the mechanisms of chain initiation and termination are analogous to those in the peroxide-induced bulk polymerization of allyl acetate. These facts do not serve to distinguish between different postulated loci reaction in emulsion polymerization.
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  • 37
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    Journal of Polymer Science 1 (1946), S. 529-534 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An elementary theory is given for the rolling of polymeric materials, for the case in which the deformation is largely an irreversible flow of the viscous type. The theory treats the rolling process as the homogeneous deformation of volume elements over the arc of contact and neglects frictional forces that may exist at the roll surface. A numerical example is given of the calculation of roll pressure, which agrees with available data to a factor of two or better. A more complete test will require parallel measurements of viscosity and roll pressure on the same material.
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  • 38
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    Journal of Polymer Science 3 (1948), S. 518-524 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymeric indene prepared in the presence of oxygen can be separated into two fractions by precipitation with methanol. Polyindene is insoluble while the methanol-soluble portion can be precipitated from benzene by petroleum ether as a white powdery “polyindene peroxide.” Fractionation yielded samples with molecular weights from 300 to 3000. Bromine titration indicated that the lower molecular samples contained about one double bond per polymer molecule. The polymer gave qualitative tests for peroxide, but iodimetric titration of one sample gave only some 42.5% of the calculated active oxygen content.
    Notes: Polymeres Indol, das in Gegenwart von Sauerstoff dargestellt wurde, kann durch Fällen mit Methylalkohol in 2 Fraktionen getrennt werden. Polyindol ist unlöslich. Die methylalkohollösliche Fraktion kann aus Benzol mit Petroläther als ein weisses, pulveriges “Polyindolperoxyd” ausgefällt werden. Fraktionierung führte zu Substanzen mit Molekulargewichten zwischen 300 und 3000. Bromtitration deutete darauf hin, dass die niedrigmolekularen Proben ungefähr eine Doppelbindung pro Polymermolekül enthielten. Die qualitative Prüfung für Peroxyd war positiv, aber die jodometrische Titration einer Probe ergab nur 42.5% des berechneten aktiven Sauerstoffgehaltes.
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    Journal of Polymer Science 3 (1948), S. 525-534 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The reaction of indene with sulfur has been shown to give a polymer containing one atom of sulfur per indene unit. The refraction and absorption characteristics of the polymer have been reported. The kinetics of the reaction of sulfur, with and without added accelerators, have been investigated with the view to establishing the influence of the accelerators on the rate and the temperature coefficient.
    Notes: Es wird gezeigt, dass die Reaktion von Indol mit Schwefel zu einem Polymer führt, das ein Schwefelatom pro Indoleinheit enthält. Der Brechungsindex und das Absorptionsspektrum des Polymers werden mitgeteilt. Die Kinetik der Schwefelreaktion, mit und ohne Zusatz von Beschleunigern, wird untersucht um den Einfluss der Beschleuniger auf die Reaktiongeschwindigkeit und die Temperaturabhängigkeit der Reaktion festzustellen.
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  • 40
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    Journal of Polymer Science 3 (1948), S. 549-563 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence has been studied of systematic alterations in the amount of cross linking in elastomers upon diffusion coefficients and permeability constants in elastomers of homologous paraffin hydrocarbons. In a number of such media the influence of chain length of the paraffins upon the transport phenomena has also been investigated, using CH4, C2H6, C2H4, C3H8, and n-C4H10.Apparent activation energies for permeation (Ep) and for diffusion (ED) for degrees of vulcanization up to 11.3% combined sulfur are in the decreasing order: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm butane } 〉 {\rm propane } 〉 {\rm }_{{\rm ethylene}}^{{\rm ethane}} {\rm } 〉 {\rm methane } 〉 {\rm nitrogen}$$\end{document} For low vulcanizates, EP is not very sensitive to the per cent sulfur. However for higher percentages of sulfur, EP tends to rise, especially when the migrating molecule is a large one. ED is rather more sensitive both to molecular size and to per cent combined sulfur.Both EP and ED for natural rubber vulcanizates show definite temperature coefficients, manifested as curvature when log10 D or log 10 P is plotted against 1/T. Such curvature was absent, however, in butyl rubber.The results have been interpreted in terms of the molecular nature of elastic networks and in terms of the kinetic-statistical (zone) theory and the transitionstate theory. All treatments indicate the need for a considerable zone of activation for each unit diffusion process, confirming an earlier investigation. When, in the Arrhenius equation, D = D0e-ED/RT, one plots log10D0 against ED/T, the clear functional relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm }D_0 {\rm } = {\rm } - 3.6{\rm } + {\rm }0.14{\rm }{{E_D } \mathord{\left/ {\vphantom {{E_D } T}} \right. \kern-\nulldelimiterspace} T}$$\end{document} emerges. A simple interpretation of this and of similar functional relationships for other “activated” physical and chemical rate processes has been given.
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  • 41
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    Journal of Polymer Science 3 (1948), S. 564-575 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility of nitrogen, ethylene, and the n-paraffins from methane to pentane has been measured in a series of natural rubber vulcanizates in relation to chain length of paraffin, temperature, and degree of cross linking of vulcanizates which contained between 1.7 to 21.9% combined sulfur.For smaller, less soluble paraffins the degree of vulcanization had little influence upon the solubility but for higher molecular paraffins such as pentane this influence became significant. A qualitative interpretation of the effects observed was given. The solubility data are in all cases represented by a statistical theory of one of the authors for a mean frequency of vibration of the solute in the medium corresponding to the infrared (0.5 to 1.0 × 1012 sec.-1). The solubility constants, σ, and critical temperature, Tc, are also empirically related by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm }\sigma {\rm } = {\rm }a{\rm } + {\rm }bT_c {\rm }\left( {a{\rm and }b{\rm are constants}} \right)$$\end{document} Heats and standard free energies of solution for the earlier homologous paraffins show steady trends as the chain length increases. The heats are exothermal and are adequately interpreted as the sum of the heats of liquefaction together with a small heat-of-mixing term for liquid and rubber which was usually close to that given by Hildebrand's cohesive energy density equation: \documentclass{article}\pagestyle{empty}\begin{document}$$q{\rm } = \;\left[ {\left( {{{E_1 } \mathord{\left/ {\vphantom {{E_1 } {V_1 }}} \right. \kern-\nulldelimiterspace} {V_1 }}} \right)^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} {\rm } - {\rm }\left( {{{E_2 } \mathord{\left/ {\vphantom {{E_2 } {^2 V_2 }}} \right. \kern-\nulldelimiterspace} {^2 V_2 }}} \right)^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} } \right]^2 V_1 v_2^2$$\end{document} As anticipated from statistical theory, entropies were usually several entropy units more negative than those for solutions of gases in monomeric solvents.
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    Journal of Polymer Science 3 (1948), S. 606-607 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 43
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  • 44
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    Journal of Polymer Science 3 (1948), S. 631-634 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An empirical method of correcting the sedimentation constant of high polymers for its concentration dependence is proposed. It should be possible to determine the sedimentation constant at infinite dilution with reasonable accuracy from experiments at concentrations where reliable measurements can be made.
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  • 45
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    Journal of Polymer Science 3 (1948), S. 635-641 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By denaturation of potato albumin by pyridine or by heat the viscosity increases; simultaneously the capability of the denatured protein t o reduce iodine increases, which, according to Anson, is due to the liberation of SH groups. A similar increase of viscosity was observed by the conversion of legumin into a water-soluble modification, and further by heating the solution of this protein; the volume of iodine required for oxidation of the denatured protein is greater than that of the native legumin. This denatured protein can be reconverted into its native state, whereupon the reducing capacity again decreases. Several fractions of green pen and horse bean legumin were denatured by urea and it was found that the viscosity and the reducing capacity thereby increase. In the case of legumelin the viscosity is low but the reducing power high; this indicates that legumelin is a degradation product having globular molecules.
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  • 46
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    Journal of Polymer Science 3 (1948), S. 609-630 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical structure of a large number of linear condensation polymers is correlated with their ability to assume a polycrystalline form possessing the right degree of thermal stability, and with the possession of fiber-forming properties. Certain structures lead to the absence of crystallinity and of fiber-forming properties, while, under certain conditions, a low degree of crystallinity or its complete absence leads to polymers possessing rubberlike properties, which may form highly elastic threads. Some properties of fibers such as solubility, sensitivity to mositure, and certain dyeing characteristics, can be correlated to some extent with chemical structure. These effects are considered on the basis of the introduction of various polar links and ring structures, according to regular patterns, into the polymethylene chain (polythee). The ehter (R—O—) and ester (—CO·O—) links lower the crystallite melting point to such an extent that some polymers containing them are completely noncrystalline at normal room temperatures. Urethan (—O·CO—NH—), amide (—CO·NH—) and urea (—NH·CO·NH—) links raise the crystallite melting point to an extent which increases in the order named. Most other polar links raise the melting point. The introduction into the aliphatic chain of ring structures, particularly aromatic rings directly attached to polar groups, raises the crystallite melting point, but in this case symmetry exerts an over-ruling effect. A low degree of symmetry may lower the melting point and even eliminate crystallinity entirely to the detriment of fiber-forming properties. Inert side chains lower the melting point considerably, and in some cases render the polymer completely noncrystalline at normal room temperatures.
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    Journal of Polymer Science 3 (1948), S. 652-662 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been demonstrated that the adhesion of high polymers to cellulose is a function of tack temperatures and dielectric constants, ∊, of the polymers and of dipole moments, μ, of polar groups. A plot of tack temperature versus mirror image force, μ1μ2/,of copolymers gives an area of adhesion bounded by a tack temperature of 100% and mirror image forces of 0.7 and 1.3 and opening toward lower tack temperatures. Outside of the area polymers do not adhere well to cellulose. By coating polymers on cellulose pretreated with Werner chromium complexes of acids bearing polar groups, it has been found that adhesion is a specific function of the polar groups within the polymer and on the modilied cellulose. Adhesion is strongest with approximately equal dipole moment substituents on the modified cellulose and in the copolymers.
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  • 48
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    Journal of Polymer Science 2 (1947), S. 142-156 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic and plastic properties of high polymeric materials are functions of the forces holding the molecules together and the ability of small segments of the chains to move about, relative to other segments. Internal plasticization is accomplished by introducing structural features which reduce intermolecular and intramolecular forces and which, in general, decrease the order of the polymer. Physical techniques used to determine the effect of such structural features have been discussed. The results of numerous investigations into the relations between structure and properties have been considered in an attempt to present a simple and consistent physical picture of these relations.
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    Journal of Polymer Science 2 (1947), S. 178-198 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic properties of plasticized Vinylite VYNW were studied over a wide range of time scale by means of the tensile creep test. A number of different plasticizers were compared as to their plasticizing effectiveness. It was found that different plasticizers imparted distinctly different shapes to the creep curve of the plasticized ferent plasticized resin. The flat creep curve, characteristic of trioctyl phosphate, is considered to be superior to the steep creep curve of tricresyl phosphate. Mixtures of plasticizers were also studied. A number of conjectures are advanced concerning the molecular mechanism of plasticizer action. One important characteristic of a plasticized formulation of the polyvinyl chloride types of resin is the existence of a three-dimensional gel structure of great permanence which prevents the occurrence of irrecoverable viscous flow.
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    Journal of Polymer Science 4 (1949), S. 597-604 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Information concerning monomer reactivity in copolymerization has been obtained for thirteen copolymerization systems. The influence of substituents and chain length in vinyl polymerization is discussed in the light of this and preceding data. Unsaturated acid behavior in copolymerizations is discussed for the first time.
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    Journal of Polymer Science 4 (1949), S. 619-628 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By applying hydrochloric acid solution at different temperatures to various fibrous cellulose samples and following the per cent loss in weight with time, hydrolysis-time curves have been obtained. These plots have been resolved into a straight line and a curve, representing the rate of removal of difficultly and easily removable components, respectively. Under the experimental conditions applied, the ratedetermining reaction in the removal of the difficultly accessible components from the fibers is essentially a kinetically zero-order reaction. This was borne out by the results of hydrolyses of hydrocellulose preparations. Within the experimental range the temperature coefficient of this rate is independent of the representative fibrous materials and is relatively high, corresponding to an energy of activation of 28-29 kcal./mol. The easily and difficultly accessible regions, assessed by resolving the rate plots, are different with the same fibers, depending on the experimental conditions. The reactivity of both the easily and difficultly hydrolyzable constituents varies with different cellulose fibers. The complex nature of the kinetics of removal (hydrolysis) of the easily accessible components is discussed.
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    Journal of Polymer Science 4 (1949), S. 639-664 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of polyisobutene, polyisoprene, polybutadiene, GR-S, and polyethylene, weighing about 25 to 50 mg., were pyrolyzed in a vacuum of about 10-6mm. of mercury in a specially designed apparatus at temperatures ranging between 300 to 475°C. The volatile products of pyrolysis were separated into four fractions: (IV) gaseous, volatile at -196°; (IIIA) liquid, at -75°, (IIIB) liquid, at 25°; and (II) waxlike fraction, volatile at the temperature of pyrolysis. The gaseous fraction was analyzed in the mass spectrometer and was found to consist in all cases of CH4. The liquid fraction, IIIA, was analyzed similarly and was found to give a mass spectrum characteristic for any given polymer. A molecular weight determination of the waxlike fraction by the micro freezing point-lowering method, showed it to vary from 543 to 739, depending on the polymer from which the fraction was obtained. It is shown that the method of pyrolytic fractionation of high molecular weight polymers, in conjunction with mass spectrometer analysis of the more volatile fractions, can serve as a means of identifying the polymers.
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    Notes: The infrared and ultraviolet absorption spectra of Koresin are very similar to those of an acid-catalyzed p-tert-butylphenol-acetal- dehyde polymer. This is believed to be evidence that Koresin has Structure I. A variety of phenol-aldehyde resins have been prepared for comparison with Koresin. The ratings of some of these materials as tackifiers have been reported. These furnish further evidence that the molecular weight of a phenol-aldehyde resin is important in its tackifying action. An alkaline-catalyzed condensation product of acetylene and p-tert-butylphenol shows no tackifying action and has no free hydroxyl in the polymer as judged by its infrared pattern.
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  • 54
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    Journal of Polymer Science 2 (1947), S. 301-305 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In contradistinction to the usual methods, the diffusion of water into a polymer has been investigated by starting from a disk of the material surrounded by water. In this way, actual service conditions are often closely approached. Since a theoretical basis is desirable, equations are given for this type of diffusion, and experiments with a wood flour containing phenol-formaldehyde material were performed from which values for the permeation constant could be derived.
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  • 55
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    Journal of Polymer Science 2 (1947), S. 314-317 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that molecules of benzidine dyes can diffuse into cellulose fibers only perpendicular, not parallel, to the fiber axis.
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  • 56
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    Journal of Polymer Science 2 (1947), S. 329-345 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A review is given of physicochemical studies on cellulose and cellulose derivatives made during the years of World War II at the Institute of Physical Chemistry, Uppsala, Sweden. Emphasis has been laid on the principles of the subject and the review deals essentially with some investigations on nitrocellulose by the present author. An outline of the problems of the cellulose chemistry of today serves as an introduction. The principles of molecular weight determinations from Svedberg's equation are briefly mentioned, and the difficulties in the extrapolation of sedimentation constants to zero concentration are discussed. The problem of what sort of average molecular weight is obtained from Svedberg's equation is treated subsequently and methods for determination of distributions from combinations of osmotic and sedimentation experiments described. A table comparing five different sorts of average molecular weights for a numbe of nitrocelluloses is discussed.
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    Journal of Polymer Science 2 (1947), S. 349-350 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 58
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    Journal of Polymer Science 3 (1948), S. 642-645 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymeric oxidation products of indole act like typical peroxides in polymerization reactions. Due to their relatively high stability the increases of the reaction is small, while fragments of the degraded peroxide enter the polymer molecule.
    Notes: Polymere Oxydationsprodukte des Indens verhalten sich in Bezug auf Polymerisationsreaktionen wie typische Peroxyde. Ihre verhältnismässig hohe Stabilität bedingt eine relative geringe Reaktionsbeschleunigung, wobei Bruchstücke des zerfallenden Peroxyds in die polymere Molekel eintreten.
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  • 59
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    Journal of Polymer Science 3 (1948), S. 646-646 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 60
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    Notes: A refractometric technique for determination of second-order transition temperatures (Tm) of polymers has been extended to include a series of alkyl acrylate and methacrylate polymers with transitions at temperatures down to -50°C. A convenient technique for determining refractive index down to -75°C. is described. Certain long-chain alkyl polymers are birefringent below Tm. Correlations of brittle point with Tm and relations between viscosity and Tm are reported.
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    Journal of Polymer Science 3 (1948), S. 795-796 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 62
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    Journal of Polymer Science 2 (1947), S. 420-431 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Bomb calorimetric measurements have yielded for the heats of combustion ( - ΔHoc) at 25°C. of liquid styrene and solid polystyrene to form gaseous carbon dioxide and liquid water the values 4394.88 ± 0.67 int. kjoule per mole (1050.58 ± 0.14 kcal. per mole), and 4325.09 ± 0.42 int. kjoule per C8H8 unit (1033.89 ± 0.10 kcal. per C8H8 unit), respectively, and for the heat of polymerization of liquid styrene to solid polystyrene at 25°C. the value 69.79 ± 0.66 int. kjoule per mole (16.68 ± 0.16 kcal. per mole). The results obtained on two samples of polystyrene of different molecular weight were in agreement within the precision of the measurements. Measurements of the heat of solution of solid polystyrene in liquid monomeric styrene gave the value 3.59 ± 0.21 int. kjoule (0.86 ± 0.05 kcal.) evolved per C8H8 unit of polystyrene at 25°C. Addition of this to the value for the heat of polymerization of liquid styrene to solid polystyrene gives the value 73.38 ± 0.69 int. kjoule (17.54 ± 0.16 kcal.) per mole of styrene for the heat of polymerization of liquid styrene at 25°C., when the final product is a solution of polystyrene in styrene containing 6.9% by weight of polystyrene.
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  • 63
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  • 64
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    Journal of Polymer Science 3 (1948), S. 804-811 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments with cross linking of nitrocellulose in butyl acetate solution by means of titanium tetrachloride are described. The gels have been examined by means of sedimentation in the ultracentrifuge and measurements with a consistometer. The yield value of the flow curves and the extent of cross linking were studied as functions of nitrocellulose concentration, amount of cross-linking substance, and time of reaction.
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  • 65
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    Notes: X-ray diffraction patterns of stretched crystallized polybutadiene polymerized at -20°C were obtained using molybdenum, copper, and chromium characteristic x-radiations on the same sample. The pattern obtained using molybdenum radiation showed diffraction effects in the 0, 1st, 2nd, 3rd, and 4th orders. The lack of detail in this pattern is partly due to the relatively intense background. By using the longer wavelength copper and chromium radiations the diffraction effects of the zero- and first-order layer lines were brought out in considerable detail. The diffraction data obtainable from these layer line patterns may be useful in carrying out a structural analysis of crystalline polybutadiene.
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  • 66
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    Notes: The fundamental basis of our work is the application of statistics involving both the energy of interaction between solute and solvent molecules and the effect of steric hindrances: the statistics of freely rotating chains (sometimes called the statistics of Kuhn) are a special limiting case. Using this we can show that in the law [η] = KNα the coefficient is a function of N having a value close to 2 for small values of N, and approaching on first approximation a value of 0.5 when N increases infinitely. This statistical method has the advantage of permitting an approach to the important problem of the variation of the intrinsic viscosity as a function of the temperature T. The behavior of intrinsic viscosity with degree of polymerization and temperature as predicted by the theory check with experiment, and, in the case of the hemipolystyrenes, it has been possible to obtain very satisfactory quantitative verification. In view of numerous experiments which show that, at a given temperature, the limiting value of α for very large N is greater than 0.5, we have altered the theory of the equivalent particle accordingly. As a basis for the change the concept of porosity is examined with several other concepts, and it is shown that it is likely to apply only with reservations when the molecular structure of the solvent is taken into account.
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    Journal of Polymer Science 3 (1948), S. 850-865 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The decrease of the limiting viscosities of unfractionated and fractionated polystyrene with time has been studied over a range of temperatures from 248 to 340°C. in vacuo. Distribution curves of several degraded samples have been determined. It has been established that the theory of random breaking of links is not applicable in the case of polystyrene. Three major deviations from the random theory have been found. The experimental results have been evaluated employing the weak link theory. The mechanisms proposed account satisfactorily for the deviations from the random theory, and give a fair representation of the experimental results, only the experimental distribution curves still showing deviations from those predicted by theory. The elementary steps for the degradation in vacuo have been discussed and the role of oxygen during polymerization has been indicated.
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    Journal of Polymer Science 3 (1948), S. 895-897 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science 3 (1948), S. 900-900 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 70
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    Journal of Polymer Science 4 (1949), S. 1-12 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The production of monomer during degradation of polystyrene in vacuo below 310°C. has been investigated. A mechanism has been proposed which explains the dependence of monomer formation on the initial breaks in the chain. The degradation in presence of oxygen has been studied. A mechanism for this reaction has been proposed which accounts for the type of curves obtained experimentally. The role of antioxidants has been briefly indicated. The elementary steps for the degradation in vacuo and in the presence of oxygen have been discussed.
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    Journal of Polymer Science 4 (1949), S. 13-36 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: An apparatus has been constructed which enables one to follow continuously the formation of monomer during degradation in vacuum. Experimental results are presented on the degradation of fractionated and unfractionated polystyrene over a range of temperatures from 340-400°C. in vacuum. A mechanism has been proposed which accounts satisfactorily for the apparent zero-order reaction and for the dependence of the rate of degradation on chain length. This mechanism allows one to estimate relative number average molecular weights and the number of weak points per original chain. The influence of a platinum surface on degradation has been indicated. The degradation of poly-alpha-methylstyrene has been investigated over a range of temperatures from 281 to 363°C. in vacuum. The mechanism of the degradation of branched polymer chains has been discussed. The degradation of cross-linked polystyrene containing various amount of m-divinylbenzene has been studied at 364°C. in vacuum. The reaction shows long induction periods depending on the amount of m-divinylbenzene and on the presence of benzoyl peroxide during polymerization. The degradation of polyethylene shows this polymer to be more heat resistant than polystyrene. Various grades of different average molecular weight have been investigated over a range of temperatures from 375 to 436°C. in vacuum. The energy of activation has been found dependent on chain length. A mechanism has been suggested to account for the observed experimental results.
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    Notes: Quantum yields for the inactivation of crystalline swine pepsin have been determined as a function of pH at 2537 A. The quantum yield is near a minimum at pH 4.08, at which point a value of 0.0019 was found, rises rapidly above pH 6, and shows a slight maximum near pH 2.7. The maximum is more pronounced with polychromatic light. The quantum yield (at pH 2.01) was found to be the same with either hemoglobin or casein as a substrate. Urea had no effect on the quantum yield although urea alone, 7 M, inactivates pepsin at an appreciable rate. Urea and light denaturation do not modify the absorption spectrum of pepsin in the same way. The data of Gates has been recalculated; it shows an increase of quantum yields with decreasing wave length. It has been concluded, from experiments with model substances, that inactivation can occur by the absorption of a quantum by any aromatic group in pepsin.
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    Journal of Polymer Science 4 (1949), S. 135-144 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method for the evaluation of the percentage crystallinity in cellulose preparations from x-ray intensity measurements, previously described in detail (J. Appl. Phys., in press) is reviewed briefly and new material presented consisting of crystallinity percentages between 8% and 70%. Cotton, flax, and ramie possess equal crystallinity (70%) and so do the majority of rayons, independent of their degree of orientation and including cuprammonium and Lilienfeld rayons. Cellulose acetates saponified under varying conditions also yield almost the same value as rayon (40%). The New product Fiber G (du Pont) holds an exceptional position with 53% crystalline substance. In the series of native celluloses, wood pulp has about 65%, Valonia 65-70%, and bacterial cellulose about 40%. By dry grinding of rayon, a powder was obtained containing only slightly less than 10% crystalline substance, which on recrystallization in water, yields 2 product having the same crystallinity as rayon. The difference between the heats of wetting of the criginal and the recrystallized powder affords additional support of the results obtained.
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  • 74
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    Notes: A series of copolymers, of 4-vinylpyridine and styrene, covering the range 1.5 to 100% vinylpyridine were prepared in 20% toluene solution at 80°. Strong electrolytes were then made by the addition of n-butyl bromide in nitromethane solution. The salts with high vinylpyridine content were soluble in water, alcohols, nitromethane, and other polar solvents. Viscosities of the parent copolymers in methyl ethyl ketone were in the range 0.15-0.20; osmotic pressures gave molecular weights in the range 50,000-80,000. The polyelectrolytes in nitromethane and nitromethane-dioxane mixtures gave viscosity-concentration curves which were strongly concave upwards: at 1 mg./100 cc., the reduced viscosity of the salt of polyvinylpyridine in nitromethane was 6.0. The salts of the different copolymers did not differ much in their viscosities at concentrations above a few tenths of a gram per 100 cc., a fact which shows a high degree of ionic association; only as zero concentration is approached, can the detailed polymer structure be seen. The extent of association at a given concentration is controlled by the amount of vinylpyridine in the copolymer and by the dielectric constant of the solvent. Addition of simple one-one electrolytes, such as tetrabuty lammonium bromide, suppresses the electrostatic increase in viscosity which otherwise appears at low concentrations. The following empirical equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ {{\eta _{{\rm sp}} } \mathord{\left/ {\vphantom {{\eta _{{\rm sp}} } {\rm C}}} \right. \kern-\nulldelimiterspace} {\rm C}} = {{\rm A} \mathord{\left/ {\vphantom {{\rm A} {\left( {1 + {\rm B}\sqrt {\rm C} } \right)}}} \right. \kern-\nulldelimiterspace} {\left( {1 + {\rm B}\sqrt {\rm C} } \right)}} + {\rm D} $$\end{document} was found to fit the data for the different systems studied. The constant A depends on copolymerization ratio and probably on molecular weight; it is a measure of the extent to which the polymer coil can spread out at infinite dilution as a consequence of the intramolecular Coulomb repulsion between charges attached to the chain. It is roughly several orders of magnitude larger than the intrinsic viscosity of the parent polymer. The constant B is a measure of the electrostatic forces and increases with decreasing dielectric constant of the solvent.
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    Journal of Polymer Science 4 (1949), S. 152-152 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 4 (1949), S. 145-151 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray measurements on 16 different specimens of regenerated cellulose reveals that there exists a pronounced negative correlation between the integrated intensity of the 101 interference and its halfwidth. The 101 plane is a preferred cleavage plane and represents the lamellar plane of the ribbon-shaped crystallites. Variations in the intensity of the other interferences are much less or nonexistent. These results show that the degree and the perfection of lateral order according to the 101 and 002 planes is little at variance, but that order according to the 101 plane is extremely variable in such a way that if the average thickness and (or) perfection of the lamellae increases, the total number of well-ordered 101 plane contacts diminishes. As a possible explanation of this phenomenon it is suggested that various degrees of recrystallization with reference to this particular plane (i.e., various degrees of lateral order) may be associated with the various rayon specimens. This, however, does not necessarily imply differences in the total amount of ordered substance. This explanation is corroborated by the fact that cellulose acetate fibers which were previously allowed to “recrystallize” by heating in methanol, after saponification yield a rayon with a particularly sharp, but also particularly weak, 101 interference, without exhibiting a higher total percentage of ordered substance than the saponification products of acetate treated in this manner.
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    Journal of Polymer Science 4 (1949), S. 153-182 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The approximations implicit in the use of the Gaussian network model for soft rubber are discussed. It is shown that the form of the stress-strain curve can be derived for this model simply, and without special assumptions about the form or behavior of the network. The common assumption that the network junctions are fixed, or can be treated as fixed, is discussed. It is shown that this picture of the situation is unrealistic: the junctions have a Brownian motion comparable to that of any portion of the intervening molecular segments. The introduction of this assumption is not generally admissible, but it will not affect the outcome of certain types of calculation; in particular, one can foresee that it need not affect the calculated form of the stress-strain curve. A particularly simple and straightforward calculation of the network entropy on this basis is given. Wall's the ory of rubber is analysed. It is shown that Wall's postulates are not consistent with the network structure of rubber, and in general lead to different results.
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    Journal of Polymer Science 4 (1949), S. 215-218 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Journal of Polymer Science 4 (1949), S. 183-202 
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism presented constitute proposals made in attempts to portray the role that electrophilic halides play in catalyzing the polymerization of unsaturated hydrocarbons. All of these halides require the presence of a Friedel-Crafts catalyst in the reaction mixture and differ primarily in the interpretation of what constitutes the active factor in the initiation, propagation, and cessation steps. Mechanisms involving a thermal activation and dehydrohalogenation are discussed briefly and rejected as rather improbable. On the other hand, mechanisms involving a cationoid complex intermediate and a carbonium ion are extensively reviewed, especially in light of the recent findings of British investigators regarding the function of the so-called third component or cocatalyst. Attention is called to the rather marked specificity of reactions involving water or other polar cocatalysts, and, in addition, it is pointed out that, although cocatalysts appear to be necessary prerequisities for activation in a number of cases, the phenomenon is not a general one, since systems exist in which proton-supplying cocatalysts have not been proved necessary to initiate growth. To date, no single mechanism seems to satisfy all of the qualitative observations and known data. It is intended that the present discussion summarize available facts in terms of possible mechanisms, and, in addition, evaluate their plausibility in the light of present knowledge.
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  • 80
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    Notes: The inhibitor and initiator action of 33 compounds on the bulk polymerization of pure isoprene has been studied. Picric acid was found to be the most powerful inhibitor at 100°C. The conclusion reached in Part I, that the initiator activity of diazoaminobenzene is superior to all other compounds has been found to be valid also between 100-150°C. The heat polymerization of isoprene between 100-150°C. in the presence of picric acid leads only to the formation of dimers. Three of the four possible isomers have been separated. The solid complex compound of diprene (I) with silver nitrate has been used to separate it from dipentene (II) and the hydrocarbon of Lebedew (III, IV) has been identified as a monochloride. The relative yields (I): (II): (III+IV) = 16:1:2 are in agreement with the relative availability and localization of π-electrons in isoprene. Observations on the properties of polyisoprene are in agreement with the more extensive work by d'Ianni. Some remarks on polymers from bulk polymerization are added. Isoprene acts as a powerful inhibitor on the polymerization of vinylidene chloride. This effect is independent of the method of polymerization.
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    Notes: The recently developed x-ray method of crystallinity determination is applied to products of heterogeneous acid hydrolysis of cellulose fibers. Upon treatment of viscose rayon fibers with boiling 2.5 N sulfuric acid, the crystalline fraction is increased from 39 to 49% within half an hour, and remains constant upon prolonged treatment. Ramie does not show any change in percentage crystallinity when subjected to the same treatment. Its crystalline fraction is, however, transformed into cellulose IV. The observed changes in moisture regain of the hydrolyzed products are in line with the x-ray results.
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    Journal of Polymer Science 4 (1949), S. 337-350 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bacterial cellulose membranes have been used successfully to measure the osmotic pressures of a number of high polymer-solvent systems. The dynamic method of Fuoss and Mead has been used in most cases, but for polyvinylxylene in benzene the rate curves are not symmetrical since the solvent passes through the membrane faster from the solution side. The molecular weight values for two polyvinyl acetates agree well with the calculated kinetic values, and for polyethyl sebacate the value obtained agrees with that found by endgroup titration. Values of the Huggins “constant” μ are given for various systems.
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    Journal of Polymer Science 4 (1949), S. 323-336 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The construction of a thermostated osmometer of the Fuoss-Mead pattern is described. The technique of preparation of bacterial cellulose membranes for osmotic measurements on high polymer systems is given. The permeability of such membranes may be controlled by growth to a thickness of 4-5 mm., drying in contact with a stainless steel surface, and reswelling in water or alcohol-water mixtures. The degree of reswelling required to give membranes suitable for use with polymers of a range of molecular weights is given. The factors affecting the behaviour of the membranes in the osmometer are discussed.
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  • 84
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    Journal of Polymer Science 4 (1949), S. 399-400 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 85
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Refractive index-temperature and volume-temperature data for polyvinyl acetate and polybutyl acrylate have been determined and used to calculate the specific refractivity as a function of temperature by the Lorentz-Lorentz and the Eyckman equations. The results show a variation of specific refractivity with temperature which exceeds experimental error. The variation is evident as an increase of specific refractivity with temperature above Tm and suggests experiments which will show the increase more clearly. A theoretical justification for the increase of specific refractivity with temperature in polymers is discussed.
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  • 86
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    Journal of Polymer Science 4 (1949), S. 515-522 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of increasing and decreasing temperature on the light transmission of polythene has been measured. On raising the temperature of a sheet of polymer the light transmitted increases steadily at an increasing rate until the sample becomes glass clear at the melting point (ca. 112°C.). On cooling from the melt the specimen becomes very opaque a few degrees below the melting point, then becomes much more transparent and thereafter the light transmission decreases as temperature falls, the transmission-temperature curve approximating to the curve for rising temperature. Changes in the spherulite structure of polythene film on heating and cooling have been observed under the microscope and recorded on a cinéfilm. Decay of spherulites on heating is seen not to occur by the reverse of the process by which they are formed from the melt, and the light transmission results are discussed in relation to the spherulitic structure of the polymer.
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  • 87
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 88
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 4 (1949), S. 533-537 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 89
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    Journal of Polymer Science 4 (1949), S. 542-542 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 90
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    Journal of Polymer Science 4 (1949), S. 539-541 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 91
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymers of 2-ethyl-, 2-isopropyl-, and 2-n-amyl-1,3-butadiene alone, and their copolymers with styrene and with butadiene have been prepared and characterized. These monomers give the same ratio of 1,2 to 1,4 addition as has been noted for isoprene. Much less mercaptan must be used with these monomers than is required for butadiene to give soluble polymers. All these monomers copolymerize with styrene readily but have higher Wall α values than butadiene. The stress-strain properties and Gehman low-temperature properties of all of the new polymers have been determined by the Government Laboratories, University of Akron, and are included in this report. There appear to be no unusual properties to be noted.
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  • 92
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The variables of casting polystyrene films from methyl ethyl ketone and from benzene are investigated. It is shown that stringent drying is necessary to remove the last traces of solvent. The differences in dry film structure, second-order transition point, and temperature at which the dynamic modulus suddenly decreases are discussed.
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  • 93
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    Die Makromolekulare Chemie 3 (1949), S. 247-250 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cellobiose wird als Glykolsäure-glykosid nach der Azid-methode mit Protein kondensiert. Ferner werden aus Lacto-bionsäure und Proteinen nach der Azid-methode Lacto-bionyl-proteine synthetisiert.
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  • 94
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    Die Makromolekulare Chemie 3 (1949), S. 223-246 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Chlorbutadien-1,3 (Chloropren) bildet schon bei niedrigen Temperaturen mit molekularem Sauerstoff ein Peroxyd. Die Bildungsgeschwindigkeit dieses Peroxyds ist so groß, daß es schwierig ist, peroxydfreies Chloropren herzustellen. Dies gelingt durch sorgfältige Destillation unter reinstem Stickstoff.Die Versuche zur Isolierung des Chloroprenperoxyds ergaben wegen seiner leichten Zersetzlichkeit keine befriedigenden Ergebnisse. Die quantitative Bestimmung des Peroxyds in Chloropren gelingt nach den üblichen Methoden nicht oder nur sehr schwierig. Chloroprenperoxyd oxydiert Antioxydantien, wie z. B. Phenyl-β-naphthylamin, zu gefärbten Produkten. Da Phenyl-β-naphthylamin die weitere Autoxydation des Chloroprens unterbindet, kann auf dieser Grundlage eine photometrische Bestimmung des Peroxyds durchgeführt werden.Die Geschwindigkeit der Sauerstoffaufnahme von Chloropren bei 0°C wurde volumetrisch gemessen. Die Sauerstoffaufnahme ist ein autokatalytischer, gleichförmig beschleunigter Vorgang. Er wird von Tetralinperoxyd stark beschleunigt, nicht aber von Benzoylperoxyde. Es wurden andere katalytisch wirkende Stoffe und der Einfluß des Lichtes untersucht.Da Chloroprenperoxyd die Polymerisation des Chloroprens auslöst und stark beschleunigt, ist es zweckmäßig, für die Stabilisierung dieser ungesättigten Verbindung solche Stoffe anzuwenden, die nicht nur die Polymerisation, sondern auch die Autoxydation hemmen. Die stabilisierende Wirkung der Antioxydantien wird bei Anwesenheit von Chloroprenperoxyd und Chlorwasserstoff nach einer Induktionsperiode durchbrochen. Dies kann dadurch erklärt werden, daß Phenyl-β-naphthylamin im Falle des Chloroprenperoxyds durch Oxydation, im Falle des Chlorwasserstoffs als Salz unwirksam gemacht wird.
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  • 95
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    Die Makromolekulare Chemie 3 (1949), S. 281-285 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wird ein einfaches Verfahren angegeben, den Transport von Wasser durch Textilfaserschichten zu messen, die einerseits in Wasser tauchen und andererseits an Luft mittlerer relativer Feuchtigkeit grenzen. Proteinfasern transportieren das Wasser langsam, Baumwolle rascher und Viskosekunstfasern sehr rasch.
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  • 96
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    Die Makromolekulare Chemie 3 (1949), S. 251-280 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wird der Einfluß von Seitenketten auf die Höhe der Viskositätszahl Zη von niedermolekularen Estern untersucht. Bei Dicetylmalonestern und Dicetylessigestern hat die Länge der Estergruppe keinen Einfluß auf die Höhe der Viskositätszahl. Bei substituierten Malonsäuredicetylestern resp. Disterylestern ändert sich dagegen die Viskositätszahl mit der Länge der in die CH2-Gruppe substituierten Alkylreste, und zwar ist sie bei kurzkettigen Substituenten kleiner, bei langgliedrigen größer als bei den unsubstituierten Verbindungen gleicher Kettenlänge. Das gleiche Verhalten zeigen β-alkylsubstituierte Stearinsäureester. Es wird weiter versucht, inwieweit das Einsteinsche Viskositätsgesetz in veränderter Fassung zur Klärung dieses Viskositätsverhaltens herangezogen werden kann.
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  • 97
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    Die Makromolekulare Chemie 4 (1949), S. 5-14 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Since the isolation of pectins by the usual technical processes is inevitably bound up with some splitting up the most preserving conditions were ascertained, by which it is possible, to extract sufficient pectin from the pulp of apples. By picking fruits of the most favourable time of fructescence, by eliminating all encymatic activity, by observing the lowest temperatures for extraction and choosing a suitable pH a pectin was obtained, that had undergone scarcely any splitting process. The percentage of methoxyl in that pectin was very nearly the same as that calculated for a completely esterifieated polygalakturonic acid. The molekular weight was determined by measuring the viscosity on a nitrate of that pectin. Here a nitration process was used, that was more preserving than that formerly applied. The values obtained were higher than those obtained so far. The „free pectin“ in apple - juice was found to have a lower molecular weight.
    Notes: Da nach den üblichen technischen Verfahren die Isolierung von Pektinen unvermeidlich mit einem gewissen Abbau verbunden ist, wurden die schonendsten Bedingungen festgestellt, unter denen es noch möglich ist, Pektin aus dem Fruchtfleisch von Äpfeln in ausreichender Menge zu gewinnen. Durch Wahl des günstigsten Reifezustandes, Ausschaltung einer Enzymtätigkeit, Einhaltung möglichst neidriger Extraktionstemperaturen und eines geeigneten pH konnte ein wenig abgebautes Pektin crhalten werden, dessen Methoxylgehalt dem für eine vollständig veresterte Polygalakturonsäure berechneten sehr nahe kommt. Die Molekulargröße wurde viskosimetrisch an einem aus diesem Material gewonnenen Pektinnitrat bestimmt, das nach einer schonenderen Nitrierungsmethode als der bisher üblichen hergestellt war. Die erhaltenen Werte liegen über den bisher beobachteten. Das im Apfelsaft vorhandene „freie Pektin“ wurde als niedriger molekular befunden.
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  • 98
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    Die Makromolekulare Chemie 4 (1949), S. 41-49 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aus einer Zusammenstellung von Viskositätsmessungen an niedermolekularen Kettenmolekülen mit Doppelbindungen geht hervor, daß die trans-Formen eine höhere und die cis-Formen eine niedrigere Viskosität haben als die analogen gesättigten Verbindungen. Die verschiedene Viskosität von trans-, cis- und gesättigten Verbindungen kann mit der verschiedenen Form und Elastizität der Kettenmoleküle erklärt werden. Maleinsäureester und Maleinsäurepolyester lassen sich mit Brom als Katalysator in die entsprechenden Fumarester umlagern.
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  • 99
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    Die Makromolekulare Chemie 4 (1949), S. 15-40 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wurde die Polymerisationsgeschwindigkeit des Vinylchlorids bei 50° unter Zusatz verschiedener Mengen Benzoylperoxyd als Katalysator untersucht, indem der Umsatz das Molekulargewicht und die Zeitdauer beginnender Trübung durch Ausfallen des Polymerisats bestimmt wurde.Der Umsatz steigt zunächst langsam, dann schneller mit der Zeit an; über 80 - 90% nimmt er nur noch sehr langsam zu, so daß die letzten 1 - 2% praktisch nicht mehr polymerisieren. Mit sinkender Katalysatorkonzentration wird die Reaktion langsamer, derart, daß sich die Umsatzzeitkurven durch Dehnung der Zeitachse proportional der Wurzel aus der ursprünglichen Katalysatorkonzentration zur Deckung bringen lassen. Bis zu 70 - 80% läßt sich der Umsatz durch die Gl. u = (eat  -  1)b gut darstellen, wobei b = 0,1 und a = 0,240 · √c20 zu setzen ist.  -  Gegen Ende der Reaktion ließ sich im restlichen Monomeren Salzsäure nachweisen.Das Molekulargewicht nimmt mit steigender Menge Benzoylperoxyd und Sauerstoff deutlich ab; bei mäßigen Peroxydkonzentrationen wird dieser Effekt in der Streuung der Versuchswerte nicht sichtbar.  -  Die Zeit bis zur beginnenden Trübung ändert sich umgekehrt proportional der Wurzel aus der Katalysatorkonzentration und ist ferner unter reinem Sauerstoff größer, unter Stickstoff kleiner als unter Luft.Der Katalysator verschwindet während der Polymerisation, und zwar in um so stärkerem Maße, je höher seine ursprüngliche Konzentration, und um so weniger, je größer die Menge an Sauerstoff ist.  -  Mit Kaliumpersulfat erfolgt die Polymerisation nur in der wäßrigen Phase.Mit den Beobachtungen im Einklang steht das folgende Reaktionsschema (B = Benzoylperoxyd, M = monomeres Vinylchlorid). Die Hemmung der Polymerisation durch eine Anzahl von dritten Stoffen wurde orientierend, etwas eingehender die durch Styrol untersucht. Schwache Reduktionsmittel, Vinylderivate und einige anorganische Stoffe hemmen die Polymerisation, während chemisch indifferente Stoff sie nicht beeinflussen. Die Hemmung beruht vermutlich auf vorzeitigem Kettenabbruch.
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  • 100
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    Die Makromolekulare Chemie 4 (1949), S. 78-90 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The determined P2O5-contents of pectin preparations in the ashes originates partly from inorganic and organic accompanying substances (phosphatides), but partly from esterfied pectin chains by H3PO4; an interlocking of the pectin chains by H3PO4-bridges to „Übermolekülen“ must be assumed in the protopectin, which are relatively set back in comparison to the interlocking by polyvalent metal ions over carboxyl groups.
    Notes: Der bei Pektinpräparaten festzustellende P2O5-Gehalt in der Asche stammt teils von anorganischen und organischen Begleitstoffen (Phosphatiden), teils aber auch von Veresterungen der Pektinketten durch H3PO4; im Protopektin der Pflanzen hat man Vernetzungen der Pektinketten durch H3PO4-Brücken zu „Übermolekülen“ anzunehmen, die zahlenmäßig jedoch gegenüber den Vernetzungen durch mehrwertige Metallionen über die Karboxylgruppen zurücktreten.
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